Geochemical behavior of rare earth elements in hydrothermally altered rocks of the Kuroko mining area,Japan

In this study we analyzed the chemical composition of hydrothermally altered dacite and basalt from the Kuroko mining area, northeastern Honshu, Japan, by REE (rare earth element). Features of rare earth element analyses include: (1) altered footwall dacite exhibits a negative Eu anomaly compared with fresh dacite, suggesting preferential removal of Eu²⁺ from the altered dacite via hydrothermal solutions, (2) altered hangingwall dacite and basalt and dacite and basalt adjacent to ore deposits exhibit positive Eu anomalies compared with fresh dacite and basalt, suggesting addition of Eu²⁺ from hydrothermal solutions, (3) LREE ratio (∑LREE/∑REE) from altered dacite of chlorite–sericite zone and K-feldspar zone show a negative relationship with δ¹⁸O, and La/Sm ratios show a positive correlation with the K₂O index. These trends indicate the addition of light rare earth elements such as La to the altered dacite from hydrothermal solution and/or leaching of heavy rare earth elements such as Sm and Yb, (4) Principal component analysis (PCA) indicates that light rare earth elements enrichment is related to the formation of sericite zone near the Kuroko deposits but not to the formations of chlorite and K-feldspar zones, and (5) The correlations among REE features (LREE ratio, MREE ratio, HREE ratio, Eu/Eu?), δ¹⁸O and K₂O index are not found for montmorillonite zone, mixed layer clay mineral zone and mordenite zone. Therefore, it is inferred that sericite, chlorite and K-feldspar alterations are related to the Kuroko and vein-type mineralization, but montmorillonite and mordenite alterations are not related to the mineralizations, and probably they formed at the post-mineralization stage.     

Behaviour of rare earth elements in geothermal systems of New Zealand

Rare earth element (REE) patterns of hydrothermally altered rhyolite from geothermal systems located in the Taupo Volcanic Zone in the North Island of New Zealand provide evidence of REE mobility. REE trends of unaltered rhyolites are characterised by moderate LREE enrichment ((La/Lu)_cn = 3.84 to 5.62) and pronounced negative Eu anomalies. In contrast, REE patterns of hydrothermally altered rhyolites commonly exhibit different signatures and may be placed into four chemically and petrographically distinct categories. Rocks with clay + quartz + feldspar + calcite (±zeolites, epidote, sphene, chlorite, opaque minerals) assemblages typically display patterns subparallel to fresh rock, whereas, samples which contain quartz + chlorite, or quartz + clay + zeolite assemblages have flat patterns without Eu anomalies, and highly silicified samples are characterised by depleted, bowed REE trends. These patterns may be produced by interaction with alkaline or acid fluids. A fourth group of very intensely altered samples, affected by interaction with acid fluids, exhibits unusual REE trends with highly enriched HREE and depleted LREE, or depleted HREE.These results indicate that some of the REE released by the breakdown of primary phases during alteration are transported away in the fluid. In addition, the degree of depletion is positively correlated with alteration intensity and the fluid/rock ratio. The similarity of REE patterns resulting from alteration by alkaline and acid fluids suggests that the shape of the REE trends is controlled principally by fluid/rock ratios and secondarily by mineralogy. The REE are retained in rocks with a diverse alteration mineralogy, whereas in samples with only one dominant alteration phase (e.g. quartz) it is more probable that not all REE liberated during alteration can be accommodated in the altered rock. Eu commonly behaves differently from the other REE, possibly due to the dominance of Eu²⁺.     

Ore-Forming Fluids of Vein-Type Fluorite Deposits of the Cerro Aspero Batholith,Southern Cordoba Province,Argentina

Vein-type fluorite deposits in the southern part of the Sierras Pampeanas, Córdoba Province, Argentina, occur mainly hosted by calc-alkaline porphyritic biotite granites, which belong to the Paleozoic, post-tectonic Cerro Aspero batholith. The fluorite veins, of Cretaceous age, occupy steeply dipping, strike-slip regional fault zones, and are composed of fluorite and chalcedony, locally with subordinate amounts of pyrite and, in some cases, coffinite and pitchblende. These veins show typical open-space-filling textures and are closely related to pervasive silicic and argillic alteration of the host granite.

