Rare earth element patterns and crustal evolution—II. Archean sedimentary rocks from Kalgoorlie,Australia

REE data, with major element and other trace element data are reported for a suite of Archean sedimentary rocks (2800 million years old) from Kalgoorlie, Western Australia. The REE patterns fall into two groups with ?LREE/?HREE ratios of 6 and 15, respectively. The first group have either no Eu anomaly relative to chondrites, or a positive Eu anomaly, in contrast to the pronounced Eu depletion (Eu/Eu ~ 0.67) shown by younger (Post-Archean) sedimentary rocks.The problem of positive Eu enrichment relative to chondritic patterns, is examined by analysing a suite of Devonian greywackes, derived from calc-alkaline volcanic rocks. Some of these samples also show positive Eu anomalies, attributable to local accumulation of feldspar. This explanation is preferred to models involving an early anorthositic crust. The group of samples showing heavy REE depletion patterns (complementary to those observed in garnet) appear to be derived from adjacent Na-rich granites which display identical REE patterns. Locally abundant K-rich granites do not appear to have made any contribution to the Archean sedimentary rocks.The majority of the sedimentary rocks have REE patterns indistinguishable from those of recent island arc calc-alkaline rocks, and so could constitute evidence that the Archean crust was principally formed by processes analogous to present day island-arc type volcanism. However, similar REE patterns may be produced by an appropriate mixture of the common bimodal tholeiitic-felsic igneous suite commonly observed in Archean terrains. The REE data presented here do not distinguish between these two models.     

Rare earth element patterns of rocks from the centre 3 igneous complex,Ardnamurchan, Argyllshire

Systematic, differences in absolute abundancies and distribution patterns of rare earth elements are shown to exist for the main rock types of the third and final phase of the Tertiary igneous complex of Ardnamurchan. Published partition coefficients of the rare earth elements between crystals and host magmas of extrusive rocks have been used, together with modes of the Ardnamurchan rocks, to estimate the rare earth element patterns of the parent magmas. The results confirm that the basic rocks formed by crystal fractionation but that continued crystal fractionation from a single parent magma could not have formed the intermediate rocks.     

Rare earth element distribution in Plio-Quaternary volcanic rocks from southern Peru

Rare-earth element abundances of calc-alkaline andesitic rocks from southern Peru show that these rocks cannot be produceed by a single stage process. The high content of LILE, particularly LREE requires their derivation from a source already enriched in these elements and having a distinctly fractionated REE pattern. It is suggested that ascending hydrous fluids, released from the subducted oceanic lithosphere, enriched the upper mantle in LILE by zone refining. The partial melting of such an enriched upper mantle, followed by fractional crystallization, could produce andesitic rocks. REE data indicate that shoshonitic rocks from southern Peru can be derived from an unfractionated garnet-bearing peridotite by a low degree of partial melting.     

Rare earth element-thorium correlations in sedimentary rocks,and the composition of the continental crust

There is a correlation between thorium and the light rare earth elements, indicated by La/Th ratios in fine grained sedimentary rocks of various ages from Australia and Greenland. The correlation between Th and the heavy rare earth elements (Th/Yb) is much less significant. Archean sedimentary rocks have a higher La/Th (3.6 ± 0.4) than post-Archean sedimentary rocks (La/Th = 2.7 ± 0.2).The cause of this correlation can be attributed to the coherent behaviour of these elements during most sedimentary processes (weathering, transport, diagenesis, etc.). Since the chondrite-normalized rare earth element distribution of clastic fine grained sedimentary rocks is accepted to be parallel to the distribution of REE in the upper continental crust, an estimate of upper crustal Th abundances can be made. Using reasonable assumptions of certain elemental ratios (K/U, Th/U, K/Rb) in the upper crust, minimum estimates of the abundances of K, U and Rb can also be made for the post-Archean and Archean upper crusts.The post-Archean values (K = 2.9%; Rb = 115 ppm; Th = 11.1 ppm; U = 2.9 ppm) compare favourably to some previous estimates made from direct sampling and theoretical considerations and help confirm a granodiorite present day upper continental crust. The Archean data (K = 0.92%; Rb = 30ppm; Th = 3.5 ppm; U = 0.92 ppm) support models which suggest a significantly more mafic exposed crust at that time.     

