Hidden melting signatures recorded in the Troodos ophiolite plutonic suite: evidence for widespread generation of depleted melts and intra-crustal melt aggregation

The main plutonic complex of the Troodos ophiolite, north of the Arakapas Fault Zone, has been re-examined both from field and geochemical perspectives. Ion microprobe analyses of clinopyroxene crystal cores show that the range of melt compositions added to the lower crust far exceeds that of published lavas in the main Troodos massif. This suggests that the lower crust acted as a filter into which a large range of melt compositions were added and out of which a homogenised (and generally fractionated) derivative was extracted. This crustal-level aggregation homogenised diverse melt fractions from a broad range of degrees of melting. Depleted melts with U-shaped rare earth element (REE) patterns were a significant component of the melts added to the crust, but because of their low incompatible element abundances, mixing with less depleted melts prior to eruption masked their signature in the lavas. The discovery that highly depleted melts constituted a significant component of the melts added to the Troodos crust, but not of the lavas, demonstrates that the spatial distribution of lava-types is not necessarily a good indicator of where different parental melt compositions are generated within the mantle. Compared with normal mid-ocean ridge basalts, the Troodos parental melts were (1) generally depleted in immobile incompatible trace elements, (2) less depleted in light REE (LREE) than would be expected for the concomitant depletion in middle and heavy REE, (3) enriched in Sr with respect to the LREE and (4) more oxidised. Modelling of these characteristics suggests a mantle source that had previously lost a significant melt fraction under relatively reducing conditions. This was followed by remelting under more oxidising conditions in an environment in which Sr and LREE were added to the source consistent with previous models of a supra-subduction zone setting.     

琼中麻粒岩的成因:稀土元素地球化学制约

稀土元素地球化学分析表明,琼中麻粒岩可以分为"高Ti"麻粒岩(TiO2含量大于1.0%)和"低Ti"麻粒岩(TiO2含量低于1.0%)两种化学类型."高Ti"麻粒岩以稀土总量高,轻稀土高度富集,轻、重稀土强烈分馏为特征,稀土配分曲线呈右倾单斜型,与本区变基性火山岩的稀土分布特征相似;低"Ti"麻粒岩以稀土总量较低,轻稀土分馏强烈,但重稀土分馏不明显为特征,稀土配分曲线呈重稀土平坦的左高右低型,与许多浅成基性岩的稀土分布特征相似;认为琼中麻粒岩形成于晋宁期的可能性最大.两类麻粒岩的识别,有利于深化对琼中杂岩形成和演化过程的认识.     

Hydrothermal Redistribution of Rare—Earth Elements in Pingxiang Dacite,Guangxi

Distribution of the rare-earth elements (REE) in dacite has been studied so as to get a better understanding of the migration behavior of REE during alteration. Both unaltered and altered samples were collected in an unpolluted area of Guangxi Zhuang Autonomous Region, southwest China. The REE concentrations were analyzed by ICP-MS. It is concluded that the REE were enriched during dacite alteration in varying degrees. The chondrite-normalized REE patterns of altered samples approximately maintain the characteristics of unaltered samples. However, if we normalize the REE concentrations of altered samples with unaltered dacite, fractionation of REE will appear. The LREE are more enriched than HREE in all altered samples with the LREE possibly precipitated as carbonate minerals. Both positive and negative Eu anomalies exist. Enrichment, immobility and depletion are noticed for the element Lu. Heavy mineral alteration, difference in stability constant between carbonate LREE and HREE complexes, downward migration of weathering fluid and microenvironment change may be responsible for the fractionation of REE in the altered dacite.     

