Insights to magmatic-hydrothermal processes in the Manus back-arc basin as recorded by anhydrite

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REE_N patterns measured in anhydrite from mid-ocean ridge deposits. The REE_N patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. ⁸⁷Sr/⁸⁶Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate δ³⁴S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate δ³⁴S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO₂ degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.     

Rare earth element abundances in hydrothermal fluids from the Manus Basin, Papua New Guinea: Indicators of sub-seafloor hydrothermal processes in back-arc basins

Rare earth element (REE) concentrations are reported for a large suite of seafloor vent fluids from four hydrothermal systems in the Manus back-arc basin (Vienna Woods, PACMANUS, DESMOS and SuSu Knolls vent areas). Sampled vent fluids show a wide range of absolute REE concentrations and chondrite-normalized (REE_N) distribution patterns (La_N/Sm_N ∼ 0.6-11; La_N/Yb_N ∼ 0.6 - 71; ). REE_N distribution patterns in different vent fluids range from light-REE enriched, to mid- and heavy-REE enriched, to flat, and have a range of positive Eu-anomalies. This heterogeneity contrasts markedly with relatively uniform REE_N distribution patterns of mid-ocean ridge hydrothermal fluids. In Manus Basin fluids, aqueous REE compositions do not inherit directly or show a clear relationship with the REE compositions of primary crustal rocks with which hydrothermal fluids interact. These results suggest that the REEs are less sensitive indicators of primary crustal rock composition despite crustal rocks being the dominant source of REEs in submarine hydrothermal fluids. In contrast, differences in aqueous REE compositions are consistently correlated with differences in fluid pH and ligand (chloride, fluoride and sulfate) concentrations. Our results suggest that the REEs can be used as an indicator of the type of magmatic acid volatile (i.e., presence of HF, SO₂) degassing in submarine hydrothermal systems. Additional fluid data suggest that near-seafloor mixing between high-temperature hydrothermal fluid and locally entrained seawater at many vent areas in the Manus Basin causes anhydrite precipitation. Anhydrite effectively incorporates REE and likely affects measured fluid REE concentrations, but does not affect their relative distributions.     

Rare earth element distribution in >400 °C hot hydrothermal fluids from 5°S, MAR: The role of anhydrite in controlling highly variable distribution patterns

Two submarine hydrothermal vent fields at 5°S, Mid-Atlantic Ridge (MAR) - Turtle Pits and Comfortless Cove - emanate vapor-phase fluids at conditions close to the critical point of seawater (407 °C, 298 bars). In this study, the concentration and distribution of rare earth element (REE) and yttrium (Y) has been investigated. Independent of the major element composition, the fluids display a strong temporal variability of their REE + Y concentrations and relative distributions at different time scales of minutes to years. Chondrite-normalized distributions range from common fluid patterns with light REE enrichment relative to the heavy REE, accompanied by positive Eu anomalies (type I), to strongly REE + Y enriched patterns with a concave-downward distribution with a maximum enrichment of Sm and weakly positive or even negative Eu anomalies (type II). The larger the sum of REE, the smaller Ce_CN/Yb_CN and Eu/Eu∗. We also observed a strong variability in fluid flow and changing fluid temperatures, correlating with the compositional variability.As evident by the positive correlation of total REE, Ca, and Sr concentrations in Turtle Pits and Comfortless Cove fluids, precipitation/dissolution of hydrothermal anhydrite controls the variability in REE concentrations and distributions in these fluids and the transformation of one fluid type to the other. The variable distribution of REE can be explained by the accumulation of particulate anhydrite (with concave-downward REE distribution and negative Eu anomaly) into a fluid with common REE distribution (type I), followed by the modification of the REE fluid signature due to dissolution of incorporated anhydrite. A second model, in which the type II fluids represent a primary REE reaction zone fluid pattern, which is variably modified by precipitation of anhydrite, can also explain the observed correlations of total REE, fractionation of LREE/HREE and size of Eu anomaly as well as Ca, Sr. The emanation of such a fluid may be favored in a young hydrothermal system in its high-activity phase with short migration paths and limited exchange with secondary minerals. However, this model is not as well constrained as the other and requires further investigations.The strongly variable REE fluid signature is restricted to the very hot, actively phase-separating hydrothermal systems Turtle Pits and Comfortless Cove at 5°S and has not been observed at the neighboring Red Lion vent field, which continuously emanates 350 °C hot fluid and displays a stable REE distribution (type I).     