Three successive stages of mineralization were distinguished on the basis of vein chronology, REE data, and fluid-inclusion study in fluorite ores. These stages generally display slightly fractionated REE patterns (La/Yb = 1.4 to 14), with REE behavior given by a relatively stronger LREE fractionation with respect to HREE. The REE composition of the fluids responsible for fluorite deposition was largely controlled by differential mobility of the REE during the silicic or argillic alteration of the host granite. Preferential leaching of HREE over LREE occurred during both alteration types, but in the argillic alteration the LREE were practically not removed. The total homogenization of primary-like aqueous inclusions took place invariably in the liquid phase at temperatures ranging from 187°C to 103°C, with concentrations of values around 160°C, 136°C, and 116°C (stages I, II, and III, respectively), defining a clear trend of fluid cooling. This cooling is accompanied by large changes in the fO₂ of the fluid, from oxidizing to reducing, as inferred from the Eu/Eu? ratios and the mineral assemblage (pyrite, pitchblende, and coffinite).

The three stages of fluorite deposition exhibit temperatures of ice melting within the interval from ?0.3°C to +0.4° C, indicating that the mineralizing fluids were exclusively aqueous and highly dilute. No evidence of fluid mixing or boiling was found. The fluid-inclusion data suggest that the proposed three stages of mineralization probably were the result of a single hydrothermal event, and strongly support a single, uniform fluid reservoir for the ore-forming solutions; evidently, the latter were heated meteoric waters rather than fluids generated in deep-seated environments within the crust.     

Geochemistry of trace and rare earth elements during weathering of black shale profiles in Northeast Chongqing,Southwestern China: Their mobilization,redistribution, and fractionation

In this study, the mobilization, redistribution, and fractionation of trace and rare earth elements (REE) during chemical weathering in mid-ridge (A), near mountaintop (B), and valley (C) profiles (weak, weak to moderate, and moderate to intense chemical weathering stage, respectively), are characterized. Among the trace elements, U and V were depleted in the regolith in all three profiles, Sr, Nb, Ta, Zr, and Hf displayed slight gains or losses, and Th, Rb, Cs, and Sc remained immobile. Mn, Ba, Zn, Cu, and Cr were enriched at the regolith in profiles A and B, but depleted in profile C. Mn, Pb, and Co were also depleted in the saprock and fractured shale zones in profiles A and B and enriched in profile C. REEs were enriched in the regolith and depleted at the saprock zone in profiles A and B and depleted along profile C. Mobility of trace and REEs increased with increasing weathering intensity. Normalized REE patterns based on the parent shale revealed light REE (LREE) enrichment, middle REE (MREE), and heavy REE (HREE) depletion patterns. LREEs were less mobile compared with MREEs and HREEs, and this differentiation increased with increasing weathering degree. Positive Ce anomalies were higher in profile C than in profiles A and B. The Ce fractionated from other REE showed that Ce changed from trivalent to tetravalent (as CeO₂) under oxidizing conditions. Minimal REE fractionation was observed in the saprock zone in profiles A and B. In contrast, more intense weathering in profile C resulted in preferential retention of LREE (especially Ce), leading to considerable LREE/MREE and LREE/HREE fractionation. (La/Yb)_N and (La/Sm)_N ratios displayed maximum values in the saprock zone within low pH values. Findings demonstrate that acidic solutions can mobilize REEs and result in leaching of REEs out of the highly acidic portions of the saprock material and transport downward into fractured shale. The overall behavior of elements in the three profiles suggests that solution pH, as well as the presence of primary and secondary minerals, play important roles in the mobilization and redistribution of trace elements and REEs during black shale chemical weathering.     

