Rare-earth elements as geochemical criteria of endogenous sources of microelements contained in oil

This article presents data on the REE contained in 50 oil samples taken from six oil and gas regions that are based on oil fraction composition analysis using ICP MS. It is shown that regardless of the geological and tectonic structure of regions, oil composition, depth of deposit occurrence, and lithology of enclosing rocks, chondritenormalized curves of REE distribution in oil are different and have a europium maximum. The europium anomaly and the regularly increasing (Eu/Sm) _N and Eu/Eu* ratios under transition from asphaltene components to tars and then to oils are geochemically substantiated. Unlike oil, Devonian domanicites and Jurassic bazhenites, as well as their bituminous substance are characterized by a prominent negative europium anomaly (in the (Eu/Sm) _N ratio), which is typical of sedimentary rocks, modern seawater, and the upper crust of the earth as a whole. Based on the data obtained, the conclusion on the participation of deep fluid systems in the formation of the geochemical appearance of naphtydes is made.

     

Carbon isotope characteristics of organic matter and bitumoids from deep-seated rocks

The distribution of stable carbon isotopes was investigated in the organic matter, bitumoids, and bitumoid fractions from the rocks of the section of the En-Yakhinskaya superdeep parametric well (8250 m) drilled in northern West Siberia, within the world’s largest gas region. The formation of the isotopic composition of organic matter and bitumoids under the conditions of advanced catagenetic stages (up to AC₃) was evaluated. A tendency was established of a decrease in the δ¹³C value of bitumoids and fractions of various polarity with increasing depth. A relation was reliably detected between the isotopic compositions of carbon from organic matter, bitumoids, and particular bitumoid fractions. The main factors affecting the distribution of carbon isotopes in the organic matter of deep-seated sequences were distinguished. The genesis of bitumoids below the oil window is related to the destruction of organic matter under the conditions of advanced catagenesis resulting in anomalous features in the distribution of carbon isotopes in bitumoids.     

Genesis of positive Eu anomalies in acid rocks from the Eastern Baltic Shield

The eastern part of the Baltic Shield contains an abundance of acid rocks with positive Eu anomalies. These rocks are vein granites and blastomylonites of similar chemical composition but with variable K₂O concentrations. The rocks are depleted in Ti, Fe, Mg, Ca, Rb, Zr, and REE, but are enriched in Ba and Sr, a fact suggesting a deep-seated nature of the fluids that participated in the genesis of these rocks. A zone favorable for the derivation of these rocks was transitional from brittle to ductile deformations. The rocks were produced during the tectonic exhumation of lower and middle crustal material a horizontal extension. Shock decompression facilitated the inflow of reduced fluids, which, in turn, ensured the partial melting of the host rocks along open fractures and controlled REE fractionation with the development of Eu maxima.     

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

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

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.     

The composition of garnet in garnet-rich rocks in the southern Proterozoic Curnamona Province, Australia: an indicator of the premetamorphic physicochemical conditions of formation