Genesis of the Jinding Zn-Pb deposit,northwest Yunnan Province,China: Constraints from rare earth elements and noble gas isotopes

The giant sediment-hosted Jinding zinc-lead deposit is located in the Lanping Basin, northwestern Yunnan Province, China. The genesis of the deposit has long been debated and the sources of the ore-forming fluids and metals are controversial. This study presents rare earth element (REE) and noble gas isotope data that constrain the origins of the ore fluids and the heat source driving the hydrothermal circulation. The early-stage sulfides are enriched in light REEs and have high ∑REE values (30.8–94.8 ppm) and weakly negative Eu (δEu 0.85–0.89) and Ce anomalies (δCe 0.84–0.95), suggesting that the fluids were likely derived from dissolution of Upper Triassic marine carbonates with input of REEs from aluminosilicate rocks in the basin. In contrast, the late-stage sulfides have irregular REE patterns, generally low ∑REE values (0.24–10.8 ppm) and positive Eu (δEu 1.22–10.9) and weakly negative Ce anomalies (δCe 0.53–0.90), which suggest that the ore-forming fluids interacted with evaporite minerals. The ³He/⁴He (0.01–0.04 R_a) and ⁴⁰Ar/³⁶Ar values (301–340) of the ore-forming fluids indicate crustal and atmospheric origins for these noble gases. These findings are in agreement with the published fluid inclusion microthermometry data and the results of H, O, C, S, Pb and Sr isotope studies. Our data, in combination with published results, support a two-stage hydrothermal mineralization model, involving early-stage basinal brines and late-stage meteoric water that acquired metals and heat from crustal sources.     

Mechanisms for anhydrite and gypsum formation in the Kuroko massive sulfide–sulfate deposits,north Japan

The Sr, Ba, and rare earth elements (REEs) concentrations and Sr isotopic composition of anhydrite and gypsum have been determined for samples from the Matsumine, Shakanai, and Hanaoka Kuroko-type massive sulfide–sulfate deposits of northern Japan to evaluate the mechanisms of sekko (anhydrite and gypsum) ore formation. The Sr isotopic compositions of the samples fall in the range of 0.7077–0.7087, intermediate between that for middle Miocene (13–15 Ma) seawater (0.7088) (Peterman et al., Geochim Cosmochim Acta, 34:105–120, 1970) and that for country rocks (e.g., 0.7030–0.7050) (Shuto, Assn Geol Collab Japan Monograph 18:91–105, 1974). The Kuroko anhydrite samples exhibit two types of chondrite-normalized REE patterns: one with a decrease from light REEs (LREEs) to heavy REEs (HREEs) (type I), and another with a LREE-depleted pattern (type II). Based on the Sr content and isotopic ratio (assuming an Sr/Ca (mM/M) of 8.7 for seawater), anhydrite is considered to have formed by mixing of preheated seawater with a hydrothermal solution of Sr/Ca (mM/M) = ca. 0.59–1.36 under the condition in which the partition coefficient (Kd) ranges between ca. 0.5 and 0.7. This results in the formation of anhydrite with higher Sr content with an Sr isotopic value close to that of seawater under seawater-dominant conditions. Larger crystals of type II anhydrite are partly replaced by smaller ones, indicating that anhydrite dissolution and recrystallization occurred after or during the formation of sekko ore. Gypsum, which partially replaces anhydrite in the Kuroko deposits, also exhibits two distinct chondrite-normalized REE patterns. Because LREEs are likely to be more readily mobilized during dissolution and recrystallization, it is hypothesized that LREEs are leached from type I anhydrite, resulting in the formation of type II anhydrite with LREE-depleted profiles.     

Rare-earth elements as source indicators of Pan-African granites from Obudu Plateau,Southeastern Nigeria

The rare-earth element （REE） concentrations of representative granite samples from the southeast of the Obudu Plateau, Nigeria, were analyzed with an attempt to determine the signatures of their source, evolutionary history and tectonic setting. Results indicated that the granites have high absolute REE concentrations （190×10^-6-1191×10^-6; av.=549×10^-6） with the chondrite-normalized REE patterns characterized by steep negative slopes and prominent to slight or no negative Eu anomalies. All the samples are also characterized by high and variable concentrations of the LREE （151×10^-6-1169×10^-6; av.= 466×10^-6）, while the HREE show low abundance （4×10^-6-107×10^-6; av.=28×10^-6）. These are consistent with the variable levels of REE fractionation, and differentiation of the granites. This is further supported by the range of REE contents, the chondrite-normalized patterns and the ratios of LaN/YbN （2.30-343.37）, CeN/YbN （5.94-716.87）, LaN/SmN （3.14-11.68） and TbN/YbN （0.58-1.65）. The general parallelism of the REE patterns, suggest that all the granites were comagmatic in origin, while the high Eu/Eu＊ ratios （0.085-2.807; av.=0.9398） indicate high fo2 at the source. Similarly, irregular variations in LaN/YbN, CeN/YbN and Eu/Eu＊ ratios and REE abundances among the samples suggest behaviors that are related to mantle and crustal sources.     