Apatite as an indicator mineral for mineral exploration: trace-element compositions and their relationship to host rock type

Over 700 apatite grains from a range of rock types have been analysed by laser-ablation microprobe ICPMS for 28 trace elements, to investigate the potential usefulness of apatite as an indicator mineral in mineral exploration. Apatites derived from different rock types have distinctive absolute and relative abundances of many trace elements (including rare-earth elements (REE), Sr, Y, Mn, Th), and chondrite-normalised trace-element patterns. The slope of chondrite-normalised REE patterns varies systematically from ultramafic through mafic/intermediate to highly fractionated granitoid rock types. (Ce/Yb)_cn is very high in apatites from carbonatites and mantle-derived lherzolites (over 100 and over 200, respectively), while (Ce/Yb)_cn values in apatites from granitic pegmatites are generally less than 1, reflecting both HREE enrichment and LREE depletion. Within a large suite of apatites from granitoid rocks, chemical composition is closely related to both the degree of fractionation and the oxidation state of the magma, two important parameters in determining the mineral potential of the magmatic system. Apatite can accept high levels of transition and chalcophile elements and As, making it feasible to recognise apatite associated with specific types of mineralisation. Multivariate statistical analysis has provided a user-friendly scheme to distinguish apatites from different rock types, based on contents of Sr, Y, Mn and total REE, the degree of LREE enrichment and the size of the Eu anomaly. The scheme can be used for the recognition of apatites from specific rock types or styles of mineralisation, so that the provenance of apatite grains in heavy mineral concentrates can be determined and used in geochemical exploration.     

河北省木吉村铜(钼)矿床蚀变分带过程中元素迁移定量分析

为了研究木吉村斑岩型铜(钼)矿床蚀变过程中元素的迁移规律,拟推流体演化规律,笔者通过对赋矿闪长玢岩体的强硅化带、钾长石化带、石英绢云母化带、青磐岩化带中分别取样测试分析,利用Grant方程定量探讨了各蚀变带围岩中主量元素、稀土元素和微量元素的带入、带出特征,结果表明:岩浆初始热液流体富K而贫Na。相对原岩(蚀变弱的青磐岩化带),在各蚀变带中Fe_2O_3、MgO、P_2O_5和TiO_2从深部强硅化带到浅部石英绢云母化带总体上由带出变为带入,SiO_2、MnO则与上述大体相反,FeO在各蚀变带主体为带出元素。各稀土元素从深部向浅部石英绢云母化带带入特征明显,同时各蚀变带在稀土元素球粒陨石标准化曲线上表现出斜率一致的右倾型特征,说明轻重稀土分馏较明显,轻稀土富集,重稀土亏损。Cu和Mo在石英绢云母化带中富集尤为明显,其次在钾长石化带也明显富集,即海拔400~500 m为主要的Cu、Mo富集区。     

Dynamic melting of the Precambrian mantle: evidence from rare earth elements of the amphibolites from the Nellore–Khammam Schist Belt, South India

