Trace element characterisation of Cretaceous Orange Basin hydrocarbon source rocks

Trace elements in the kerogen fraction of hydrocarbon source rock samples from two wells obtained from the Cretaceous units of the Orange Basin, South Africa were determined using X-ray fluorescence spectrometry, in order to determine their distribution and geochemical significances. The concentrations of the elements (As, Ce, Co, Cu, Fe, Mo, Ni, Pb and V) determined ranged from 0.64 to 47,300 ppm for the samples analysed. The total organic carbon (TOC) values indicate that the samples are organic rich but did not show any trend with the distribution of the trace metals except Ce, Mo and Pb. Dendrogram cluster analysis discriminated the samples into three groups on the basis of their level of thermal maturity. Thermal maturity has a significant effect on the distribution of the trace metals. Cobalt/Ni and V/Ni ratios and cross plots of the absolute values of V and Ni indicate that the samples had significant marine organic matter input. The V and Ni contents and V/(V + Ni) ratio indicate that the organic matter of the source rocks had been deposited in reducing conditions. Despite the similarities in the organic matter source input and depositional environment of the organic matter of the samples from the two well, cross plots of Co/Ni versus V/Ni and Mo/Ni versus Co/Ni were able to reveal subtle differences. Cluster analysis of the samples was also able to reveal the subtle thermal maturity differences of the samples.     

Trace element mineral transformations associated with hydration and recarbonation of retorted oil shale

A laboratory study was conducted to evaluate the influence of hydration and recarbonation on the solidphase distribution of trace elements in retorted oil shale. The oil shale samples were retorted by the Paraho direct heating process and equilibrated with deionized—distilled water under controlled carbon dioxide conditions. A sequential extraction technique was then used to fractionate trace elements into soluble, KNO₃-extractable (easily exchangeable), H₂O-extractable (easily adsorbed), NaOh-extractable (organic), EDTA-extractable (carbonate), HNO₃-extractable (sulfide), and residual (nonextractable silicate) phases. The chemical fractions present in retorted oil shale and hydrated and recarbonated retorted oil shale were compared to identify trace element mineralogical changes that may occur in retorted oil shale disposal environments.Trace elements examined in this study were found to reside predominantly in the HNO₃-extractable and residual fractions. Hydration of retorted oil shale resulted in a shift in the majority of trace elements from residual to extractable forms. Cobalt, nickel, and zinc extractabilities were not significantly influenced by hydration, whereas antimony increased in the residual fraction. Subjecting retorted oil shale to atmospheric (0.033%) and 10% CO₂(g) levels over a nine-month equilibration period resulted in partial and full recarbonation, respectively. As the influence of recarbonation increased, trace elements reverted to residual forms. Vanadium, choromium, copper, zinc, antimony, and molybdenum in the 10% CO₂(g) recarbonated material were more resistant to sequential extraction than in retorted oil shale, whereas strontium, barium, and manganese were less resistant to sequential extraction. The extractabilities of cobalt, nickel, and lead were not affected by recarbonation. Recarbonation did not result in a predicted increase in EDTA-extractable trace elements. In general, the amounts of trace elements extracted by EDTA (and correlated to carbonate forms) were invariant with respect to equilibrium CO₂(g) levels.A significant result of this study was that the mineralogical residencies of trace elements in retorted oil shale were altered in response to conditions that may be present in a disposal environment. Thus, the long-term release of trace elements in retorted oil shale disposal environments may not be adequately predicted by applying the toxicity characteristic leaching procedure (TCLP).     