Seawater-like trace element signatures (REE + Y) of Eoarchaean chemical sedimentary rocks from southern West Greenland,and their corruption during high-grade metamorphism

Modern chemical sediments display a distinctive rare earth element + yttrium (REE + Y) pattern involving depleted LREE, positive La/La*_SN, Eu/Eu*_SN, and Y_SN anomalies (SN = shale normalised) that is related to precipitation from circumneutral to high pH waters with solution complexation of the REEs dominated by carbonate ions. This is often interpreted as reflecting precipitation from surface waters (usually marine). The oldest broadly accepted chemical sediments are c. 3,700 Ma amphibolite facies banded iron-formation (BIF) units in the Isua supracrustal belt, Greenland. Isua BIFs, including the BIF international reference material IF-G are generally considered to be seawater precipitates, and display these REE + Y patterns (Bolhar et al. in Earth Planet Sci Lett 222:43–60, 2004). Greenland Eoarchaean BIF metamorphosed up to granulite facies from several localities in the vicinity of Akilia (island), display REE + Y patterns identical to Isua BIF, consistent with an origin by chemical sedimentation from seawater and a paucity of clastic input. Furthermore, the much-debated magnetite-bearing siliceous unit of “earliest life” rocks (sample G91/26) from Akilia has the same REE + Y pattern. This suggests that sample G91/26 is also a chemical sediment, contrary to previous assertions (Bolhar et al. in Earth Planet Sci Lett 222:43–60, 2004), and including suggestions that the Akilia unit containing G91/26 consists entirely of silica-penetrated, metasomatised, mafic rock (Fedo and Whitehouse 2002a). Integration of our trace element data with those of Bolhar et al. (Earth Planet Sci Lett 222:43–60, 2004) demonstrates that Eoarchaean siliceous rocks in Greenland, with ages from 3.6 to 3.85 Ga, have diverse trace element signatures. There are now geographically-dispersed, widespread examples with Isua BIF-like REE + Y signatures, that are interpreted as chemically unaltered, albeit metamorphosed, chemical sediments. Other samples retain remnants of LREE depletion but are beginning to lose the distinct La, Eu and Y positive anomalies and are interpreted as metasomatised chemical sediments. Finally there are some siliceous samples with completely different trace element patterns that are interpreted as rocks of non-sedimentary origin, and include metasomatised mafic rocks. The positive La/La*_SN, Eu/Eu*_SN and Y_SN anomalies found in Isua BIFs and other Eoarchaean Greenland samples, such as G91/26 from Akilia, suggests that the processes of carbonate ion complexation controlling the REE − Y patterns were already established in the hydrosphere at the start of the sedimentary record 3,600–3,850 Ma ago. This is in accord with the presence of Eoarchaean siderite-bearing marbles of sedimentary origin, and suggests that CO₂ may have been a significant greenhouse gas at that time.     

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+.     

Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn-Pb and Yoshiwara-Sannotake Cu(–Fe) Deposits in Japan