The Nellore–Khammam Schist Belt (NKSB) in South India is a Precambrian greenstone belt sited between the Eastern Ghats Mobile Belt (EGMB) to the east and the Cratonic region to the west. The belt contains amphibolites, granite gneisses and metasediments including banded iron formations. Amphibolites occurring as dykes, sills and lenses—in and around an Archaean layered complex—form the focus of the present study. The amphibolites are tholeiitic in composition and are compositionally similar to Fe-rich mafic rocks of greenstone belts elsewhere. The NKSB tholeiites show highly variable incompatible trace element abundances for similar Mg#s, relatively constant compatible element concentrations, and uniform incompatible element ratios. Chondrite-normalized REE patterns of the tholeiites range from strongly LREE depleted ((La/Yb) _N = 0.19) to LREE enriched ((La/Yb) _N = 6.95). Constant (La/Ce) _N ratios but variable (La/Yb) _N values are characteristic geochemical traits of the tholeiites; the latter has resulted in crossing REE patterns especially at the HREE segment. Even for the most LREE depleted samples, the (La/Ce) _N ratios are > 1 and are similar to those of the LREE enriched samples. There is a systematic decrease in FeO^t, K₂O and P₂O₅, as well as Ce and other incompatible elements from the LREE enriched to the depleted samples without any variation in the incompatible element ratios and Mg#s. Neither batch and fractional melting, nor magma chamber processes can account for the non-correlation between the LREE enrichment and HREE concentrations. We suggest that dynamic melting of the upper mantle is responsible for these geochemical peculiarities of the NKSB tholeiites. Polybaric dynamic melting within a single mantle column with variable mineralogy is the likely mechanism for the derivation of NKSB tholeiitic melts. It is possible that the NKSB tholeiites are derived from a source with higher FeO/MgO than that of present day ridge basalts.     

Geochemical features of the Matomb alluvial rutile from the Neoproterozoic Pan-African belt,Southern Cameroon

The Matomb region constitutes an important deposit of detrital rutile. The rutile grains are essentially coarse (> 3 mm), tabular and elongated, due to the short sorting of highly weathered detritus. This study reports the major, trace, and rare-earth element distribution in the bulk and rutile concentrated fractions. The bulk sediments contain minor TiO₂ concentrations (1–2 wt%), high SiO₂ contents (∼77–95 wt%) and variable contents in Al₂O₃, Fe₂O₃, Zr, Y, Ba, Nb, Cr, V, and Zn. The total REE content is low to moderate (86–372 ppm) marked by high LREE-enrichment (LREE/HREE ∼5–25.72) and negative Eu anomalies (Eu/Eu^* ∼0.51–0.69). The chemical index of alteration (CIA) shows that the source rocks are highly weathered, characteristic of humid tropical zone with the development of ferrallitic soils. In the concentrated fractions, TiO₂ abundances exceed 94 wt%. Trace elements with high contents include V, Nb, Cr, Sn, and W. These data associated with several binary diagrams show that rutile is the main carrier of Ti, V, Nb, Cr, Sn, and W in the alluvia. The REE content is very low (1–9 ppm) in spite of the LREE-abundance (LREE/HREE ∼4–40). The rutile concentrated fractions exhibit anomalies in Ce (Ce/Ce^* ∼0.58 to 0.83; ∼1.41–2.50) and Eu (Eu/Eu^* ∼0.42; 1.20–1.64). The high (La/Sm)_N, (La/Yb)_N and (Gd/Yb)_N ratios indicate high REE fractionation.     

Behaviour of REE and mass balance calculations in a lateritic profile over chlorite schists in South Cameroon

An in situ weathering profile overlying chlorite schists in the Mbalmayo-Bengbis formations (South Cameroon) was chosen for the study of the behaviour of REE and the evaluation of geochemical mass balance. After physical and mineralogical studies, the chlorite schists and the undisturbed weathered materials were chemically analyzed for major elements (X-ray fluorescence and titrimetry) and REE (ICP-MS). The behaviour of the REE in the Mbalmayo weathering system was established in comparison with the REE of the reference parent rock. Mass balance calculations were applied to both major elements and REE. The mineralogy of the materials was determined with the aid of a Philips 1720, diffractometer. The chlorite schists of the Mbalmayo sector show low REE contents (Σ=153.44 ppm). These rocks are relatively rich in LREE (about 125 times the chondritic value) and relatively poor in HREE (about 20 times the chondritic value). The REE diagram normalized to chondrites shows a slightly split graph ((La/Yb)_N=6.18) with marked enrichment in LREE (LREE/HREE=9.50) in relation to HREE. Moreover, these spectra do not present any Ce anomaly, but a slightly positive Eu anomaly. The imperfectly evolved profile, whose materials are genetically linked, shows an atypical behaviour of REE. In effect, the LREE are more mobile than the HREE during weathering ((La/Yb)NASC<1) with weak Ce anomalies. This has been rarely reported in lateritic profiles characterized by higher HREE mobility than LREE during weathering processes with high Ce anomalies. This is either due to the difference in the stability of REE-bearing minerals, or to the weak acidic to basic pH conditions (6.70<pH<7.80), or even due to the average evolution of the weathering materials. The pathway of the REE along the profile is as follows: (1) leaching in the saprolites and summit of the profile, except for Ce, which precipitates very weakly in the nodular materials and the coarse saprolite materials, (2) at the base of the profile, solutions come in contact with chlorite schist formations, at this level, the pH increases (pH=7.79), HREE and a part of LREE partially void of Ce precipitate and (3) the other part of LREE precipitates further up in the profile. The geochemical mass balance calculations reveal that these elements are leached in the same phases as the relatively high Si, Al, K and Fe²⁺ contents.     