Trace element distribution in mineral separates of the Allende inclusions and their genetic implications

Concentrations of the REE, Sc, Co, Fe, Zn, Ir, Na and Cr were determined by instrumental neutron activation and mass spectrometric isotope dilution analysis for mineral separates of the coarseand fine-grained types (group I and II of Martin and Mason's classification) of the Allende inclusions.These data, combined with data on mineral/liquid partition coefficients, oxygen isotope distributions and diffusion calculations, suggest the following: (1) Minerals in the coarse-grained inclusions (group I) crystallized in a closed system with respect to refractory elements. On the other hand, differences in oxygen isotope distributions among minerals preclude a totally molten stage in the history of the inclusion. Group I inclusions were formed by rapid condensation (either to liquid or solid) in a supercooled solar nebula; extrasolar pyroxene and spinel dust were included but not melted in the condensing inclusions, thus preserving their extrasolar oxygen isotope composition. REE were distributed by diffusion during the subsequent heating at subsolidus temperatures; because oxygen diffuses much more slowly at these temperatures, the oxygen isotope anomalies were preserved. (2) The fine-grained (group II) inclusions were also formed by condensation from a super-cooled nebular gas; however, REE-rich clinopyroxene and spinel were formed early and REE-poor sodalite and nepheline were formed later and mechanically mixed with clinopyroxene and spinel to form the inclusions. The REE patterns of the bulk inclusions and the mineral separates are fractionated, indicating that REE abundances in the gaseous phase were already fractionated at the time of condensation of the minerals. (3) Pre-existing Mg isotope anomalies in the coarse-grained inclusions must have been erased during the heating stage thus resetting the ²⁶Al-²⁶Mg chronometer.     

Interferometric study of the dolomite dissolution: a new conceptual model for mineral dissolution

The dissolution rate and mechanism of three different cleavage faces of a dolomite crystal from Navarra (near Pamplona), Spain, were studied in detail by vertical scanning interferometry techniques. A total of 37 different regions (each about 124 × 156 μm in size) on the three sample surfaces were monitored as a function of time during dissolution at 25°C and pH 3. Dissolution produced shallow etch pits with widths reaching 20 μm during 8 h of dissolution. Depth development as a function of time was remarkably similar for all etch pits on a given dolomite surface.On the basis of etch pit distribution and volume as a function of time, the calculated dissolution rate increases from near zero to 4 × 10⁻¹¹ mol cm⁻² s⁻¹ over 5 h. The time variation is different for each of the three cleavage surfaces studied. In addition, the absolute dissolution rates of different parts of the dolomite crystal surface can be computed by using a reference surface. The different surfaces yield an “average” rate of 1.08 × 10⁻¹¹ mol cm⁻² s⁻¹ with a standard deviation of 0.3 × 10⁻¹¹ mol cm⁻² s⁻¹ based on about 60 analyses. The mean absolute rate of the dolomite surface is about 10 times slower than the rate calculated from etch pit dissolution alone. On the other hand, earlier batch rate data that used BET surface areas yield rates that are at least 30 to 60 times faster than our directly measured mean dissolution rate for the same pH and temperature.A conceptual model for mineral dissolution has been inferred from the surface topography obtained by the interferometry investigations. In this model, mineral dissolution is not dominated by etch pit formation itself but rather by extensive dissolution stepwaves that originate at the outskirts of the etch pits. These stepwaves control the overall dissolution as well as the dependence on temperature and saturation state.     

Trace element partitioning between carbonatitic melts and mantle transition zone minerals: Implications for the source of carbonatites

The occurrence of CO₂-rich lavas (carbonatites, kimberlites) and carbonate-rich xenoliths provide evidence for the existence of carbonatitic melts in the mantle. To model the chemical composition of such melts in the deep mantle, we experimentally determined partition coefficients for 23 trace elements (including REE, U-Th, HFSE, LILE) between deep mantle minerals and carbonatite liquids at 20 and 25 GPa and 1600 °C. Under these conditions, majoritic garnet and CaSiO₃ perovskite are the main reservoirs for trace elements. This study used both femtosecond LA-ICP-MS and SIMS techniques to measure reliable trace element concentrations. Comparison of the two techniques shows a general agreement, except for Sc and Ba. Our experimentally determined partition coefficients are consistent with the lattice strain model. The data suggest an effect of melt structure on partition coefficients in this pressure range. For instance, strain-free partition coefficient (D₀) for majorite-carbonatite melts do not follow the order of cation valence, , observed for majorite-CO₂-free silicate melts. The newly determined partition coefficients were combined with trace element composition of majoritic garnets found as inclusions in diamond to model trace element patterns of deep-seated carbonatites. The result compares favorably with natural carbonatites. This suggests that carbonatites can originate from the mantle transition zone.     