The geochemical characteristics of aqueous rare-earth elements in shallow karst groundwater in Guiyang City,China

Fifty-seven shallow groundwater samples were collected from Guiyang karst basin, China, to analyze the aqueous rare-earth elements in low-water seasons and it is shown that the total amount of rare-earth elements (ΣREE) in karst groundwater is exceedingly low compared with that in carbonate rocks or weathering crusts of carbonate rocks, and ranges from 0.01 to 0.43, from 0.03 to 0.27, from 0.03 to 0.19 and from 0.05 to 1.38 μg·L-1 for dolomite, dolomitic & limestone, limestone and clastic rock aquifer, respectively. Both distributions and contents of rare-earth elements (REE) in karst groundwater reflect the lithology of host rocks or weathering crusts of carbonate rocks through which groundwater flows. The chondrite-normalized patterns show a non-flat profile with higher enrichment of slightly light rare-earth elements (LREE) than heavy rare-earth elements (HREE), prominent fractionation between LREE and HREE, negative Ce anomalies and negative or positive Eu anomalies. There is more obvious fractionation between LREE and HREE in groundwater than that in carbonate rocks and their weathering crusts due to high contents of HCO3? and PH in groundwater. In shallow karst groundwater, REE(CO3)n2n-3 (n=1 and 2) is the main inorganic species of REE. But for a clastic rock aquifer, both REESO4+ and REECO3+ are the main inorganic species of REE. Species of REE in groundwater is closely associated with the hydrochemical type of groundwater which is predominated by the lithology of host rocks, groundwater-rock interaction and weathering-pedogenesis of carbonate rocks.     

REE concentrations of garnet and omphacite in eclogites from the Dabie Mountain, central China

Distributions of the rare-earth elements (REE) in omphacite and garnet and REE behaviors during metamorphic processes were discussed. The REE concentrations of garnet and omphacite in six eclogite samples from the Dabie Mountain, central China, were measured by inductively coupled plasma-mass spectrometry (ICP-MS). The correlation of δEu ratios between garnet and omphacite indicated that chemical equilibrium of REE distribution between garnet and omphacite could be achieved during ultra-high pressure (UHP) metamorphism. Most of the partition coefficients (Kd=CiOmp/CiGrt) of light rare-earth elements (LREE) are higher than 1. However the partition coefficients of heavy rare-earth elements (HREE) are lower than 1. This indicated that the LREE inclined to occupy site M2 in omphacite, but the HREEs tended to occupy eightfold coordinated site in garnet during the eclogite formation. The REE geochemistry of the eclogites indicated that LREE could be partially lost during the prograde metamorphic process of protolith, but be introduced into the rocks during the symplectite formation. LREE are more active than HREE during the UHP metamorphism. The results are favorable to highlighting the REE behavior and evolution of UHP metamorphic rocks.     

Petrogenetic significance of rare-earth element behavior in the basement rocks of southern Obudu Plateau, Bamenda Massif, southeastern Nigeria

Rock samples representing various igneous and metamorphic rocks of southern Obudu Plateau were analyzed for rare-earth element ( REE ) behavior by ICP-MS. Results of the analyses indicate a range of REE abundances and distinctive patterns from highly fraetionated patterns with negative Eu anomalies in granitic rocks to relatively low abundances and less REE fractionated flat patterns with little Eu anomaly in some paragneisses, schists, enderbites and dolerites to unfractionated patterns with positive Eu anomalies in some paragneisses and charnockites. Over all, there are low to high ∑ REE contents with negative to positive Eu anomalies. The ratios of different parameters, especially La/Yb and Ce/Yb, show behaviors consistent with crustal to mantle derivation. The heterogeneity of REE abundances and REE patterns reflects mantle to crustal petrogenetic variations of different rock suites on the Plateau. The LREE content is higher than the HREE content in the highly differentiated rocks, as evidenced by their La/Yb,Ce/Yb and La/Sm ratios, which are normally higher in residual products than in primary melts. The dominantly intermediate nature of the source rock of the orthogneisses is suggested by the generally low ∑ REE. The granites enriched in LREE and depleted in HREE and some of the charnockites with negative Eu anomalies were probably formed by partial melting and crystallization.     

The Behaviour of Rare—Earth Elements（REE） During Weathering of Granites in Southern Guangxi,China

The behaviour of the rare-earth elements(REE)during the weathering of granites was studied in southern Guangxi,China.Based on the study of the weathering profiles,the soil,weathered and sub-weatereb zones are identified with different REE geochemical behaviours throug the weathering profiles of granite.The Ce anomalies of the weathering profiles cover a large range of values with most falling between 1.02 and 1.43in the soil zone and 0.16and 0.40in the weathered and sub-weathered zones.Light rare-earth elements(LREE) and heavy rare-earth elements(HREE)are enriched to varying degree in the weathering profiles as compared to host granites.In the soil zone,more HREEs are leached than LREEs,and HREEs are more enriched than LREE in the weathered and sub-weathered zones.It is considered that infiltration and adsorption on clays are two processes controlling the enrichment and formation of REE deposits in the weathering profiles of granite.     