Abstract: Systematic data of rare earth elements (REEs) are presented in order to put some constraints on the origin of hydrothermal fluids responsible for two contrastive skarn deposits in Japan; the Kamioka Zn-Pb and Yoshiwara-Sannotake Cu(-Fe) deposits. Carbon and oxygen isotopic studies have demonstrated that the hydrothermal fluids responsible for the Kamioka Zn-Pb deposits are of meteoric water origin whereas those for the Yoshiwara-Sannotake Cu(-Fe) deposits are of magmatic water origin. The REE abundances of epidote skarn derived from aluminous rocks, garnet and clinopyroxene in calcic exoskarn derived from limestone, and interstitial calcite associated with sulfide minerals were determined for these contrastive skarn deposits by inductively-coupled plasma mass spectrometry (ICP-MS). A significant difference in the REE concentrations is not found between epidote skarn and aluminous original rock (plagioclase-clinopyroxene rock, called Inishi rock) from the Kamioka Zn-Pb deposits, indicating that the REEs are generally immobile during the formation of epidote skarn, and that the REE concentrations of the hydrothermal fluid are considerably low relative to the aluminous original rock. In contrast, the epidote skarn exhibits enrichment of Eu with increasing total REE concentrations relative to the aluminous original rock (quartz diorite) in the Yoshiwara-Sannotake Cu(-Fe) deposits, implying a contribution of magmatic fluid derived from granitoids during the skarn formation. Limestone generally has much lower REE concentrations related to surrounding aluminous rocks, and thus the REE concentrations of garnet and clinopyroxene in calcic exoskarn, originated from limestone, are variable due to the interaction with the hydrothermal fluids. The chondrite-normalized REE patterns of garnet, clinopyroxene, and interstitial calcite exactly provide useful information on origins of hydrothermal fluids. The REE patterns of these minerals from the Kamioka Zn-Pb deposits show lower (Pr/Yb)cn ratios, and negative Ce and Eu anomalies inherited from limestone with the decrease of This suggests that the hydrothermal fluids responsible for the Kamioka Zn-Pb deposits were depleted in REEs, and were not magmatic water in origin, but presumably meteoric one. In striking contrast, the REE patterns of exoskarn minerals and calcite from the Yoshiwara-Sannotake Cu(-Fe) deposits exhibit a positive Eu anomaly, and high (Pr/Yb)cn ratios with the considerable increase of σREE and the disappearance of negative Ce anomaly, implying that the fluids were dominantly of magmatic origin. The REE indices are very likely to be an excellent indicator to origins of the skarn deposits.     

Geochemical Features of Vein Anhydrite from the Kakkonda Geothermal System, Northeast Japan

Abstract. Cathodoluminescence (CL) color, rare earth element (REE) content, sulfur and oxygen isotopes and fluid inclusions of anhydrite, which frequently filled in hydrothermal veins in the Kakkonda geothermal system, were investigated to elucidate the spatial, temporal and genetical evolution of fluids in the deep reservoir. The anhydrite samples studied are classified into four types based on CL colors and REE contents: type-N (no color), type-G (green color), type-T (tan color) and type-S (tan color with a high REE content). In the shallow reservoir, only type-N anhydrite is observed. In the deep reservoir, type-G anhydrite occurs in vertical veins whereas type-T and -N in lateral veins. Type-S anhydrite occurs in the heat-source Kakkonda Granite. The CL textures revealed that type-G anhydrite deposited earlier than type-T in the deep reservoir, implying that fracture system was changed from predominantly vertical to lateral.
Studies of fluid inclusions and δ³⁴S and δ¹⁸O values of the samples indicate that type-N anhydrite deposited from diluted fluids derived from meteoric water, whereas type-G, -T and -S anhydrites deposited from magmatic brines derived from the Kakkonda Granite with the exception of some of type-G with recrystallization texture and no primary fluid inclusion, which deposited from fossil seawater preserved in the sedimentary rocks. Type-G, -T and -S anhydrites exhibit remarkably different chondrite-normalized REE patterns with a positive Eu anomaly, with a convex shape (peak at Sm or Eu) and with a negative Eu anomaly, respectively. The difference in the patterns might result from the different extent of hydrothermal alteration of the reservoir rocks and contribution of the magmatic fluids.     