Garnet-rich rocks occur throughout the Proterozoic southern Curnamona Province, Australia, where they are, in places, spatially related to Broken Hill-type Pb-Zn-Ag deposits. Fine-scale bedding in these rocks, their conformable relationship with enclosing metasedimentary rocks, and their enrichment in Mn and Fe suggest that they are metamorphosed chemical precipitates. They formed on the floor of a 1.69?Ga continental rift basin from hydrothermal fluids mixed with seawater and detritus. Garnet in garnet-quartz and garnet-amphibole rocks is generally light rare earth element (LREE) depleted, and has flat heavy REE (HREE) enriched chondrite-normalized REE patterns, and negative Eu anomalies (Eu/Eu*?<?1). Garnet in garnet-rich rocks from the giant Broken Hill deposit has similar REE patterns and either positive (Eu/Eu*?>?1) or negative Eu anomalies. Manganese- and Mn-Ca-rich, Fe-poor garnets in garnetite, garnet-hedenbergite, and garnet-cummingtonite rocks at Broken Hill have Eu/Eu*?>?1, whereas garnet in Mn-poor, Fe-rich quartz garnetite and quartz-garnet-gahnite rocks from Broken Hill, and quartz garnetite from other locations have Eu/Eu*?<?1. The REE patterns of garnet and its host rock and interelement correlations among REEs and major element contents in garnet and its host rock indicate that the Eu anomaly in garnet reflects that of its host rock and is related to the major element composition of garnet and its host rock. The value of Eu/Eu* in garnet is related to its Mn, Fe, and Ca content and that of its host rock, and the distribution of REEs among garnet and accessory phases (e.g., feldspar). Positive Eu anomalies reflect high amounts of Eu that was preferentially incorporated into Mn- and Mn-Ca-rich oxides and carbonates in the protolith. In contrast, Eu/Eu*?<?1 indicates the preferential discrimination against Eu by Fe-rich, Mn-poor precursor minerals. Precursors to Mn-rich garnets at Broken Hill formed by precipitation from cooler and more oxidized hydrothermal fluids compared to those that formed precursors to Mn-poor, Fe-rich garnet at Broken Hill and the other locations. Garnet from the Broken Hill deposit is enriched in Zn (> 400?ppm), Cr (> 140?ppm), and Eu (up to 6?ppm and positive Eu anomalies), and depleted in Co, Ti, and Y compared to garnet in garnet-rich rocks from other localities. These values, as well as MnO contents ?>?15 wt. % and Eu/Eu*?>?1 are only found at the Broken Hill deposit and are good indicators of the presence of Broken Hill-type mineralization.     

Geochemistry of the early proterozoic metasedimentary rocks of the alligator rivers region,Northern Territory,Australia

The early Proterozoic metasedimentary sequence of the Alligator Rivers Region (a part of the Pine Creek Geosyncline) in the Northern Territory, Australia, overlies an Archaean granitoid basement. Early Proterozoic sedimentary sequences, in general, record important changes in the composition of the upper continental crust about the Archaean-Proterozoic boundary. However, the geochemistry of only a few of these sequences has been documented. The geochemistry of the early Proterozoic succession in the Alligator Rivers Region is reported here and the results are interpreted in terms of differences between the stratigraphic units, their provenance—particularly in relation to crustal evolution, and their subsequent metamorphism and weathering.Clastic metasedimentary rocks throughout the Alligator Rivers Region have a remarkably uniform major and trace element geochemistry. The Kakadu Group and upper member of the Cahill Formation are relatively more enriched in SiO₂ and correspondingly more depleted in Al₂O₃ than the rest of the sequence, reflecting the greater dominance of metapsammitic assemblages. The lower member of the Cahill Formation, which hosts the major U deposits of the Alligator Rivers Region, and the metasedimentary sequence in general, exhibit no significant enrichment in U above normal background values. Rare earth element (REE) concentrations in the metasedimentary units within the Alligator Rivers Region are uniform, though in detail there are some important differences within and between formations.The composition of the early Proterozoic clastic metasediments in the Alligator Rivers Region is consistent with the composition of similar material of the same age from other areas, and supports current ideas on crustal evolution. The Alligator Rivers metasediments are enriched in Si and K, and depleted in Mg, Ca, and Na relative to the Archaean average for clastic sedimentary rocks, and their REE geochemistry resembles typical post-Archaean sedimentary rocks having a light REE enriched pattern and a distinct Eu/Eu1 depletion compared to typical Archaean sediments. However, the REE data indicate that two compositionally distinct sources are involved in the provenance of the Kakadu Group, and possibly the lower member of the Cahill Formation, where two types of REE patterns can be distinguished on their HREE concentration and Eu/Eu1 anomaly.     