Rare-Earth Elements in the Atmospheric Precipitation of the City of Blagoveshchensk

The mineral composition, distribution and fractionation of rare-earth elements in dissolved and suspended forms (solid residue) of atmospheric precipitation were studied by analyzing the snow sampled over urbanized territory by the example of the city of Blagoveschensk. Electron-microscopic studies revealed the own minerals of rare-earth elements in dust aerosols. It is shown that the main sources of the atmospheric pollution by rare-earth elements were emissions of TPP (heat and power plants) and boiler houses. Contrasting geochemical anomalies of rare-earth elements were found in the snow cover of the city. The REE concentrations in the solid phase of snow are few orders of magnitude higher than those of the liquid phase. The snow solid phase provides insight into the REE behavior, because it directly reflects the impact of different anthropogenic sources. The characteristic feature of the REE distribution in the solid residue of snow is their LREE enrichment relative to MREE and HREE. The average HREE content is 10% of total REE. In the snow water–solid phase system, most samples show weak fractionation between LREE and HREE owing to the low total mineralization of the snow liquid phase and the small content of organic matter.     

REE Geochemistry of Loess in Xinjiang ,China

The total rare-earth element values(ΣREE)of loess in the Xinjiang region vary over a range of 128-200 ppm ,with an average of 153ppm .The average REE content of loess lies between the earth‘s crust (155ppm) and sedimentary rocks(151ppm).The Xinjiang loess,with the REE distribu-tion patterns characterized by negative slopes ,is rich in the Ce-family elements, and has a distribu-tion pattern characteristic of sedimentary rocks.The North Xinjiang loess is relatively depleted in Tb,but rich in Yb and Lu.The South Xinjiang loess is relatively rich in light rare-earth elements.This is full proof that the Xinjiang loess comes partly from weathered materials(clay rock,sandstone)in the region studied.The REE distribution patterns in the Xinjiang loess are similar to those in the precipitated dust and Aeolian sand,indicating the same material source.The REE distribution pat-terns in the Xinjiang loess are also similar to those in loess from the middle Yellow River Valley,China and Taskent,the former USSR.This implies that loesses of the three locations(Xinjiang,the mid-dle Yellow River Valley and Taskent) come from a common material source.But the REE patterns in the Xinjiang loess are different from those in wall rocks (volcanic rock,K-bearing volcanic rock).Generally ,LREE/HREE,Eu/Eu* and Ce/Ce* ratios reflect the features of parent materials of loess,indicating that the parent rocks were probably in the early stage of alkaline weathering and the weathered materials existed in an oxidation environment with basic mediums under arid-climatic conditions before transport.As a result,the migration ability of the REE is weak.     

姑婆山花岗岩主岩体的稀土元素赋存状态研究

稀土元素在姑婆山花岗岩主岩体过渡相中,主要以稀土矿物和类质同象两种形式存在,并以稀土矿物形式为主,其中稀土元素含量占全岩含量的64％以上。轻稀土元素主要赋存于褐帘石和独居石中,重稀土元素主要赋存于褐钇铌矿等矿物中。岩石中至少有65％以上的稀土元素赋存于抗风化能力小的矿物中,为花岗岩风化壳离子吸附型稀土矿床提供了物质来源。     

Geochemistry and petrogenesis of the Late Cretaceous Haji‐Abad ophiolite (Outer Zagros Ophiolite Belt,Iran): implications for geodynamics of the Bitlis–Zagros suture zone

