REE and C-O Isotopic Geochemistry of Calcites from the World-class Huize Pb-Zn Deposits,Yunnan,China:Implications for the Ore Genesis

The world-class Huize Pb-Zn deposits of Yunnan province,in southwestern China,located in the center of the Sichuan-Yunnan-Guizhou Pb-Zn polymetallic metallogenic province,has Pb＋Zn reserves of more than 5 million tons at Pb＋Zn grade of higher than 25%and contains abundant associated metals,such as Ag,Ge,Cd,and Ga.The deposits are hosted in the Lower Carboniferous carbonate strata and the Permian Emeishan basalts which distributed in the northern and southwestern parts of the orefield.Calcite is the only gangue mineral in the primary ores of the deposits and can be classified into three types,namely lumpy,patch and vein calcites in accordance with their occurrence.There is not intercalated contact between calcite and ore minerals and among the three types of calcite,indicating that they are the same ore-forming age with different stages and its forming sequence is from lumpy to patch to vein calcites. This paper presents the rare earth element（REE） and C-O isotopic compositions of calcites in the Huize Pb-Zn deposits.From lumpy to patch to vein calcites,REE contents decrease as LREE/ HREE ratios increase.The chondrite-normalized REE patterns of the three types of calcites are characterized by LREE-rich shaped,in which the lumpy calcite shows（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〈1,the patch calcite has（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〉1,and the vein calcite displays（La）_N〉（Ce）_N〉（Pr）_N〉（Nd）_N with Eu/Eu~＊〉1.The REE geochemistry of the three types of calcite is different from those of the strata of various age and Permian Emeishan basalt exposed in the orefield.Theδ^（13） C_（PDb） andδ^（18）O_（Smow） values of the three types of calcites vary from-3.5‰to-2.1‰and 16.7‰to 18.6‰,respectively,falling within a small field between primary mantle and marine carbonate in theδ^（13）C_（PDb） vsδ^（18）O_（Smow） diagram. Various lines of evidence demonstrate that the three types of calcites in the deposits are produced from the same source with different stages.The ore-forming fluids of the deposits resulted from crustal -mantle mixing processes,in which the mantle-derived fluid components might be formed from degassing of mantle or/and magmatism of the Permian Emeishan basalts,and the crustal fluid was mainly provided by carbonate strata in the orefield.The ore-forming fluids in the deposits were homogenized before mineralization,and the ore-forming environment varied from relatively reducing to oxidizing.

REE Geochemistry of Sulfides from the Huize Zn-Pb Ore Field, Yunnan Province: Implication for the Sources of Ore-forming Metals

REE abundances in sulfides from the Huize Zn-Pb ore field were determined with the ICPMS after preconcentration. The REE abundances in 26 sulfide samples （including pyrite, galena and sphalerite） are very low, with the ~REE ranging from 1.6×10^-9 to 166.8×10^-9. Their LREE/HREE ratios range from 7.6 to 98, showing LREE enrichment relatively. The JEu values are below 1, indicating that they were deposited from an Eu-depleted and reducing fluid-system. Similar to the ore-hosting carbonate strata, calcite separates from carbonate veinlets filling in the fractures or faults crosscutting the carbonate strata also show clear Eu-depletion. This indicates that the carbonate veinlets and their parent fluid was possibly sourced from the strata and inherited the REE geochemical features of the strata. Therefore, REE-geochemical characteristics of both the sulfides and calcites, which were deposited from an ore-forming hydrothermal system, are similar to those of carbonate strata, and strongly suggest that the ore metals were mainly sourced from carbonate strata.

Rare Earth Elements Geochemistry of Laowan Gold Deposit in Henan Province: Trace to Source of Ore-Forming Materials

The compositions of REE in quartz and pyrite from the main stage of the Laowan gold deposit in Henan Province and that in quartz from Laowan granite were determined by inductively coupled plasma-mass-spectrometry （ICP-MS） to trace the source of ore-forming materials. Meanwhile, the REE compositions of the deposit ore, granite and metamorphic wall rock were also considered for comparative studies in detail. The range of ∑REE of quartz and pyrite from the deposit ores is 4.18 × 10^-6- 30.91 × 10^-6, the average of ∑REE is 13.39 × 10^-6, and the average of ∑REE of quartz in the Laowan granite is 6.68 × 10^-6. There is no distinct difference of REE parameters between the deposit ore quartz and granite quartz. The quartz in gold deposit has the same REE particular parameters as quartzes from Laowan granite, such as δEu, δCe, （La/Yb）N and （La/Sm）N, partition degree of LREE to HREE, especially, the chondrite-normalized REE patterns, but no similarity to those from metamorphic wall rock, which shows that ore-forming hydrothermal fluid is mainly the fluid coming from the Laowan granite magma, rather than metamorphic fluid. Meanwhile, comparison studies on REE features between minerals from the deposit ores and related geological bodies in the deposit show that REE characteristics of minerals can serve as an indicator of ore-forming fluid properties and sources, while the REE characteristics of the bulk samples （such as deposit ores, granites and wall rocks） can not trace the source of the ore-forming materials exactly.