Geochemical Constraints of Sediments on the Provenance, Depositional Environment and Tectonic Setting of the Songliao Prototype Basin

The geochemistry of sediments is primarily controlled by their provenances, and different tectonic settings have distinctive provenance characteristics and sedimentary processes. So, it is possible to discriminate provenances, depositional environments and tectonic settings in the development of a sedimentary basin with the geochemistry of the clastic rocks. The analytical results of the present paper demonstrate that sediments in the Songliao prototype basin are enriched in silica (SiO2=66.48-80.51 %), and their ΣREE are 30-130 dmes of that of chondrite with remarkable Eu anomalies. In discriminating diagrams of Eu/Eu vs eeeeeREE and (La/Yb)N vs ΣREE, most samples locate above the line Eu/ Eu=l, on the right of the line Eu/Eu/ΣREE=1 and under the line La/Yb)N/eeeeeREE=1/8, which indicates that the depositional environment of sediments in the basin was oxidizing. In addition, variations of MgO, TiO2, A12O3, FeO+Fe2O3, Na2O and CaO vs SiO2 reflect a tendency of increasing mineral maturity of sediments     

REE Geochemistry of Precambrian Metamorphic Rocks in Wutaishan Region

The metasedimentary-volcanic series of the Wutai and Hutuo groups experienced regional metamorphism and thus turned into moderate-to low-grade metamorphic rocks.REE abundances and REE distribution patterns in the Shizui and Taihuai Subgroup metasedimentary-volcanic rocks are typical of the Archean,whereas the Gaofan Subgroup and the Hutuo Group show post-Archean REE geochemical char-acteristics.Five types of REE distribution pattern are distinguished:(1)rightward inclined smooth curves with little REE anomaly(Eu/Eu*=0.73-0.95) and heavy REE depletion (e.g.the Late Archean metasedimentary rocks);(2)rightward inclined V-shaped curves with sharp Eu anoma-ly (Eu/Eu*=0.48-0.76) and slightly higher ∑REE (e.g.the post-Archean metasedimentary rocks);(3) rightward inclined steep curves with negative Eu anomaly(Eu/Eu*=0.73-0.76) and the lowest ∑REE (e.g.the post-Archean dolomites);(4)rightward inclined,nearly smooth curves with both positive Eu anomaly and unremarkable positive Eu anomaly(Eu/Eu*=0.95-1.25)(e.g.the meta-basic volcanic rocks);and (5) rightward inclined curves with Eu anomaly(Eu/Eu*=1.09-1.19)and heavy REE depletion(e.g.the meta-acid volcanic rocks).Strata of the two groups are considered to have been formed in an island-arc belt-an instable continental petrogenetic environment.     

Petrology and geochemistry of mafic and ultramafic cumulate rocks from the eastern part of the Sabzevar ophiolite (NE Iran): Implications for their petrogenesis and tectonic setting

The Late Cretaceous Sabzevar ophiolite represents one of the largest and most complete fragments of Tethyan oceanic lithosphere in the NE Iran. It is mainly composed of serpentinized mantle peridotites slices; nonetheless, minor tectonic slices of all crustal sequence constituents are observed in this ophiolite. The crustal sequence contains a well-developed ultramafic and mafic cumulates section, comprising plagioclase-bearing wehrlite, olivine clinopyroxenite, olivine gabbronorite, gabbronorite, amphibole gabbronorite and quartz gabbronorite with adcumulate, mesocumulate, heteradcumulate and orthocumulate textures. The crystallization order for these rocks is olivine ​± ​chromian spinel → clinopyroxene → plagioclase → orthopyroxene → amphibole. The presence of primary magmatic amphiboles in the cumulate rocks shows that the parent magma evolved under hydrous conditions. Geochemically, the studied rock units are characterized by low TiO₂ (0.18–0.57 ​wt.%), P₂O₅ (<0.05 ​wt.%), K₂O (0.01–0.51 ​wt.%) and total alkali contents (0.12–3.04 ​wt.%). They indicate fractionated trends in the chondrite-normalized rare earth element (REE) plots and multi-element diagrams (spider diagrams). The general trend of the spider diagrams exhibit slight enrichment in large ion lithophile elements (LILEs) relative to high field strength elements (HFSEs) and positive anomalies in Sr, Pb and Eu and negative anomalies in Zr and Nb relative to the adjacent elements. The REE plots of these rocks display increasing trend from La to Sm, positive Eu anomaly (Eu/Eu1 ​= ​1.06–1.54) and an almost flat pattern from medium REE (MREE) to heavy REE (HREE) region [(Gd/Yb)_N ​= ​1–1.17]. Moreover, clinopyroxenes from the cumulate rocks have low REE contents and show marked depletion in light REE (LREE) compared to MREE and HREE [(La/Sm)_N ​= ​0.10–0.27 and (La/Yb)_N ​= ​0.08–0.22]. The composition of calculated melts in equilibrium with the clinopyroxenes from less evolved cumulate samples are closely similar to island arc tholeiitic (IAT) magmas. Modal mineralogy, geochemical features and REE modeling indicate that Sabzevar cumulate rocks were formed by crystal accumulation from a hydrous depleted basaltic melt with IAT affinity. This melt has been produced by moderate to high degree (~15%) of partial melting a depleted mantle source, which partially underwent metasomatic enrichment from subducted slab components in an intra-oceanic arc setting.     