带源项浅水方程的通量平衡离散

以Roe的近似Riemann解为基础,将源项按特征方向进行特征分解,建立了带源项浅水方程的通量平衡Godunov求解格式。此格式具有迎风的性质并保证了变宽、非平底坡浅水方程计算的和谐性和存在底摩擦时的收敛性。通过实例验证了此法具有和谐、健全、通用性好、分辨率高等优点。     

Trace element abundances in andesites

Abundance data for Cs, Rb, Tl, Ba, Pb, Sr, the rare earths, Th, U, Zr, Hf, Sn, Nb, Mo, Mn, Cu, Co, Ni, Sc, V, Cr, Ag, Sb and the major elements are reported for two andesites and a dacite from Saipan, nine andesites and a dacite from Bougainville and two andesites from Fiji. The Saipan rocks are low-K varieties and contain notably low abundances of Rb, Ba, Th and U and have rare earth patterns subparallel to chondritic patterns. The Bougainville andesites include low-Si and high-K varieties which have higher concentrations of the large cations. The Fijian samples are close to the average circum-Pacific andesite and have rareearth patterns sub-parallel to those of sedimentary rocks.All the andesites contain characteristically low (< 20 ppm) values for Ni and have Ni/Co ratios < 1, and V/Ni ratios > 10.These data preclude derivation of calc-alkaline rocks by mixing of upper crustal material or by fractional crystallisation from basaltic parents. A two stage model is proposed involving sea-floor spreading and transportation of the oceanic crust down the dipping seismic plane into the mantle where it is remelted to form andesites.     

Trace element associations with Fe- and Mn-oxides in soil nodules: Comparison of selective dissolution with electron probe microanalysis

Selective dissolution methods have been largely used to get insight on trace element association with solid phases. Modern instrumental techniques offer many tools to test the validity of selective dissolution methods and should be systematically used to this end. The association of trace elements with Fe- and Mn-oxides in soil nodules has been studied here by electron probe microanalysis. The results were compared with findings from an earlier study on selective dissolution of the same nodules by hydroxylamine hydrochloride, acidified hydrogen peroxide, and Na-citrate-bicarbonate-dithionite. Electron probe microanalysis results were consistent with previous findings using selective dissolution and showed that P, As and Cr were mainly present in Fe-oxides, while Co was mainly associated with Mn-oxide phases. These results support the applicability of the studied selective dissolution methods for fractionation of trace elements in soils and sediments containing appreciable amounts of Fe and Mn-oxide phases.     

Trace element distribution in Chilean ignimbrites

The geochemistry of Chilean ignimbrites is discussed in terms of major and trace elements. The variation in the major elements and in the distribution of Ba, Co, Cu, Ga, Pb, Sn, Sr, V, and Zr with the differentiation factor (1/3Si+K)-(Ca+Mg) has been studied. The general trend is that characteristic of calc-alkaline rhyolite-dacite-andesite associations. Exceptionally high values of copper reported and high values of Sn and Zr provide further evidence of the anatectic origin of these ignimbrites.     