Rare Earth Element Geochemistry on Magmatic Rocks and Gold Deposits in Shizishan Ore-Field of Tongling, China

REE geochemical characteristics of the magmatic rocks and gold deposits in Shizishan ore-field of Tongling were studied. Three types of the magmatic rocks have almost the same chondrite-normalized REE patterns, Eu and Ce anomalous values, and ∑REE, ∑LREE/∑HREE regular changes, which indicates that their magmas come from the same source and their digenetic mechanism is fractional crystallization. In three gold deposits, the mineral ores and related altered rocks have similar chondrite-normalized REE patterns and sharp Eu positive anomalous values. The REE contents reduced from the magmatic rocks to skamization or alteration magmatic rocks, skam type ores, sulphide type ores, wall-rocks limestone or marble. The REE geochemical characteristics of the ores and related rocks show that primary fluids originated from magmatic differentiation in lower pressure of shallow crust, ore-forming hydrothermal solutions gained REE and mineralization elements further from leaching the magmatic rocks, then superimposed and reformed the limestones or marbles and deposited ore-forming material.

REE Geochemistry in the Weathered Crust of Granites, Longnan Area,Jiangxi Province

Warm and humid climate and gentle hilly topography have provided favourable conditions for the devel-opment of the weathering crust of the granite intrusions in the Longnan area, Jiangxi Province. REE is mostlyconcentrated in an adsorption state in clay in the wholly weathered zone. The rare-earth minerals enriched inthe parent rocks provided the source material for the REE enrichment. Exchangeable REE accounts for48-86%. Extraction experiments and stable isotopic study of clay minerals suggest that the downward infiltra-tion of meteoric water and increasing gradient of pH values have played an important role in the enrichment ofREE during the progressive weathering. Slight fractionation of individual REE can not change their distribu-tion patterns in the profiles. which are inherited from the parent rocks.

REE Geochemistry of VMS and SEDEX Ores in China

REE ratios and patterns for massive pyrite ore and massive cuprous pyrite ore ofthe Baiyinchang orefield are quite similar to those for quartz keratophyritic tuff and quartzalbitophyre of the same orefield. However, massive cuprous pyrite ore of the Ashele Cu-Zn de-posit is similar to basalt-diabase of the same district in REE geochemistry. Comparison of theChinese VMS ores with those from Rio Tinto, Spain and Que River, Australia, in REEgeochemistry has been made. REE ratios and patterns of bedded-massive and massive ores ofthe Changba-Lijiagou Zn-Pb deposit, the second largest SEDEX deposit in China are similarto those of their host rocks, the Qinling shales of Devonian age and the Changba adamellite.The three types of ore and their host rocks of the Dongshengmiao pyrite (pyrrhotite)-Zn-Pbdeposit have parallel REE ratios and patterns.

REE Geochemistry of Fluorite from the Maoniuping REE Deposit,Sichuan Province,China:Implications for the Source of Ore-forming Fluids

Fluorite is one of the main gangue minerals in the Maoniuping REE deposit, Sichuan Province, China. Fluorite with different colors occurs not only within various orebodies, but also in wallrocks of the orefield. Based on REE geochemistry, fluorite in the orefleld can be classified as the LREE-rich, LREE-flat and LREE-depleted types. The three types of fluorite formed at different stages from the same hydrothermal fluid source, with the LREE-rich fluorite forming at the relatively early stage, the LREE-flat fluorite in the middle, and the LREE-depleted fluorite at the latest stage. Various lines of evidence demonstrate that the variation of the REE contents of fluorite shows no relation to the color. The mineralization of the Maouiuping REE deposit is associated spatially and temporally with carbonatite-syenite magmatism and the ore-forming fluids are mainly derived from carbonatite and syenite melts.

REE Geochemistry and Mineralization Characteristics of the Zudong and Gnanxi Granites, Jiangxi Province

The Zudong and Guanxi granites are original rocks of the ion adsorption-type HREE and LREE deposits in weathering crust of granites. The ΣREE value and LREE/HREE ratio of the Zudong granite are 264 ppm and 0.81-0.24 respectively, and the average Y/ΣREE ratio is 35.8-54.5%. This is mainly due to magmatic crystallization and evolution and deuteric metasomatism (albitization, muscovitization and fluorite-doveritization). These alterations resulted in endogenic mineralizations of yttrium-group REE fluorine carbonates, silicates and arsenates. The Guanxi granite is characterized by LREE enrichment (the average LREE/HREE ratio is 2.43).