Rare earth element patterns in Archean high-grade metasediments and their tectonic significance

Metasediments from two contrasting types of Archean high-grade terrains are interpreted as being derived from distinct tectonic settings. The Kapuskasing Structural Zone, Canada, represents the deep roots of a typical greenstone belt, whereas the Limpopo Province, southern Africa and Western Gneiss Terrain, Australia, mainly consist of shelf sediments deposited on a granitic basement and then buried to the depths required for granulite fades metamorphism. Upper amphibolite to granulite fades paragneisses from the Kapuskasing Structural Zone have REE patterns similar to those of greenstone belt sediments, except where partial melting has occurred, forming restites with Eu enrichment and melts with Eu depletion. Except in this latter instance, metamorphism has not affected the primary REE patterns. REE patterns in Archean upper amphibolite to granulite facies metasediments from the central Limpopo Province and Western Gneiss Terrain show wide differences, ranging from patterns which resemble those in post-Archean terrigenous sediments, to typical Archean sedimentary rock patterns. The diversity in REE patterns for these shallow shelf metasediments is interpreted as resulting from derivation from local provenances. Samples with “post-Archean” patterns, displaying Eu depletion, are interpreted as being derived from K-rich granitic plutons which were portions of small, stable early Archean terrains, precursors of the widespread late Archean-Proterozoic episode of major cratonic development.     

Rare earth element patterns in manganese nodules and micronodules from northwest Atlantic

The shale-normalized REE patterns of manganese nodules from the northwest Atlantic show enrichment in Sm and Eu relative to the heavier and lighter REE, excluding Ce, and are similar to the patterns previously observed in deep water (> 3000m) nodules from the Pacific. The inverse relation of this pattern to that of sea water and the high Ce anomaly (average 5.5) indicate that probably the REE in the nodules originate from sea water and the nodules are possibly hydrogenous. The patterns for micronodules are similar to those of the nodules but the concentrations of REE were substantially higher in two of them.The red clay occurring on abyssal hills where nodules and micronodules are found also shows higher REE concentrations over terrigenous gray clay. The latter is devoid of nodules and micronodules and occurs in abyssal plains. The excess REE in the red clay also show a pattern similar to those of the nodules and micronodules. Most of the micronodule samples show a lower Ce anomaly (1.7) and lower Co concentration compared to the nodules, so it is inferred that at least some micronodules were formed during post-depositional periods when the conditions were less oxidizing than average.     

Rare earth element geochemistry of Archean metasedimentary rocks from Kambalda,Western Australia

Archean sedimentary rocks of very limited lateral extent from horizons within basaltic and ultramafic volcanic sequences at Kambalda, Western Australia, are extremely variable in major elements, LIL and ferromagnesian trace element compositions. The REE patterns are uniform and do not have negative Eu anomalies. Two samples have very low total REE abundances and positive Eu anomalies attributed to a very much greater proportion of chemically deposited siliceous material. Apart from these two samples, the Kambalda data are similar to REE abundances and patterns from Archean sedimentary rocks from Kalgoorlie, Western Australia and to average Archean sedimentary rock REE patterns. These show a fundamental distinction from post-Archean sedimentary rock REE patterns which have higher $\text{La}\text{Yb}$ ratios and a distinct negative Eu anomaly.     

辽西义县旋回火山岩的稀土元素特征

义县火山旋回可分为4个亚旋回。从早期至晚期,义县旋回火山岩逐渐由基性向中基性、中性和酸性演化。义县旋回火山岩稀土总量较高,稀土分布模式呈右倾型,轻稀土分馏作用高于重稀土的分馏作用,为轻稀土富集型,总体显示弱负铕异常、弱的正铈异常。稀土元素具有陆内火山岩的基本特征。成因分析表明:义县旋回火山岩的形成,受地幔热流和壳幔物质的再循环制约,火山岩的成因以部分熔融为主。     

Rare earth element geochemistry of the Permo-Carboniferous clastic sedimentary rocks from the Spiti Region,Tethys Himalaya: significance of Eu and Ce anomalies

Acta Geochimica - Siliciclastic sedimentary rocks, including sandstones and associated shales, from the Permo-Carboniferous Kanawar Group of NW Tethys Himalaya, Spiti Region, India were examined...     