Trace element modelling of pelite-derived granites

The presence or absence of a vapour phase during incongruent-melt reactions of muscovite and biotite together with the composition of the protolith determines the trace-element characteristics of the resulting melt, provided that equilibrium melting occurs for those phases that host the tracc elements of interest. For granitic melts, Rb, Sr and Ba provide critical constraints on the conditions that prevailed during melting, whereas REE are primarily controlled by accessory phase behaviour. Mass-balance constraints for eutectic granites that are formed by the incongruent melting of muscovite in pelites indicate that melting in the presence of a vapour phase will result in a large melt fraction, and deplete the restite in feldspar. Hence the melt will be characterized by low Rb/Sr and high Sr/Ba ratios. In contrast, vapour-absent melting will result in a smaller melt fraction, and an increase in the restitic feldspar. Consequently high Rb/Sr and low Sr/Ba ratios are predicted. Vapour-absent melting will also enhance the negative Eu anomaly in the melt. Granites that result from the incongruent melting of biotite in the source will be characterized by higher Rb concentrations than those that result from the incongruent melting of muscovite. The Himalayan leucogranites provide an example of unfractionated, crustally derived eutectic melts that are enriched in Rb but depleted in Sr and Ba relative to their metasedimentary protoliths. These compositions may be generated by the incongruent melting of muscovite as a low melt fraction (F0.1) from a pelitic source under vapour-absent conditions.     

The effect of Fe-oxidizing bacteria on Fe-silicate mineral dissolution

Acidithiobacillus ferrooxidans are commonly present in acid mine drainage (AMD). A. ferrooxidans derive metabolic energy from oxidation of Fe²⁺ present in natural acid solutions and also may be able to utilize Fe²⁺ released by dissolution of silicate minerals during acid neutralization reactions. Natural and synthetic fayalites were reacted in solutions with initial pH values of 2.0, 3.0 and 4.0 in the presence of A. ferrooxidans and in abiotic solutions in order to determine whether these chemolithotrophic bacteria can be sustained by acid-promoted fayalite dissolution and to measure the impact of their metabolism on acid neutralization rates. The production of almost the maximum Fe³⁺ from the available Fe in solution in microbial experiments (compared to no production of Fe³⁺ in abiotic controls) confirms A. ferrooxidans metabolism. Furthermore, cell division was detected and the total cell numbers increased over the duration of experiments. Thus, over the pH range 2–4, fayalite dissolution can sustain growth of A. ferrooxidans. However, ferric iron released by A. ferrooxidans metabolism dramatically inhibited dissolution rates by 50–98% compared to the abiotic controls.

Two sets of abiotic experiments were conducted to determine why microbial iron oxidation suppressed fayalite dissolution. Firstly, fayalite was dissolved at pH 2 in fully oxygenated and anoxic solutions. No significant difference was observed between rates in these experiments, as expected, due to extremely slow inorganic ferrous iron oxidation rates at pH 2. Experiments were also carried out to determine the effects of the concentrations of Fe²⁺, Mg²⁺ and Fe³⁺ on fayalite dissolution. Neither Fe²⁺ nor Mg²⁺ had an effect on the dissolution reaction. However, Fe³⁺, in the solution, inhibited both silica and iron release in the control, very similar to the biologically mediated fayalite dissolution reaction. Because ferric iron produced in microbial experiments was partitioned into nanocrystalline goethite (with very low Si) that was loosely associated with fayalite surfaces or coated the A. ferrooxidans cells, the decreased rates of accumulation of Fe and Si in solution cannot be attributed to diffusion inhibition by goethite or to precipitation of Fe–Si-rich minerals. The magnitude of the effect of Fe³⁺ addition (or enzymatic iron oxidation) on fayalite dissolution rates, especially at low extents of fayalite reaction, is most consistent with suppression of dissolution by interaction between Fe³⁺ and surface sites. These results suggest that microorganisms can significantly reduce the rate at which silicate hydrolysis reactions can neutralize acidic solutions in the environment.     

Do clay mineral dissolution rates reach steady state?