Geochemistry and origin of the Neoproterozoic Dahongliutan banded iron formation (BIF) in the Western Kunlun orogenic belt,Xinjiang (NW China)

The Neoproterozoic (593–532 Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al₂O₃ and TiO₂, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al₂O₃ (<3 wt%), TiO₂ (<0.15 wt%), ∑REE (5.06–39.6 ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10 ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al₂O₃ (>3 wt%), TiO₂, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9 ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu¹_PAAS = 2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu¹_PAAS = 1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe³⁺/(Fe³⁺/Fe²⁺) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ¹³C_V-PDB (−4.0‰ to −6.6‰) and δ¹⁸O_V-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ¹³C_V-PDB = −0.8‰ to + 3.1‰ and δ¹⁸O_V-PDB = −8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu¹_PAAS and δ¹³C_V-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO₂, with the deeper water, from which the carbonate facies BIF formed, depleted in δ¹³C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe²⁺-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe²⁺-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.     

Major Element Compositions and Rare—earth Element Abundaces of Cenozoic Basalts in Eastern China：Implications for a Pressure Control over LREE／HREE Fractionation in Continental Basalt

Major element compositions and rare-earth element (REE) and transition element(Ni,Cr and V) abundances have been determined on 44 basalt samples from eastern China.These basalts have SiO2 contents ranging from 38.63 to 55.24(wt.%),and Na2O K2O from 3.1 to 9.4(wt.%).Ni and Cr abundances are largely variable,respectively falling in ranges 60-605 and 78-1150 ppm.REE abundances,especially light rare-earth elements(LREE), are highly variable.La/Sm and La/Yb ratios vary 2.8 to 7.6 and 1.8 to 8.1. Although the segregation mainly of olivine and clinopyroxene is requested to account for the vari-able and low MgO,CaO/Al2O3,Cr and Ni characteristic of these basalts studied here,the differ-ences in REE composition of the basalts are still related mainly to the partial melting process.Obvious varations in REE abundances could be principally attributed to the partial melting process.Obvious variations in REE abundances could be principally attributed to the partial melting processes that took place at different depths,in spite of some variations caused by the fractional crystallization processes.REE abundances and La/Sm and La/Yb ratios systematically decrease with increasing SiO2,which probably indicated that the basaltic magma derived from a deeper level has higher LREE and LREE/HREE ratios than that from a shallower level.As viewed from the fact that the D^Yb/D^La ratios of clinopyroxenes in the basaltic system increase with increasing pressure,the increase of LREE/HUEE ratios with increasing melting depth can be interpreted as the pressure dependence of bulk D^HREE/D^LREE ratios of silicate minerals,in addition to the pressure control over the melting degree.     

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, TiO₂, Al₂O₃, 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.     