The Haji‐Abad ophiolite in SW Iran (Outer Zagros Ophiolite Belt) is a remnant of the Late Cretaceous supra‐subduction zone ophiolites along the Bitlis–Zagros suture zone of southern Tethys. These ophiolites are coeval in age with the Late Cretaceous peri‐Arabian ophiolite belt including the Troodos (Cyprus), Kizildag (Turkey), Baer‐Bassit (Syria) and Semail (Oman) in the eastern Mediterranean region, as well as other Late Cretaceous Zagros ophiolites. Mantle tectonites constitute the main lithology of the Haji‐Abad ophiolite and are mostly lherzolites, depleted harzburgite with widespread residual and foliated/discordant dunite lenses. Podiform chromitites are common and are typically enveloped by thin dunitic haloes. Harzburgitic spinels are geochemically characterized by low and/or high Cr number, showing tendency to plot both in depleted abyssal and fore‐arc peridotites fields. Lherzolites are less refractory with slightly higher bulk REE contents and characterized by 7–12% partial melting of a spinel lherzolitic source whereas depleted harzburgites have very low abundances of REE and represented by more than 17% partial melting. The Haji‐Abad ophiolite crustal sequences are characterized by ultramafic cumulates and volcanic rocks. The volcanic rocks comprise pillow lavas and massive lava flows with basaltic to more‐evolved dacitic composition. The geochemistry and petrology of the Haji‐Abad volcanic rocks show a magmatic progression from early‐erupted E‐MORB‐type pillow lavas to late‐stages boninitic lavas. The E‐MORB‐type lavas have LREE‐enriched patterns without (or with slight) depletion in Nb–Ta. Boninitic lavas are highly depleted in bulk REEs and are represented by strong LREE‐depleted patterns and Nb–Ta negative anomalies. Tonalitic and plagiogranitic intrusions of small size, with calc‐alkaline signature, are common in the ophiolite complex. The Late Cretaceous Tethyan ophiolites like those at the Troodos, eastern Mediterranean, Oman and Zagros show similar ages and geochemical signatures, suggesting widespread supra‐subduction zone magmatism in all Neotethyan ophiolites during the Late Cretaceous. The geochemical patterns of the Haji‐Abad ophiolites as well as those of other Late Cretaceous Tethyan ophiolites, reflect a fore‐arc tectonic setting for the generation of the magmatic rocks in the southern branch of Neotethys during the Late Cretaceous. Copyright © 2012 John Wiley & Sons, Ltd.     

大冶-武山矿化夕卡岩的稀土元素地球化学研究

用ICP-MS分析了25个含矿夕卡岩样品的REE含量,其中对8个样品的石榴子石等矿物中的熔融包裹体进行了均一温度测定,还对5个夕卡岩样品石榴子石中的熔融包裹体进行了电子探针分析.在这些样品的石榴子石、辉石或方解石中都观察到熔融包裹体.夕卡岩的球粒陨石标准化REE分布模式具有两个突出特点:其一是以富集轻稀土元素(LREE)右倾为特征;其二是多数以具有Eu正异常为特征.夕卡岩球粒陨石标准化REE分布模式有三种类型:第一类型显示斜率不大的右倾直线;第二类型具有以Ce为峰值的折线的特征,即REE线段向上凸,在Ce处有一极大值(个别无峰值,LREE曲线向上凸,呈穹隆状);第三类型为过渡型REE分布模式.在当今REE资料有限的情况下,利用稀土元素地球化学特点鉴别夕卡岩成因是困难的.     

Garnet and Zircon U-Pb Geochronology and Geochemistry Reveal Genesis of the Dafang Au-Pb-Zn-Ag Deposit, Southern Hunan

Garnet is a primary mineral in skarn deposits and plays a significant role in recording copious mineralization and metallogenic information. This study systematically investigates the geochemistry and geochronology of garnet and zircon in the Dafang Au-Pb-Zn-Ag deposit, which represents prominent gold mineralization in southern Hunan, China. Garnet samples with distinct zoning patterns and compositional variations were identified using various analytical techniques, including Backscattered Electron (BSE) imaging, Cathodoluminescence (CL) response, textural characterization, and analysis of rare-earth elements (REE), major contents, and trace element compositions. The garnet was dated U-Pb dating, which yielded a lower intercept age of 161.06 ± 1.93 Ma. This age is older than the underlying granodiorite porphyry, which has a concordia age of 155.13 ± 0.95 Ma determined by zircon U-Pb dating. These results suggest that the gold mineralization may be related to the concealed granite. Two groups of garnet changed from depleted Al garnet to enriched Al garnet, and the rare earth element (REE) patterns of these groups were converted from light REE (LREE)-enriched and heavy REE (HREE)-depleted with positive europium (Eu) anomalies to medium REE (MREE)-enriched from core to rim zoning. The different REE patterns of garnet in various zones may be attributed to changes in the fluid environment and late superposition alteration. The development of distal skarn in the southern Hunan could be a significant indicator for identifying gold mineralization.     