Geochemistry of Paleozoic ignimbrites in central Kazakhstan and their petrogenetic significance

Ignimbrites in the Devonian and Late Paleozoic volcanic belts in central Kazakhstan were produced in various geotectonic environments and are diverse in composition. The bulk composition of the Devonian ignimbrites is rhyolitic. The Eifelian rocks of the Chingiz island-arc system belong to the calc-alkaline series and are enriched in Zr, Nb, Y, and REE (predominantly LREE). The Frasnian ignimbrites that were formed in unusual island arcs of the Mediterranean type are ultrapotassic. Compared to the Eifelian ignimbrites, they bear lower concentrations of Zr, Nb, Y, and REE but are richer in Rb and Ba. Both rock varieties show clearly pronounced Eu minima and Ce anomalies. The Carboniferous and Permian ignimbrites were generated within a volcanic belt in a continental margin. The Carboniferous ignimbrites are mostly of dacite-rhyolite and sometimes of dacitic andesite composition. Compared to the Devonian ignimbrites, they are depleted in Zr, Nb, and Y at higher concentrations of Ba and low REE sums, which are notably dominated by LREE; their Eu minima are small, and they have no Ce anomalies. The Permian ignimbrites are predominantly of rhyolite composition. The Early Permian rocks have REE sums close to those in the Carboniferous rocks, but the former have clearly pronounced Eu minima and Ce anomalies. The Late Permian ignimbrites have total REE concentrations close to those in the Devonian ignimbrites, but the former are strongly enriched in LREE and have prominent Eu minima and Ce anomalies. The major-and trace-element composition of fiamme in all ignimbrite varieties varies depending on the relative age of the fiamme. The REE patterns of the fiamme differ from massif to massif, but their systematic changes from older to younger fiamme are similar. Along with the identity of the isotopic characteristics of whole-rock ignimbrite samples and fiamme of different ages in them, this testifies that the ignimbrites were formed not via the mixing of various melts but by the systematic evolution of a parental melts, which were different for different massifs.     

Sources of stream sediments in the granulite terrain of the Walawe Ganga Basin,Sri Lanka,indicated by rare earth element geochemistry

Thirty-eight samples of stream sediments draining high-grade metamorphic rocks in the Walawe Ganga (river) Basin, Sri Lanka, were analysed for their REE contents, together with samples of metamorphic suites from the source region. The metamorphic rocks are enriched in light REE (LREE) compared to heavy REE (HREE) and are characterised by high La/Lu ratios and negative Eu anomalies. The chondrite-normalised patterns for these granulite-grade rocks are similar to that of the average post-Archaean upper crust, but they are slightly enriched with La and Ce. The REE contents of the <63-μm fraction of the stream sediments are similar to the probable source rocks, but the other grain size fractions show more enriched patterns. The <63-μm stream sediments fraction contains lower total REE, more pronouncd negative Eu anomalies, higher Eu_N/Sm_N and lower La _N/Lu_N ratios relative to other fractions. The lower La _N/Lu_N ratio is related to the depletion of heavy minerals in the <63-μm fraction. The 63–125-μm and 125–177-μm grain size fractions of sediments are particularly enriched in LREE (average ΣLREE=2990 μg/g and 3410 μg/g, respectively). The total HREE contents are surprisingly uniform in all size fractions. However, the REE contents in the Walawe Ganga sediments are not comparable with those of the granulite-grade rocks from the source region of the sediments. The enrichment of REE is accounted for by the presence of REE containing accessory mineral phases such as zircon, monazite, apatite and garnet. These minerals are derived from an unknown source, presumably from scattered bodies of granitic pegmatites.     