山东沂水雪山岩体和林家官庄岩体的同位素年代学

研究了山东沂水地区的两个太古宙花岗岩类岩体,雪山岩体是花岗闪长岩-花岗岩体。林家官庄岩体属奥长花岗岩-英云闪长岩系列。稀土元素均具轻稀土富集型的分配型式。分别具轻微到明显,和轻微负Eu异常。用质谱计双带源逐层蒸发法进行了单颗粒锆石的详细定年。确定了雪山岩体侵入时代为2530Ma(2531,2532).林家官庄岩体的侵入时代为2507Ma,两个岩体都形成于新太古代。雪山岩体中还发现了年龄为2910Ma的继承性锆石。推测这种错石来自于表壳岩包体。     

Origin of natural sulfur-metal chimney in the Tangyin hydrothermal field,Okinawa Trough: constraints from rare earth element and sulfur isotopic compositions

For the first time, we present the rare earth element (REE) and sulfur isotopic composition of hydrothermal precipitates recovered from the Tangyin hydrothermal field (THF), Okinawa Trough at a water depth of 1206 m. The natural sulfur samples exhibit the lowest ΣREE concentrations (ΣREE= 0.65×10^–6–4.580×10^–6) followed by metal sulfides (ΣREE=1.71×10^–6–11.63×10^–6). By contrast, the natural sulfur-sediment samples have maximum ΣREE concentrations (ΣREE=11.54×10^–6–33.06×10^–6), significantly lower than those of the volcanic and sediment samples. Nevertheless, the δEu, δCe, (La/Yb)_N, La/Sm, (Gd/Yb)_N and normalized patterns of the natural sulfur and metal sulfide show the most similarity to the sediment. Most hydrothermal precipitate samples are characterized by enrichments of LREE (LREE/HREE=10.09–24.53) and slightly negative Eu anomalies or no anomaly (δEu=0.48–0.99), which are different from the hydrothermal fluid from sediment-free mid-oceanic ridges and back-arc basins, but identical to the sulfides from the Jade hydrothermal field. The lower temperature and more oxidizing conditions produced by the mixing between seawater and hydrothermal fluids further attenuate the leaching ability of hydrothermal fluid, inducing lower REE concentrations for natural sulfur compared with metal sulfide; meanwhile, the negative Eu anomaly is also weakened or almost absent. The sulfur isotopic compositions of the natural sulfur (δ³⁴S=3.20‰–5.01‰, mean 4.23‰) and metal sulfide samples (δ³⁴S=0.82‰–0.89‰, mean 0.85‰) reveal that the sulfur of the chimney is sourced from magmatic degassing.     

Geochemistry and Si–O–Fe isotope constraints on the origin of banded iron formations of the Yuanjiacun Formation,Lvliang Group,Shanxi, China

Banded iron formations (BIFs) within the Lvliang region of Shanxi Province, China, are hosted by sediments of the Yuanjiacun Formation, part of the Paleoproterozoic Lvliang Group. These BIFs are located in a zone where sedimentation changed from clastic to chemical deposition, indicating that these are Superior-type BIFs. Here, we present new major, trace, and rare earth element (REE) data, along with Fe, Si, and O isotope data for the BIFs in the Yuanjiacun within the Fe deposits at Yuanjiacun, Jianshan, and Hugushan. When compared with Post Archean Australian Shale (PAAS), these BIFs are dominated by iron oxides and quartz, contain low concentrations of Al₂O₃, TiO₂, trace elements, and the REE, and are light rare earth element (LREE) depleted and heavy rare earth element (HREE) enriched. The BIFs also display positive La, Y, and Eu anomalies, high Y/Ho ratios, and contain ³⁰Si depleted quartz, with high δ¹⁸O values that are similar to quartz within siliceous units formed during hydrothermal activity. These data indicate that the BIFs within the Yuanjiacun Formation were precipitated from submarine hydrothermal fluids, with only negligible detrital contribution. None of the BIF samples analyzed during this study have negative Ce anomalies, although a few have a positive Ce anomaly that may indicate that the BIFs within the Yuanjiacun Formation formed during the Great Oxidation Event (GOE) within a redox stratified ocean. The positive Ce anomalies associated with some of these BIFs are a consequence of oxidization and the formation of surficial manganese oxide that have preferentially adsorbed Ho, LREE, and Ce^4 +; these deposits formed during reductive dissolution at the oxidation–reduction transition zone or in deeper-level reducing seawater. The loss of Ce, LREE, and Ho to seawater and the deposition of these elements with iron hydroxides caused the positive Ce anomalies observed in some of the BIF samples, although the limited oxidizing ability of surface seawater at this time meant that Y/Ho and LREE/HREE ratios were not substantially modified, unlike similar situations within stratified ocean water during the Late Paleoproterozoic. Magnetite and hematite within the BIFs in the study area contain heavy Fe isotopes (⁵⁶Fe values of 0.24–1.27‰) resulting from the partial oxidation and precipitation of Fe^2 + to Fe^3 + in seawater. In addition, mass-independent fractionation of sulfur isotopes within pyrite indicates that these BIFs were deposited within an oxygen-deficient ocean associated with a similarly oxygen-deficient atmosphere, even though the BIFs within the Yuanjiacun Formation formed after initiation of the GOE.     