The temporal evolution of natural illite du Puy dissolution rates was measured from Si release rates in single-pass flow-through experiments lasting at least 100 days at 25°C and pH ranging from 2 to 12. Si release rates decreased by a factor of five and three at pH 12 and 2, respectively, during the experiments. These observations are interpreted to stem from changes in illite du Puy reactive surface area during these experiments. As the edges of clay minerals dissolve faster than the basal planes, dissolution tends to change clay mineral morphology decreasing the percentage of reactive edge sites. This continuously changing morphology prevents illite dissolution rates from attaining steady state during laboratory experiments lasting 100 to 200 days. A similar temporal decrease in dissolution rates is evident for many different sets of clay mineral dissolution rate data available in the literature. It seems reasonable, therefore, to expect that clay mineral dissolution does not attain steady state in nature, but rather their dissolution rates decrease continuously during their dissolution.     

Trace element partitioning in plagioclase feldspar

Compilation and interpretation of experimental and natural Nernst partition coefficient (^{plagioclase/melt}D) data show that, with a few exceptions, increases in ^{plagioclase/melt}D correlate with decreasing anorthite-content of plagioclase. In contrast, increases of ^{plagioclase/melt}D for Ga, Sc, Cu, Zn, Zr, Hf and Ti, are better correlated against decreasing melt MgO or increasing melt SiO₂ contents. ^{plagioclase/melt}D for Ti and the rare earth elements (REE) show little dependence on temperature, but increase as the melt water content increases. ^{plagioclase/melt}D for K and Sr are sensitive to pressure. Variations of D₀ (the strain compensated partition coefficient), r₀ (the size of the site into which REE substitute), and E (Young’s Modulus of this site) were parameterized against variations of melt SiO₂, the An-content of plagioclase, and other combinations of variables, allowing ^{plagioclase/melt}D_REE-Y to be calculated from a variety of input parameters. The interrelations of temperature, melt MgO and SiO₂ content, and plagioclase anorthite-content for wet and dry systems were also parameterized to facilitate interpolation where such data are lacking. When combined, these semi-empirical parameterizations yield ^{plagioclase/melt}D results comparable to available experimental and natural data.     

Trace element abundances and mineral/melt distribution coefficients in phonolites from the Laacher See volcano (Germany)

Twenty six whole rocks, seven matrix and fifty three mineral separates from the compositionally zoned late Quaternary Laacher See tephra sequence (East Eifel, W Germany) were analyzed by instrumental neutron activation. These data document the chemical variation within the Laacher See magma chamber prior to eruption with a highly fractionated phonolite at the top and a more mafic phonolite at its base as derived from other data. Incompatible elements such as Zn, Zr, Nb, Hf, U, light and heavy rare earths are extremely enriched towards the top whereas compatible elements (e.g. Sr, Sc, Co, Eu) are strongly depleted. Semicompatible elements (Ta and some middle REE) are depleted at intermediate levels. This chemical variation is shown by whole rock and matrix data indicating the phonolite liquid was compositionally zoned regardless of phenocryst content. Hybrid rocks (phonolite-basanite) show the largest concentrations for compatible elements. All elements (except Rb) display continuous compositional variations with regard to the stratigraphic position of pumice samples. From these data we are able to distinguish three main units: An early erupted highly fractionated magma, the main volume of evolved phonolite and a mafic phonolite as the final products. The extreme variation of trace element distribution coef ficients (K) for 9 mineral phases with respect to stratigraphic position (resp. matrix composition) cannot be explained by conventional mechanisms. We postulate a significant modification of the trace element content of the phonolite melt by liquid-liquid controlled differentiation processes subsequent to and/or contemporaneous with (fractional) crystallization which caused disequilibrium between phenocrysts and host matrix. Therefore, our “distribution coefficients” deviate from equilibrium partition coefficients equivalent to the amount of this post crystallization modification of the matrix composition. The relationship between varying K and matrix composition is demonstrated by a ΔK-ΔM-diagram (variation of K versus variation of matrix, M). Different parts of this diagram relate to different parameters (T, P, polymerization, complex-building, equilibrium crystallization in a zoned magma column and post crystallization disequilibrium effects) which are responsible for the variation of distribution coefficients in general. The ΔK-ΔM-diagram may allow to distinguish between different processes affecting the distribution coefficients measured in natural volcanic rocks from a differentiating magma system.     