Geochemistry and provenance of stream sediments of the Ganga River and its major tributaries in the Himalayan region,India

Major, trace and REE compositions of sediments from the upper Ganga River and its tributaries in the Himalaya have been examined to study the weathering in the Himalayan catchment region and to determine the dominant source rocks to the sediments in the Plains. The Ganga River rises in the Higher Himalaya from the Higher Himalayan Crystalline Series (HHCS) bedrocks and traverses over the Lesser Himalayan Series (LHS) and the Himalayan foreland basin (Siwaliks) rocks before entering into the Gangetic Plains. The major element compositions of sediments, reflected in their low CIA values (45.0–54.7), indicate that silicate weathering has not been an important process in the Himalayan catchment region of the Ganga River. Along the entire traverse, from the HHCS through LHS and the Siwaliks, the sediments from the tributaries and the mainstream Ganga River show higher Na₂O, K₂O, CaO and silica. This, and the higher ratios of La/Sc, Th/Sc and lower ratios of Co/Th, suggest that the source rocks are felsic. The fractionated REE patterns and the significant negative Eu anomalies (Eu/Eu? = 0.27–0.53) indicate highly differentiated source. Moreover, the comparison of the sediments with different source rock lithologies from the HHCS and the LHS for their major elements clearly suggests that the HHCS rocks were the dominant source. Further, comparison of their UCC (upper continental crust) normalized REE patterns suggests that, among the various HHCS rocks, the metasediments (para-gneiss and schist) and Cambro-Ordovician granites have formed the major source rocks. The Bhagirathi and Alaknanda River sediments are dominantly derived from metasediments and those in the Mandakini River from Cambro-Ordovician granites. The resulting composition of the sediments of the Ganga River is due to the mixing of sediments supplied by these tributaries after their confluence at Devprayag. No further change in major, trace and rare earth element compositions of the sediments of the Ganga River after Devprayag up to its exit point to the Plains at Haridwar, suggests little contribution of the Lesser Himalayan and Siwalik rocks to the Ganga River sediments.     

Geochemistry of mafic rocks of the PGE-bearing Vurechuaivench Massif (Monchegorsk Complex,Kola region)

The platinum-bearing Paleoproterozoic Vurechuaivench Massif in the Monchegorsk Pluton is made up of amphibolized and saussuritized gabbronorites, anorthosites, and norites. The geochemical features of the massif rocks are considered at four detailed areas. It was confirmed that the Vurechuaivench and Nyud-Poaz massifs are geochemically similar. The rare-earth element (REE) distribution in the rocks of the Vurechuaivench Massif is peculiar in the low total REE content (9.4–27.6 ppm), negative REE slope, significant LREE enrichment [La/Yb] _n = 3.7–8.7), and distinctly expressed positive Eu anomaly ([Eu/Eu*] _n = 1.2–2.2). The REE distribution pattern remains unchangeable throughout the entire section, including the rocks of the Pt reef, with a gradual upsection REE increase. It is suggested that the PGE reef of the Vurechuaivench Massif, as the Platinova Reef (Skaergaard massif) and Sonju-Lake Intrusion (Duluth complex), was formed during fractional crystallization in a large magma chamber without new magma influx. It is conceivable that the Vurechuaivench Massif is the allochthonous fragment of a large loppolith-like body, the lower portions of which compose the Nyud-Poaz Massif, while the middle part was almost completely eroded.     