Nature of the crust in Maine,USA: evidence from the Sebago batholith

 Neodymium and lead isotope and elemental data are presented for the Sebago batholith (293±2 Ma), the largest exposed granite in New England. The batholith is lithologically homogeneous, yet internally heterogeneous with respect to rare earth elements (REE) and Nd isotopic composition. Two-mica granites in the southern/central portion of the batholith (group 1) are characterized by REE patterns with uniform shapes [Ce_N/Yb_N (chondrite normalized) = 9.4–19 and Eu/Eu* (Eu anomaly) = 0.27–0.42] and ɛ _Nd(t) = −3.1 to −2.1. Peripheral two-mica granites (group 2), spatially associated with stromatic and schlieric migmatites, have a wider range of total REE contents and patterns with variable shapes (Ce_N/Yb_N = 6.1–67, Eu/Eu* = 0.20–0.46) and ɛ _Nd(t) = −5.6 to −2.8. The heterogeneous REE character of the group 2 granites records the effects of magmatic differentiation that involved monazite. Coarse-grained leucogranites and aplites have kinked REE patterns and low total REE, but have Nd isotope systematics similar to group 2 granites with ɛ _Nd(t) = −5.5 to −4.7. Rare biotite granites have steep REE patterns (Ce_N/Yb_N = 51–61, Eu/Eu* = 0.32–0.84) and ɛ _Nd(t) = −4.6 to −3.8. The two-mica granites have a restricted range in initial Pb isotopic composition (²⁰⁶Pb/²⁰⁴Pb = 18.41–18.75; ²⁰⁷Pb/²⁰⁴Pb = 15.60–15.68; ²⁰⁸Pb/²⁰⁴Pb = 38.21–38.55), requiring and old, high U/Pb (but not Th/U) source component. The Nd isotope data are consistent with magma derivation from two sources: Avalon-like crust (ɛ _Nd>−3), and Central Maine Belt metasedimentary rocks (ɛ _Nd<−4), without material input from the mantle. The variations in isotope systematics and REE patterns are inconsistent with models of disequilibrium melting which involved monazite. Received: 8 December 1995 / Accepted: 29 April 1996     

Geochemical Behaviors of REE and Other Trace Elements during the Formation of Strata-bound Skarns and Related Deposits: A Case Study of the Dongguashan Cu (Au) Deposit, Anhui Province, China

REE and other trace elements in the altered marbles, massive skarns and ores, as well as garnet and quartz were determined in order to examine the behaviors of trace elements during hydrothermal alteration. It is demonstrated that the high-field-strength (HFS) elements Zr, Hf, Th and Nb were immobile while other trace elements were mobile during the formation of skarns and related deposits. REE and ore-forming elements such as Cu and Ag in hydrothermally-altered marbles and skarns were provided primarily by hydrothermal fluids. In the direction transverse of the strata, the more deeply the marbles were altered, the higher the total REE abundance and the larger the negative Eu anomalies would be. The chondrite-normalized REE patterns of skarns are similar to those of the marbles, but the former are distinguished by much higher REE contents and more remarkable negative Eu anomalies. Those patterns were apparently not inherited from the marble protolith, but were controlled by garnets, which were determine     

海底热液系统高温流体的稀土元素组成及其控制因素

研究稀土元素在流体中的地球化学行为及其控制因素,对利用稀土示踪与流体有关的地球化学过程具有重要意义。海底高温流体稀土组成研究表明,不同背景、岩性热液系统喷口流体的稀土含量差别较大,与海水之间可达几个数量级,但配分模式却非常类似,即普遍具有LREE富集、高的正Eu异常特征。流体的稀土组成与岩石或矿物的蚀变程度、结构构造有关,同时受流体的温压、pH值、Eh值、络合介质种类等因素的影响,其配分模式是流体循环、迁移过程中络合、吸附、矿物沉淀等不同因素共同作用而再次调整的结果。正Eu异常作为高温流体的特征标志,可以用来示踪与高温流体有关的地球化学作用过程,同时Y/Ho比值、负Ce异常可以用来示踪与流体/海水混合有关的化学过程。     

BIF微量稀土元素分析方法及其在冀东司家营铁矿中的应用

以硅铁条带交替出现为特征的条带状铁建造(BIF)是世界上最重要的铁矿资源类型,精确分析磁铁矿的化学组成具有重要意义。本文开展了磁铁矿样品不同溶样方法分析结果的比对,并详细分析和讨论了冀东司家营铁矿磁铁矿与燧石单条带的微量及REE元素分析的地球化学特征。分析结果表明,对于磁铁矿样品,常规HF+HNO₃溶样法与HBr+HNO₃组合溶样法具有一致的溶样效果;司家营BIF的Zr,Sc,Th含量极低,表明未受陆源碎屑的污染;铁质与硅质具有低LREE、高HREE、La和Y正异常的海水REE特征,同时具有Eu正异常的热液REE特征;Ce负异常的缺乏,说明当时的古海洋是一个缺氧的环境。研究发现富铁条带的稀土总量大于富硅条带的稀土总量,这可能与硅、铁沉积物的地球化学习性相关,铁质沉积物更易吸收稀土元素。富矿和普通矿石具有原生的热液与海水的混合来源,部分富矿受到后期流体的强烈扰动,甚至表现出热液流体的特征。     

Rare earth geochemistry in the dissolved, suspended and sedimentary loads in karstic rivers, Southwest China

The watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) is a karstic area. Rare earth elements (REEs) of dissolved loads, suspended particulate material (SPM) and sediments of riverbed are first synthetically reported to investigate REE geochemistry in the three phases in karstic watershed during the high-flow season. Results show that the low dissolved REE concentrations in the CQW are attributed to these rivers draining carbonate rocks. The dissolved REE have significant negative Eu anomaly and coexistence of middle and light REE (MREE??PAAS-normalized La _N /Sm _N and Gd _N /Yb _N ; LREE??PAAS-normalized La _N /Yb _N )-enrichment, which are due to the dissolution of impure Triassic carbonates. REE concentrations in most of SPM exceed that of sediments in the CQW and the average continental crust (UCC). The SPM and the sediments show some common features: positive Eu, Ce anomalies, and MREE enrichment. The controls on the patterns seem to be from weathering profiles: the oxidation state, the REE-bearing secondary minerals (cerianite, potassium feldspar and plagioclase), which are also supported by the evidence of Y/Ho fractionations in the three phases.     

Thermodynamic modeling of REE behavior in oxidized hydrothermal fluids of high sulfate sulfur concentrations

Thermodynamic calculations using the HCh software were made for mineral equilibriums including REEs in the fluoride–sulfide–chloride–carbonate–sulfate–system in the presence of Na, Ca, and P with fluids of various acidities–alkalinities [11]. The obtained thermodynamic characteristics of thenardite allowed us to carry out the calculations for this phase under complicated hydrothermal conditions simulating the presence of oxidized fluids at 500–100°C and 2000–125 bar. Among other solid phases, REEs–fluorite, monazite, and REE–F–apatite were formed as CaF₂–(Ln,Y)F₃, LnPO₄, and Ca₅(PO₄)₃F–(Ln,Y)₃(PO₄)₃ ideal solid solutions, respectively, where Ln is La, Ce, Pr, Nd, Sm, Eu, and Gd. Xenotime, anhydrite, elemental sulfur, and calcite were found as well.     

Geochemistry and petrogenesis of granitoids of Lesser Himalayan crystallines,Western Arunachal Himalaya

Low to medium grade crystalline rocks locally known as Bomdila Group extensively covers the Lesser Himalayan region in Western Arunachal Himalaya. This Group consists dominantly of mylonitic gneisses of granitic composition of Palaeoproterozoic age, named as Bomdila mylonitic gneiss (BMG) and a small body of hornblende bearing granite of Mesoproterozoic age known as Salari granite (SG). The BMG is affinity to peraluminous (A/CNK > 1.1) with high content of SiO₂, K₂O/Na₂O ratio, normative corundum, high ratio of FeO^t/MgO in biotite (3.21–5.11) that shows characteristics of S-type granite whereas SG has granodiorite composition with high Na₂O, low K₂O, presence of hornblende, normative diopside, low A/CNK ratio (<1.1) and low FeO^t/MgO ratio in biotite (1.58–1.60) indicates metaluminous I-type granite affinity. The SG has more fractionated nature of REE [(Ce/Yb)_N = 9.06–18.53] and minor negative Eu anomalies [Eu_N/Eu* = 0.69–0.94] as compared to BMG which has less fractionation of REE [(Ce/Yb)_N = 5.95–9.16] and strong negative Eu anomalies [Eu_N/Eu* = 0.37–0.43]. Geochemical and petrological studies suggest that the SG and BMG are not genetically related; SG appears to have derived from igneous source whereas the BMG have been derived from sedimentary source, however these granitoids might have produced during the same thermal event.     

Rare earth element study of exhalites within the Willyama supergroup,Broken Hill Block,Australia

A wide variety of unusual rock types, exhalites, are commonly associated with or host to exhalative mineralisation within the Willyama Supergroup. Chondrite normalised REE patterns of feldspar-, gahnite-, calcite-, magnetite-and garnet-rich lithologies in the vicinity of stratiform Broken Hill-type Pb-Zn-Ag mineralisation are LREE and Eu enriched similar to the REE patterns of pure metalliferous sediments and hydrothermal fluids of the East Pacific Rise and the Red Sea. In contrast, tourmaline-, garnet-, amphibole-, feldspar- and gahnite-rich exhalites in strike extension of Broken Hill-type orebodies possess LREE enrichments and negative Eu anomalies and also HREE enrichments and negative Ce anomalies. These REE patterns are the result of decreasing temperatures of the hydrothermal fluids, changing oxidation-reduction conditions and increasing influence of basic volcanism with increasing distance from the sulphide mineralisation.     

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.