Trace element distribution in mineral inclusions in zoned garnets from eclogites of the Atbashi Range (South Tianshan)

Ion microprobe data for minerals from the eclogites of the Atbashi Range (South Tianshan) constrain the distribution of trace (Rb, Sr, Ba, Cr, V, Zr, Hf, Nb, Ta, U, Th, and Y) and rare-earth elements (REE) in zoned garnets and mineral inclusions in them. This study showed that garnets from the Atbashi eclogites are the main hosts for heavy REE; epidotes are important hosts for REE, Y, Sr, Th, and U; and omphacites are depleted in almost all trace elements compared with the bulk-rock compositions. Garnet, as well as epidote and omphacite inclusions exhibit systematic rimward depletion in a number of trace elements, which is related to the depletion of the rock matrix in these elements during crystallization. Deviations from this trend, including the enrichment of garnet rims in HREE and strong variations in the REE contents of garnets and mineral inclusions, can be explained by metamorphic reactions involving the destabilization of REE-bearing minerals. Our data suggest that the mobility of trace elements under eclogites-facies conditions is mainly controlled by the stability of certain minerals.     

Connections between surface complexation and geometric models of mineral dissolution investigated for rhodochrosite

Mineral dissolution rates have been rationalized in the literature by surface complexation models (SCM) and morphological and geometric models (GM), and reconciliation of these conceptually different yet separately highly successful models is an important goal. In the current work, morphological alterations of the surface are observed in real time at the microscopic level by atomic force microscopy (AFM) while dissolution rates are simultaneously measured at the macroscopic level by utilizing the AFM fluid cell as a classic flow-through reactor. Rhodochrosite dissolution is studied from pH = 2 to 11 at 298 K, and quantitative agreement is found between the dissolution rates determined from microscopic and macroscopic observations. Application of a SCM model for the interpretation of the kinetic data indicates that the surface concentration of >CO₃H regulates dissolution for pH < 7 while the surface concentration of >MnOH₂⁺ regulates dissolution for pH > 7. A GM model explains well the microscopic observations, from which it is apparent that dissolution occurs at steps associated with anisotropic pit expansion. On the basis of the observations, we combine the SCM and GM models to propose a step-site surface complexation model (SSCM), in which the dissolution rates are quantitatively related to the surface chemical speciation of steps. The governing SSCM equation is as follows: R = χ_1/2(k_co + k_ca)[>CO₃H] + χ_1/2(k_mo + k_ma)[>MnOH₂⁺ ], where R is the dissolution rate (mol m⁻² s⁻¹), 2χ_1/2 is the fraction of surface sites located at steps, [>CO₃H] and [>MnOH₂⁺ ] are surface concentrations (mol m⁻²), and k_co, k_ca, k_mo, and k_ma are the respective dissolution rate coefficients (s⁻¹) for the >CO₃H and the >MnOH₂⁺ surface species on obtuse and acute steps. We find k_co = 2.7 s⁻¹, k_ca = 2.1 × 10⁻¹ s⁻¹, k_mo = 4.1 × 10⁻² s⁻¹, k_ma = 3.7 × 10⁻² s⁻¹, and χ_1/2 = 0.015 ± 0.005. The rate coefficients quantify the net result of complex surface step processes, including double-kink initiation and single-kink propagation. We propose that the SSCM model may have general applicability for dissolution far from equilibrium of flat mineral surfaces of ionic crystals, at least those that dissolve by step retreat.     