Petrology, REE Geochemistry and Tetrad Effect of Some Muscovite Granites at Wadi El Gemal Area, South Eastern Desert, Egypt

The muscovite granites at the study area are being emplaced into biotite granites and ophiolitic mélange settings. They occur in four exposures namely;Umm Seleimat, Sikait, Umm El Kheran and Umm Addebaa exposure. The presence of garnet and muscovite flakes may reflect the peraluminous nature of the studied muscovite granites. Petrographically, the studied granites are mostly subsolvus and consist of plagioclase, K-feldspars, quartz, muscovite and biotite. Garnet, zircon, allanite and opaques are accessories. The textural features of these granites are expressed by bent plagioclase lamellae, distorted microcline twinning, deformed mica flakes and development of myrmekite and recrystallization of feldspars into fine-grained aggregates. Umm Seleimat and Sikait exposures are more differentiated due to the presence of high content of K-feldspar and LREEs. The REE budget decreased from Umm Seleimat-Sikait exposures to Umm El Kheran-Umm Addebaa exposures as (514.5 - 495.6) to (195.9 - 197.7), respectively. Umm Seleimat-Sikait exposures have lower HREE/LREE (0.12 - 0.67), relative to Umm El Kheran-Umm Addebaa exposures (0.99 - 2.06). The studied granites revealed that the chondrite normalized REE patterns are the normal M-type of tetrad effect, where TE1,3 tetrad effect is higher than 1 in all samples which implies that there was an interaction between melt and water-haloid-rich fluid when these granites are crystallized from magma. Spectrometric values of Umm Seleimat and Umm Addebaa indicate that U content is more than Th content. Applying the U mobilization equation proved that the studied granites have been originated from a late magmatic phase of magma very rich in radioelements, also the majority of measurements lie above the zero line indicating that the studied granites affected with hydrothermal solutions rich in uranium than thorium which indicates uranium addition.

Behaviours of REE and Other Trace Elements During Pedological Weathering-Evidence from Chemical Leaching of Loess and Palaeosol from the Luochuan Section in Central China

The chemical leaching method is used for a systematic analysis of distribution characteristics of acid-soluble and acid-insoluble REE and other trace elements from the Luochuan loess deposits. The study shows that the acid-insoluble phase in loess and palaeosol is a stable component of old aeolian dusts and is characteristic of the provenance; the acid-soluble phase is the unstable component in the weathering pedogenic process and reflects rock-forming features after accumulation of aeolian dusts. The acid-insoluble REE and acid-soluble Sr and Pb can be used as geochemical indicators respectively to trace the provenance characteristics and the weathering pedogenic process.

The Lanthanide Tetrad Effect in Argillic Alteration: An Example from the Jizvan District, Northern Iran

Intrusion of quartz-monzodioritic igneous bodies of Oligocene age into Eocene lithic crystal tufts and trachy-basalts resulted in the occurrence of a widespread argillic alteration zone in the Jizvan district （northern Iran）. Mineralogically, the argillie alteration zone includes minerals such as kaolinite, quartz, smectite, pyrophyllite, muscovite-illite, alunite, rutile, calcite, feldspar, chlorite, hematite and goethite. Therefore, the non-CHARAC behaviour for trace elements in the argillic samples is reflected in the non-chondritic Y/Ho and Zr/Hf ratios and the irregular REE patterns, which appear related to the tetrad effect phenomenon. The chondrite-normalized REE distribution patterns indicate both concave （W-shaped） and convex （M-shaped） tetrad effects in the argillic samples. Based on the field evidence and the results from geochemical studies, it can be concluded that the samples from the argillic alteration zone having high fourth tetrad effect values （〉0.30） were developed in the fault and breccia zones. The results indicate that factors such as preferential scavenging by Mn-oxides, crystallization of clay minerals, fluid-rock interaction, overprint of hypogene mineral assemblage by supergene ones, and the structural control, have all played an important role in the occurrence of tetrad effects in samples of the argillic zone in the Jizvan district.