Petrologic significance of rare earths distribution in granites

Granitic rocks of various ages and composition are found in the Schwarzwald region of West Germany. These granites range in age from Upper Devonian to Upper Carboniferous (370-280 m.y.) and in composition from granodiorites to alkali feldspar granites. 14 representative samples of twelve different types were analysed for their La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, Lu by instrumental neutron activation. The studies reveal that there are characteristic differences between the different types of granitic rocks both as regards to their total REE content as well as the distribution pattern of these elements. These differences can not be directly related to the variations in the major element chemistry or the mineralogy of the granites. On the other hand, a relationship is found between the age of the granitic rocks and the total REE as well as their distribution pattern. In general the ΣREE varies from 22 to 215 ppm in different types. The ΣLa-Lu increases gradually in the direction Upper Devonian→Lower Carboniferous, however, in the granitic rocks of the Upper Carboniferous this trend is reversed and there is again a marked depletion in the content of REE. The chondrite normalised patterns of all the older types give a smooth concave curve with decrease of concentration from La to Lu. All the Upper Carboniferous granites on the other hand are characterised by a progressive pronounced negative Eu anomaly. The gradual increase of the ΣREE in the older granites is related to their evolution by progressive anatexis, whereas, the decrease in the total REE content in case of the younger Upper Carboniferous granites is due to processes of magmatic differentiation. The depletion of Eu in these K-feldspar rich types of granite is probably related to the breakdown of biotite in the anatectic starting material.     

Geochemistry and Provenance of Maastrichtian Clastic Rocks in the Dikmendede Formation of Orhaniye in Kazan-Ankara-Turkey Region

An integrated petrographic and geochemical study of the sandstones of the Maastrichtian-aged in the Orhaniye (Kazan-Ankara-Turkey) was carried out to obtain more information on their provenance, sedimentological history and tectonic setting. Depending on their matrix and mineralogical content, the Maastrichtian sandstones are identified as lithic arenite/wacke. The Dikmendede sandstones derived from types of provenances, the recycled orogen and recycled transitional. The chemical characteristics of the Dikmendede sandstones, i.e., fairly uniform compositions, high Th/U ratios (>3.0), negative Eu anomalies (Eu/Eu* 0.72–0.99) and Th/Sc ratios (mostly less than 1.0), favor the OUC (old upper continental crust) provenance for the Dikmendede sandstones. The SiO2/Al2O3, Th/Sc (mostly <1.0) and La/Sc (<4.0) ratios are; however, slightly lower than typical OUC, and these ratios may suggest a minor contribution of young arc-derived material. The rare earth element (REE) pattern, and La/Sc versus Th/Co plot suggests that these sediments were mainly derived from felsic source rocks. The Dikmendede sandstones have high Cr (123–294 ppm) and Ni (52–212 ppm) concentrations, Cr/Ni ratio of 1.93, and a medium correlation coefficient between Cr and Ni and corresponding medium to high correlation of both (Cr and Ni, respectively) elements with Co. These relationships indicate a significant contribution of detritus from ophiolitic rocks. As rare earth element data are available for the Dikmendede sandstones, the Eu/Eu* is compared with LaN/YbN. Samples plot in the area of overlapping between continental collision, strike-slip and continental arc basins. The predominantly felsic composition of the Dikmendede sandstones is supported by the REE plots, which show enriched light REE, negative Eu anomaly and flat or uniform heavy REE. The Dikmendede sandstones have compositions similar to those of the average upper continental crust and post-Archean Australian shales. This feature indicates that the sediments were derived mainly from the upper continental crust. The Dikmendede sandstones have chemical index of alteration (CIA) values of 28–49, with an average of 40 indicating a low degree of chemical weathering in the source area. The compositional immaturity of the analyzed sandstone samples is typical of subduction-related environments, and their SiO2/Al2O3 and K2O/Na2O ratios and Co, Sc, Th and Zr contents reflect their oceanic and continental-arc settings. The Dikmendede sandstones were developed as flysch deposits derived from mixed provenance in a collision belt.     