Rare earth element distributions in some Precambrian rocks and their phyllosilicates,Numedal, Norway

Mass spectrometric analyses for rare earth elements (REE) have been carried out on some Precambrian mica schists, gneisses and granites from the Precambrian Numedal area, Norway and on their phyllosilicates. The rocks, which are metamorphosed in the upper greenschist to amphibolite facies, were originally partly sedimentary, partly magmatic.The total REE contents for rocks varies from 145 to 761 ppm. An average of 16 phyllosilicate samples gave 417 ppm REE (max. of 1809 ppm, min. of ca. 50 ppm). Coexisting light and dark phyllosilicates have similar abundances of REE. For the micas of high REE content most of the REE was extractable by rinsing with EDTA. The data thus support the possibility of an extensive adsorption of REE ions on micaceous minerals. The REE distribution patterns do not provide a clear distinction between the sedimentary and magmatic origin for the rocks examined.     

Rare earth element abundances and distribution patterns in hydrothermally altered basalts: Experimental results

Oceanic tholeiites that have been experimentally reacted with seawater at 500–600° C, 800–1000 bars, have rare earth element (REE) abundances and distribution patterns that are essentially identical to those of the unaltered basalts. Although the data indicate the possibility of some REE leaching and redistribution, the net effects are small and the REE patterns of basalts affected by submarine hydrothermal processes may still be valid petrogenetic indicators.     

The development of acidic groundwaters in coal-bearing strata: Part I. Rare earth element fingerprinting

This study examines the rare earth element (REE) pattern of acidic mine discharges in the Durham basin (NE England) as a means of fingerprinting their sources and understanding the water-rock interactions Although whole rock compositions proved to be unhelpful, mimicking acid mine water generation in a series of selective leachates of the coal and coal-bearing strata gave REE patterns similar to those measured in the emergent waters. REE ratios and anomalies were used as indicators of specific interactions in the development of acidic groundwater. The implications of the findings for the classification and evolution of acid mine discharges are discussed.     

Rare earth elements in Huronian (Lower Proterozoic) sedimentary rocks: Composition and evolution of the post-Kenoran upper crust

The Huronian sequence (Lower Proterozoicl. north of Lake Huron, contains tillites and abundant fine-grained sedimentary rocks. Analyses of rare earth elements (REE) in the matrix of tillite samples from the Gowganda Formation (~ 2.3 Gal is considered to be a reasonable estimate of upper crustal REE abundances for the region north of Lake Huron at the time of Gowganda deposition. The average is characterized by a moderately steep pattern (σLREEσHREE = 9.1) and a slight negative europium anomaly ($\text{Eu}\text{Eu1}\text{= 0.89}$). This pattern is similar to estimates of the composition of the surface of the Canadian Shield and is intermediate between estimates of typical Archean and post-Archean sedimentary rocks. REE patterns for framework granitoid clasts from the tillite suggest that K-rich granites, which were apparently unimportant in the formation of Archean sedimentary rocks, were abundant in the source regions of the Gowganda Formation. This may explain the intermediate nature of the Gowganda pattern.Comparison of the tillites and associated Gowganda mudstones suggests that previous estimates of upper crustal REE abundances, which were based on the analyses of fine-grained sedimentary rocks, may be systematically high. Relative distributions, however, are the same.Analyses of mudstones from the McKim. Pecors. Serpent Gowganda Lorrain and Gordon Lake Formations suggest rapid evolution in the composition of the exposed upper crust at the close of the Kenoran orogeny. REE patterns at the base of the Huronian are similar to typical Archean sedimentary rocks. REE characteristics change up section: patterns at the top resemble typical post-Archean sedimentary rocks.It is inferred that an essentially episodic change from an early exposed upper crust dominated by a tonalite-greenstone suite to one approximating granodioritic composition is recorded in Huronian sedimentary rocks. A deviation from the evolutionary trend of the Huronian, documented in the Gowganda Formation, may be related to the glacial origin of the Gowganda.     

Consistent patterns of rare earth element distribution in accessory minerals from rocks of mafic-ultramafic complexes