华北北缘东段开原地区三叠纪侵入岩年代学及岩石地球化学研究

本文报道了位于华北北缘东段开原地区尖山子岩体、宝兴岩体和树德屯岩体的岩相学、岩石地球化学及年代学特征,探讨了上述岩体的形成时代、岩石成因及其构造环境。锆石U-Pb定年结果表明,尖山子岩体形成于251±1.3Ma,宝兴岩体形成于235±1.3Ma,树德屯岩体形成于224±1.9Ma,说明开原地区三叠纪存在早三叠世、中三叠世和晚三叠世三个时期的岩浆活动。尖山子岩体以二长花岗岩为主,具高硅低镁特征,属钙碱性系列;富集大离子亲石元素Rb、K、Ba、Th,相对亏损Ta、Nb、P、Hf、Zr等高强场元素;δEu=0.55~1.87,(La/Yb)N=6.23~47.9,轻重稀土分馏明显,富集轻稀土,亏损重稀土。宝兴岩体以花岗闪长岩为主,Si O2含量变化较大(52.36%~74.06%),Al2O3含量(14.5%~17.34%),Mg O含量(0.61%~3.66%),属钙碱性系列;富集大离子亲石元素Rb、K、Ba、Th,相对亏损Ta、Nb、P、Ti等高强场元素;无明显的Eu异常,(La/Yb)N=6.81~25.6,轻重稀土分馏较明显,富集轻稀土,亏损重稀土。树德屯岩体以闪长岩为主,岩石具有低硅高镁特征,K2O/Na2O比值为0.33~0.76,显示富K贫Na特征,属钙碱性系列;富集大离子亲石元素Rb、K、Ba、Th,相对亏损Ta、Nb、P、Ti、Hf、Zr等高强场元素;无明显的Eu异常,(La/Yb)N=3.87~10.2,轻重稀土分馏不明显。上述岩石地球化学特征表明,尖山子岩体和宝兴岩体的原始岩浆起源于下地壳基性物质的部分熔融,树德屯岩体的原始岩浆起源于亏损的地幔楔。研究区三叠纪岩浆岩形成于造山阶段挤压环境下。华北北缘东段的挤压碰撞作用一直持续到晚三叠世(224Ma),而造山阶段向造山后阶段的构造转换(挤压地壳加厚向伸展垮塌的环境转换)发生于晚三叠世-早侏罗世(224~180Ma)期间。华北北缘东段中生代岩石圈减薄或破坏始于晚三叠世-早侏罗世(224~180Ma)期间。     

Geochronological and Geochemical Constraints on the Petrogenesis and Geodynamic Setting of the Daheishan Porphyry Mo Deposit,Northeast China