The impact of vegetation on fractionation of rare earth elements (REE) during water–rock interaction

Previous studies on waters of a streamlet in the Vosges mountains (eastern France) have shown that Sr and rare earth elements (REE) principally originate from apatite dissolution during weathering. However, stream water REE patterns normalized to apatite are still depleted in light REE (LREE, La–Sm) pointing to the presence of an additional LREE depleting process. Speciation calculations indicate that complexation cannot explain this additional LREE depletion. In contrast, vegetation samples are strongly enriched in LREE compared to water and their Sr and Nd isotopic compositions are comparable with those of apatite and waters. Thus, the preferential LREE uptake by the plants at the root–water–soil (apatite) interface might lead to an additional LREE depletion of the waters in the forested catchment. Mass balance calculations indicate that the yearly LREE uptake by vegetation is comparable with the LREE export by the streamlet and, therefore, might be an important factor controlling the LREE depletion in river waters.     

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.     

滇西北白秧坪多金属矿集区东矿带方解石REE地球化学特征及意义

方解石是白秧坪多金属矿集区东矿带矿石中的主要脉石矿物。不同产状矿体中方解石的REE地球化学特征研究表明,3个矿段成矿期方解石具有2种稀土模式:LREE(轻稀土元素)富集型和相对平坦型;前者表明成矿过程中没有LREE明显带出的迹象,残余热液继承了前期成矿热液的特征,而后者表明成矿过程中有LREE带出。不同类型矿体方解石中REE含量、有关参数和稀土配分模式等均变化较大,但在地球化学特征上具有连续变化规律,显示为同源不同阶段的产物。方解石为热液成因方解石,结合其他同位素的资料和矿区的地质背景,得出成矿流体以大气降水与围岩反应形成的热卤水为主、深部流体参与其成矿作用的观点。成矿过程中,由早到晚,成矿环境表现为还原向氧化环境变化。     

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.     

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.     

Light Rare Earth Elements enrichment in an acidic mine lake (Lusatia,Germany)

The distribution of Rare Earth Elements (REE) was investigated in the acidic waters (lake and groundwater) of a lignite mining district (Germany). The Fe- and SO₄-rich lake water (pH 2.7) displays high REE contents (e.g. La∼70 μg/l, Ce∼160 μg/l) and an enrichment of light REE (LREE) in the NASC normalised pattern. Considering the hydrodynamic model and geochemical data, the lake water composition may be calculated as a mixture of inflowing Quaternary and mining dump groundwaters. The groundwater of the dump aquifer is LREE enriched. Nevertheless, the leachates of dump sediments generally have low REE contents and display flat NASC normalised patterns. However, geochemical differences and REE pattern in undisturbed lignite (LREE enriched pattern and low water soluble REE contents) and the weathered lignite of the dumps (flat REE pattern and high water soluble REE contents) suggest that lignite is probably the main REE source rock for the lake water.     

The impact of vegetation on REE fractionation in stream waters of a small forested catchment (the Strengbach case)

Previous studies on waters of a streamlet in the Vosges Mountains (Eastern France) have shown that strontium and rare earth elements (REE) mainly originate from preferential dissolution of apatite during weathering. However, stream water REE patterns normalized to apatite are still depleted in the light REE (LREE, La-Sm) pointing to the presence of an additional LREE depleting process. Vegetation samples are strongly enriched in LREE compared to stream water and their Sr and Nd isotopic compositions are comparable with those of apatite and stream water. Thus, the preferential LREE uptake by vegetation might lead to an additional LREE depletion of surface runoff in the forested catchment. Mass balance calculations indicate, that the yearly LREE uptake by vegetation is comparable with the LREE export by the streamlet and, therefore, might be an important factor controlling LREE depletion in river water. This is underlined by the observation that rivers from arctic and boreal regions with sparse vegetation appear to be less depleted in LREE than rivers from tropical environments or boreal environments with a dense vegetation cover.