This paper summarizes analytical data accumulated in the world literature and other materials about the regularities of the REE distribution in minerals contained in ultramafic and mafic rocks as accessory phases. These minerals are tentatively divided into two groups. The first includes garnets, zircons, apatites and perovskites, which can accumulate increased amounts of REE in their structure. The second consists of minerals whose structure can accumulate only limited contents of these trace elements. These are chrome-spinels, ilmenites, and micas. These minerals, in respect of REE geochemistry, are studied to a varying degree because of the different levels of accumulations of these elements, different degrees of occurrence in rocks, tiny sizes of their grains and other reasons. The analytical database formed on their basis includes about 600 original analyses. The overwhelming majority of presently available data on REE geochemistry in accessory minerals from ultramafic and mafic rocks have been published only in the recent 15 years. The studies became possible due to the development and introduction of new highly sensible microprobe analyses allowing detection of REE and many other trace elements in minerals grains directly in thin sections. The greatest numbers of these analyses were performed for garnets and zircons, fewer for apatites, and the fewest for chrome-spinels, ilmenites, micas, and perovskites. In general, the regularities of REE distribution in these minerals from ultramafic and mafic rocks are less studied compared to the rock-forming minerals from ultramafic and mafic rocks. Among the analytical methods, which were used to study the REE composition of accessory minerals, the most efficient was the mass-spectrometry with inductively coupled plasma (ICP-MS).     

Petrogenesis of some Ligurian peridotites—II. Rare earth element chemistry

REE compositions of nine partially serpentinized Iherzolitic rocks from Liguria have been investigated: eight samples are from the Erro-Tobbio thrust sheet of the Gruppo di Voltri (western Liguria); one sample is from an allochthonous eastern Liguria mass within the External Ligurides. As previously described (Ernst and Piccardo, 1979, Geochim. Cosmochim. Acta43, 219–237), all specimens are spinel (±plagioclase) Iherzolites. They possess major element bulk rock chemistries which are more or less ‘primitive’ or only slightly depleted compared to estimated upper mantle compositions. Mineral chemistries, varying insignificantly from rock to rock, evidently reflect mantle equilibration in the range 1000–1150°C and 14–16 kbar; pervasive retrograde effects testify to later decompression at shallower levels characterized by temperatures exceeding a typical intraplate oceanic geothermal gradient.The investigated lherzolitic samples show concordant REE patterns, LREE-depleted with respect to chondrites. A wide range in values is observed among the LREE: the observed depletion of LREE in most of the samples is accompanied by a Ce-negative anomaly. Inasmuch as the analyzed samples have been affected to a variable extent by serpentinization, REE mobility during hydrous alteration is treated employing both a theoretical approach and natural evidence.Effects of partial melting prior to serpentinization (resulting chiefly in depletion in LREE) can be rationalized by postulating a two-times chondritic REE abundance in the original unaltered peridotitic material and by considering the HREE contents to have been unaffected by hydrous alteration. When comparison is made with REE compositions for residual material after different degrees of partial melting (computed using an equilibrium, non-modal partial melting model and selected REE partition values), the analyzed Ligurian samples show effects of incipient melting on only a small scale, i.e. 1–5%. Judging from their major and REE compositions, the investigated lherzolites cannot have produced substantial amounts of tholeiitic melt, hence they cannot have provided the primary magmas for the oceanic crustal sequences so widespread within the Northern Apennine and Gruppo di Voltri ophiolitic terranes.     

Rare earth element and gallium diffusion in yttrium aluminum garnet

Diffusion of four rare-earth elements and gallium has been measured in yttrium aluminum garnet (YAG). Sources of diffusant were mixtures of alumina and rare-earth element oxides for REE diffusion, and mixtures of gallium and yttrium oxides for Ga diffusion. Diffusion profiles were measured with Rutherford backscattering spectrometry (RBS). For the rare-earth elements investigated, the following Arrhenius relations were obtained: D_La=6.87×10^–1 exp (–582±21 kJ mol^–1 /RT) m²s^–1 D_Nd=1.63×10^–1 exp (–567±15 kJ mol^–1 /RT) m²s^–1 D_Dy=2.70×10⁰ exp (–603±35 kJ mol^–1 /RT) m²s^–1 D_Yb=1.50×10^–2 exp (–540±26 kJ mol^–1 /RT) m²s^–1 Diffusion rates for the rare earths are quite similar, in contrast with trends noted for zircon. It is likely that these differences are a consequence of the relative ionic radii of the REE and the cations for which they substitute in the mineral lattice. For gallium, the following Arrhenius relation was determined: D_Ga=9.96×10^–6 exp (–404±19 kJ mol^–1 /RT) m²s^–1 Gallium diffuses faster than the REE in YAG and has a smaller activation energy for diffusion. These data mirror relative trends in diffusion rates for YIG, in which trivalent cations occupying tetrahedral and octahedral sites (i.e., Al, Ga, Fe) diffuse faster than trivalent cations occupying dodecahedral sites (i.e., Y and the REE), and suggest that the rate-limiting process in the diffusion-controlled regime of solid-state creep of YAG is the diffusion of yttrium. Received: 10 November 1997 / Revised; accepted: 13 March 1998     