The Daheishan Mo deposit of the Lesser Xing'an–Zhangguangcai Range metallogenic belt in northeast China is a super‐large molybdenum deposit with Mo reserves of 1.09 Mt. The Mo mineralization occurs mainly in a granodiorite porphyry. Zircon SIMS U–Pb dating yields a crystallization age of 168.3 ± 1.4 Ma for the granodiorite porphyry. Molybdenite Re–Os dating indicates that Mo mineralization occurred at 169.2 ± 1.2 Ma. These geochronological data indicate that these magmatic and hydrothermal activities occurred during the Middle Jurassic. The granodiorite porphyry can be classified as high‐K calc‐alkaline series, and the rare earth elements (REE) are characterized by a significant fractionation between light REE (LREE) and heavy REE (HREE) with slightly positive Eu anomalies (Eu/Eu^* = 1.08–1.12). Large ion lithophile elements (e.g., Rb, U, K, and Pb) are enriched, whereas high field strength elements (e.g., Nb, Ta, Ti, HREEs, and Yb) are strongly depleted. The granodiorite porphyry is also characterized by initial strontium isotope ratios (⁸⁷Sr/⁸⁶Sr)_i of 0.70460–0.70482 and magmatic zircon δ¹⁸O values of 5.2–6.5 ‰ that are similar to those of the mantle. Zircon ɛ_Hf(t) and whole‐rock ε _Nd(t) values range from 5.6 to 9.9 and 0.8 to 1.1, respectively. The two‐stage Nd model ages (T_DM2) are in the range of 868–894 Ma, similar to Hf model ages, indicating that the parent magma has a uniform source and primarily originated from a juvenile crustal source. Combined with the regional geological history, geochemistry of the Daheishan granodiorite porphyry, and new isotopic age data, we propose that the formation of the Daheishan porphyry Mo deposit is likely related to the subduction of the Paleo‐Pacific Plate.     

The Mobility of Rare—Earth Elements During Hydrothermal Activity：A Review

The mobility of the rare-earth elements(REE)during hydrothermal activities is increasingly documented.Geological and experimental evidence suggests that REE may be mobile in solutions rich in F^-,Cl^-,HCO3^-,CO^2- 3,HPO4^2-,PO4^3-,or in combinations of the above ligands,even though little has been known about which ligand or which combination is most effective in mobilizing REE. The fractionation of REE resulting from hydrothermal activities is inconsistent.One set of field data implies the prererential mobility of the light rare-earth elements(LREE).whereas another set of field observations indicates the dominant mobilization of the heavy rare earth elements(HREE),and some theoretical prediction is comtradictory to the field evidence.The Eu anomalies due to hydrothermal activities are complex and plausible explanation is not available.The existing experimental approaches dealing with REE are not adequate for explanation ofREE behaviour in aqueous solutions.Systematic experimental approaches are suggested.     

云南兰坪盆地古近系细碎屑岩地球化学特征及其地质意义

采用电感耦合等离子体质谱(ICP-MS)方法对兰坪盆地古近系104件细碎屑岩样品进行了稀土元素及微量元素分析,结果显示∑LEE含量较高,轻稀土含量较富集、重稀土含量较亏损,显示出明显的"右倾"型配分模式。根据稀土元素和微量元素特征、w(Zr)-w(Th)、La-Th-Sc、Th-Sc-Zr/10等多种沉积构造背景判别图解及多种交叉分析方法,对兰坪盆地古近系细碎屑源岩构造背景进行了详细研究。利用La/Th-Hf和La/Yb-∑REE判别图解对兰坪盆地古近系源岩属性进行了分析,结果表明:兰坪盆地古近系碎屑源岩主要以上地壳长英质岩石为主,并混有少量基性岩,反映其物源区构造背景为早期为大陆岛弧构造背景,至晚期逐渐过渡为被动大陆边缘构造背景。