Rare—Earth Element Geochemistry of Elogites from the Ultra—High Pressure Metamorphic Belt in Central China

Based on their REE contents and REE patterns,eclogites from the ultra-high pressure metamorphic belt in central China may be roughly divided into xis types including LREE-rich.LREE-rich positive Eu anomaly,LREE-rich negative Eu anomaly,REE pattern-smooth,MREE-rich and HREE-rich.The LREE_rich,LREE-rich positive Eu anomaly and LREE-rich negative Eu anomaly types of eclogites are dominant .REE types of eclogites in different areas can be compared and the REE feactures of the same REE type of eclogites in different areas are similar.The results of reconstruction of the primary rocks show that the primary rocks of eclogites possibly are dominated by continental tholeiites which are the product of partial melting of relatively fertile mantle and the rocks of tholeiite crystallization-differentiation.There is perfect evolution relationship among the primary rocks of the LREE-rich, LREE-rich positive Eu anomaly and LREE-rich negative Eu anomaly types of eclogites and among those of the REE pattern smooth and MREE-rich types of eclogites,the former three types were deried from continental settings and the latter two from nearly oceanic settings.Meanwhile,it is concluded that the mantle sources of primary rocks of the eclogites are inhomogeneous and the primary rocks of eclogites in this area appear to have undergone varying degree of crustal contamination.     

Rare earth element mobility at constant inter-REE ratios in the alteration zone at the Phelps Dodge massive sulphide deposit,Matagami, Quebec

Rare earth elements (REE) from La to Ho were mobile and enriched in hydrothermally altered rocks below the Archean Phelps Dodge Cu-Zn volcanogenic massive sulphide deposit in northwestern Quebec. Largest net enrichment was in the moderately altered quartz-chlorite zone where La concentration increased six-fold and La_NYb_N steepened from 1.9 to 13.0; the intensely altered chloritite zone had both minor net REE enrichment and depletion. Yb and Lu were immobile throughout both zones. The mobile REE were added and subtracted in constant chondrite-normalized inter-REE proportions: 1.0 La, 0.79 Ce, 0.57 Nd, 0.49 Sm, 0.01 Eu, 0.10 Tb and 0.02 Hb. Small additions of Eu relative to generally larger additions of LREE and Tb produced enhanced negative Eu-anomalies. The REE were mobilized at the hot (>300 C) core of the alteration system and deposited at the cooler periphery. Other sites of intense alteration and water/rock interaction display similar REE changes, indicating that selective REE enrichment at constant inter-REE ratios is a widespread phenomenon.     

相山铀矿田成矿流体特征:来自微量、稀土元素地球化学证据

相山铀矿田的成矿流体性质和来源存在争议,为进一步探讨相山铀矿田成矿流体的性质和来源,本文对相山铀矿田西部的居隆庵铀矿床和北部的沙洲铀矿床中的新鲜围岩、蚀变围岩及矿石的微量、稀土元素含量及其变化进行了研究。结果显示:在含较多热液成因萤石的居隆庵铀矿床中,从新鲜围岩到蚀变围岩到矿石,Zr、Hf含量先降低再升高;而在含少量热液萤石的沙洲铀矿床中,新鲜围岩、蚀变围岩和矿石的Zr、Hf含量基本一致。鉴于富F流体易汲取岩石中的Zr、Hf,因此,这两个矿床中不同类型样品Zr、Hf含量的不同变化趋势,可能与居隆庵铀矿床的成矿流体富F、而沙洲铀矿床的成矿流体相对贫F有关。这两个铀矿床中矿石的稀土配分曲线与其各自的新鲜及蚀变围岩的稀土配分曲线形态相似但又存在差异,说明每个矿床的新鲜围岩、蚀变围岩和矿石之间的稀土元素既具有继承性、又受到不同性质的流体的影响。居隆庵铀矿床中矿石显示Eu负异常,可能主要是继承了围岩的Eu负异常;沙洲铀矿床中矿石Eu显示弱负异常至弱正异常的特征,可能与围岩中斜长石因热液蚀变作用而释放出的Eu的进入流体有关。基于新鲜围岩、蚀变围岩及矿石的U和REE研究,推断居隆庵铀矿床成矿流体中U和REE均以F的络合物形式迁移;但沙洲铀矿床中铀矿石品位较低,可能是与流体中相对贫F有关。