Rare earth element partitioning between titanite and silicate melts: Henry’s law revisited

We present detailed experimental results on the partitioning of rare earth elements (REE) between titanite and a range of different silicate melts. Our results show that Henry’s law of trace element partitioning depends on bulk composition, the available partners for heterovalent substitution, crystal composition, and melt composition. We illustrate that the partition coefficients for Sm depend very strongly on the bulk concentration of Sm in the system. The substitution mechanism, by which rare earth elements are incorporated into the crystal structure, plays an important role for trace element partitioning and also for the onset of Henry’s law. Our data show that there are clear differences between substitution mechanisms of major elements compared to elements which are present only as traces. Our experiments also clearly show that the onset of Henry’s law depends on the concentrations of the sum of all trace elements which are incorporated into the crystal by the same substitution mechanism. For geochemical modelling of magmatic processes involving titanite, and indeed other accessory phases, it is of crucial importance to first evaluate whether the REE, and other trace elements, are present as traces or as major elements, only then appropriate D values may be chosen.     

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.     

Rare earth element fractionation in metamorphogenic hydrothermal calcite,magnesite and siderite

Summary Normalized REE patterns of aqueous solutions and their precipitates bear information on the physico-chemical environments a fluid experienced during REE mobilization, fluid migration and minerogenesis. Positive Eu and Yb anomalies indicate REE mobilization by a F^–-, OH^–- and CO₃ ^2–-poor fluid in a high-temperature regime, but are only retained by a precipitating mineral if precipitation occurs in a low-temperature environment. Negative Ce anomalies are typical of oxidizing conditions and are unlikely to develop during siderite precipitation. LREE/HREE fractionation is controlled by fluid composition and mineralogical control. REE patterns of Ca minerals allow to class the reacting fluids in normal (Ca/ligand 1) and ligand-enriched (Ca/ligand 1), the latter being characteristic for remobilization processes.The Radenthein magnesite and Hüttenberg siderite deposits, both Carinthia, Austria, are discussed and shown to be of non-sedimentary, non-metamorphic, but metamorphogenic metasomatic origin.

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Fraktionierung der seltenen Erd-Elemente in metamorphogenen hydrothermoclen Calciten, Magnesiten und Sideriten

Zusammenfassung Normierte Lanthaniden-Verteilungsmuster wässeriger Lösungen und deren Präzipitate enthalten Informationen über die verschiedenen physiko-chemischen Bedingungen, denen die Fluidphase während der Mobilisierung der Lanthaniden, der Migration und der Minerogenese ausgesetzt war. Positive Eu- und Yb-Anomalien weisen auf eine Mobilisierung der Lanthaniden bei erhöhten Temperaturen durch eine F^–-, OH^–-und CO₃ ^2–-arme Lösung. Die positiven Anomalien der Lösung werden jedoch nur dann auf ein Mineral übertragen, wenn dessen Präzipitation in einem niedrigen Temperaturbereich erfolgt. Negative Ce-Anomalien sind Indikatoren oxischer Bedingungen, weshalb ihre Entwicklung im Verlauf einer Siderit-Präzipitation weitgehend ausgeschlossen werden kann. Die Fraktionierung von leichten und schweren Lanthaniden wird von der chemischen Zusammensetzung der Fluidphase und der mineralogischen Kontrolle bestimmt. Die Lanthaniden-Verteilungsmuster von Ca-Mineralen erlauben es, deren Mutter-Lösungen in normal (Ca/Liganil 1) und Liganden-reich (Ca/Liganil 1) zu untergliedern, wobei letztere für Remobilisierungsprozesse typisch sind.Verschiedene minerogenetische Modelle für Spatmagnesite aus der Lagerstätte Radenthein und Siderite aus der Lagerstätte Hüttenberg, beide Kärnten, Österreich, werden vor dem Hintergrund deren Lanthaniden-Verteilung diskutiert. Es wird gezeigt, daß sowohl für die Radenthein-Magnesite als auch für die Hüttenberg-Siderite nur ein nicht-sedimentäres, nicht-metamorphes, wohl aber metamorphogen-metasomatisches minerogenetisches Modell mit der Lanthaniden-Verteilung kompatibel ist.

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This paper was presented at the IGCP 291 Project Symposium Metamorphic Fluids and Mineral Deposits, ETH Zürich, March 2I–23,1991.