基于岩石元素含量确定岩石矿物组分的方法

岩石中矿物组分和含量对岩性划分、沉积环境判断及物源方向分析等方面均有非常重要的意义。岩石中各元素百分含量与矿物组成和演化有着密切的关系,通过确定元素含量与矿物含量之间的转换系数,依托转换系数这一桥梁,可以将元素含量转换成矿物含量。文章结合岩芯元素含量结果及全岩测试数据资料,通过对比"逐级分离"法计算结果与全岩计算结果,其结果表明:①转换系数具有一定的专一性;②该方法与多元回归方法相比,该方法可以依据较少的数据确定该地区的转换系数;③利用"逐级分离"法获得的计算结果,较符合该地区的转换系数,可以应用于岩性识别与分类。     

Trace element and isotopic composition of baddeleyite

Summary Baddeleyite from Palabora Igneous Complex, South Africa, is among the purest natural ZrO₂ phases. This has been demonstrated by using various methods, i.e. microprobe, neutron activation, spark source and thermal ion mass spectrometry. HfO₂ with 1.87% is the only other major component. The concentrations of other HFSE are also relatively high, compared to most other elements, that reach only a few ppm.The REE display a U-shaped pattern that is interpreted to be superimposed by a strongly LREE enriched source component. The high⁸⁷Sr/⁸⁶Sr initial of 0.713085 and the negative Nd_t of –10.7 prove that this component was LILE enriched for a long time prior to the formation of the Palabora Igneous Complex. These data indicate that the baddeleyite crystallized from a magma which was derived from an enriched mantle reservoir, similar to that involved in the formation of group II kimberlites.

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Spurenelemente und Isotopenzusammensetzung von Baddeleyit

Zusammenfassung Baddeleyit vom Palabora Igneous Complex, Südafrika, gehört zu den reinsten natürlichen Vorkommen von ZrO₂. Dies wurde durch Analysen mit verschiedenen Methoden wie Mikrosonde, Neutronenaktivierung, Funken- und Thermionenmassenspektrometrie bestätigt. HfO₂ ist mit 1.87 die einzige andere Hauptkomponente, auch die Konzentrationen der anderen HFSE sind relativ hoch im Vergleich zu den anderen Elementen, die nur wenige ppm erreichen.Die REE bilden ein U-förmiges Muster, das als Ausdruck einer stark LREE angereicherten Komponente im Ausgangsgestein gedeutet wird. Das hohe⁸⁷Sr/⁸⁶Sr-Initialverhältnis von 0.713085 und das negative Nd_t von -10.7 belegen, daß diese Komponente über einen langen Zeitraum vor der Bildung des Palabora Igneous Complex angereichert gewesen war. Diese Daten deuten an, da der Baddeleyit aus einem Magma kristallisierte, das aus einem angereicherten Mantelreservoir stammte, ähnlich dem, das bei der Bildung der Gruppe 11 Kimberlite beteiligt war.

     

Trace element geochemistry of Archean volcanic rocks

K, Rb, Sr, Ba and rare earth elements of some Archean volcanic rocks from the Vermilion greenstone belt, northeast Minnesota, were determined by the isotopic dilution method. The characteristics of trace element abundances, supported by the field occurrences and major element chemistry, suggest that these volcanic rocks were formed in an ancient island arc system. A felsic rock is suggested to be derived by partial melting of a basaltic source, presumably in an ancient subduction zone.It is well known that the distribution coefficients (liquid/source) for the above trace elements are almost invariably greater than one. Continuous extraction of volcanic liquids from the upper mantle through geologic time would result in depletion of these elements in the upper mantle. However, all trace element abundances in many Archean volcanic rocks are almost identical to their modern equivalents. This gross constancy of trace element concentration in rocks of different geologic age raises some important questions as to the evolution of the upper mantle. It is proposed that the trace elements have been repeatedly and fully recycled in a restrictive and closed system of crust and upper mantle during the last three billion years (recycled mantle), or the trace elements have been replenished from the lower part of the mantle by some undefined process (replenished mantle). It is believed that interplay of both recycling and replenishment have been responsible for crust-mantle evolution in geological history.