Geochemical Characteristics of Rare Earth Elements in Gejiu Tin Polymetallic Deposits, Yunnan Province, China

In order to get a better understanding of metallogeny, the geochemical characteristics of REE and trace element for Gejiu tin polymetallic deposits were studied by comparing concentrations of REE and trace elements in different type ores and rocks, including skarn-type ore, bedded-type ore, vein-type ore, altered granite, country rocks. Results of this study indicated that the metallogenic matters for different type ores in the study area might be derived from the same origin source, which may be mainly related to granitic activities. Furthermore, there are some differences in concentrations of REE in different ores due to their different depositional mechanism during that time. LREE concentrations were enriched relatively in the vein-type ores and the bedded-type ores with relatively low total REE concentrations, whereas total REE concentrations were higher in the skarn-type ores with LREE and HREE concentrations in wide variation ranges.

Distribution pattern and geochemical analysis of rare earth elements in deep-ocean sediments

The content and distribution pattern of rare earth elements(REEs)in surface sediments from the Eastern and Western Pacifi c Ocean,the Northern and Southern Atlantic Ocean,and the Southwestern Indian Ocean were explored and the resources and geochemical characteristics of REEs in deep-ocean sediments from diff erent oceans were studied.The total REE abundances(ΣREE)in the diff erent oceans ranged as follows:Eastern Pacifi c,56.88–500.02μg/g;Western Pacifi c,290.68–439.94μg/g;Northern Atlantic,55.33–154.90μg/g;Southern Atlantic,40.83–69.30μg/g;and Southwestern Indian Ocean,20.24–64.76μg/g.Their corresponding LREE(La-Eu)/HREE(Gd-Lu)average values were 5.18,5.86,9.01,5.21,and 4.59,which indicated that the light REEs were all evidently enriched.δEu andδCe showed slight Eu-negative anomalies and signifi cant Ce-positive anomalies in all sediments.Although the contents of REEs in the sediments varied among the diff erent oceans,the distribution patterns of REEs were similar,and the correlation coeffi cient was greater than 0.9290.In the Eastern Pacifi c sediments,ΣREE showed a signifi cantly positive correlation with Co,Cu,Zn,Mn,Mo and a weak correlation with Fe.In the Western Pacifi c and Southern Atlantic sediments,ΣREE presented no obvious correlation and a weakly negative correlation with Co,Cu,Zn,Mn,Mo and Fe,respectively.ΣREE in the Southwestern Indian Ocean sediments positively correlated with Cu,Zn,Mn,Mo,Fe,and had a weakly negative correlation with Co.

Zircon U-Pb Geochronology Recorded Late Cretaceous Fluid Activation in the Central Aldan Gold Ore District, Aldan Shield, Russia: First Data

The gold mineralization in the Central Aldan ore district is genetically related to potassic calc-alkaline and alkaline magmatism dated at 115–150 Ma.The objective of this study is to establish the age of hydrothermal processes that accompanied the formation of Au-Te mineralization at the Samolazovsky Deposit.Based on the isotope-geochemical study of zircons from quartz-feldspar metasomatic rocks of the deposit,the granitoids and charnokites of the Nimnyr Complex(1900–1960 Ma)at the contact with the Yukhta monzonite-syenite massif(~127 Ma)were studied.Zircon U-Pb dating was performed on a SHRIMP-II ion microprobe,and rare-earth and trace elements analyses of zircon were carried out in the same craters by secondary-ion mass spectrometry on a Cameca IMS-4f ion microprobe.It is revealed that the studied zircons have heterogeneous structures:dark core and lighter rim,which differ greatly in isotope-geochemical parameters.Zircon rims are cut by a network of fractures,extending into the central part of zircon grains.The rims yield a subconcordant age of 1937±24 Ma,with an average total REE content of 550 ppm,which corresponds to the formation age of the Nimnyr Complex.All zircon cores yield a discordant age of 83±11 Ma and are characterized by a higher total REE content(~1812 ppm),as well as higher contents of U and non-formula elements(Ca,Sr,and Y)with respect to rims,due to the effect of fluid on zircons.Despite the limited number of zircon grains,the additional geochronological study of zircons from syenites of the ore-bearing Ryabinovy Massif has revealed the presence of two distinct age clusters:~125–138 and 76–83Ма.The older ages of zircons from syenites are typical for the Central Aldan ore district.Until now,there is still no explanation for an age range(76–83 Ma)of single zircon grains from ore-bearing syenites of the Ryabinovy Massif.The obtained data suggest that the processes of activation(the effect of fluid)within the Central Aldan ore district continued until Late Mesozoic.With regards to the equivocal geotectonic position of the Mesozoic potassic magmatism in the study area and its high metallogenic potential,there exists an absolute necessity to determine the geochronological age of the rock formations.Therefore this study presents the Late Cretaceous geochronological data for the first time which can constrain the time-frame for the formation of gold-bearing magmatic and metasomatic rocks of the Aldan ore district.