Constraints on mantle source compositions imposed by phosphorus and the rare-earth elements

There is a positive correlation between the concentration of P₂O₅ in basic magmas and the concentration of the REE and also between their light: heavy ratio, represented by both Ce/Yb and Nd/Sm. This suggests that a phosphate mineral, such as apatite or whitlockite, both of which can contain high concentrations of REE, is present in the magma source regions. Thermodynamic calculations indicate that fluorapatite is stable over the whole P-T range of magma generation, but at the greatest depths it may co-exist with whitlockite in the presence of fluorphlogopite. Using published REE crystal-liquid distribution coefficients, it is evident that for P₂O₅-rich basic magmas with 700–1000 times chondritic abundances of LREE, garnet need not have contributed significantly to their composition. The most convincing match of hypothetical liquid with actual basic magma is for the derivation of mid-ocean ridge (MOR) basalts from plagioclase- or spinel-lherzolite containing 3 times chondritic REE by ∼5% partial melting. The more P₂O₅-rich, and hence REE-rich, basic magmas are apparently derived from crystalline sources which are progressively impoverished in garnet and clinopyroxene, or in other words, the greater the REE concentration of basic magma, the more refractory is the mineral assemblage of the source. There is some evidence for a compositional dependence of radiogenic neodymium and lead in basic magma, and one way that this can be reconciled with mantle source-region evolution is to postulate that fusion is not always accompanied by isotopic equilibrium.     

Phosphorus and the rare earth elements in felsic magmas: an assessment of the role of apatite

The solubility of fluorapatite in 17 silica-rich melts in the system Na₂O-K₂O-Al₂O₃-SiO₂ (with and without CaO or CaF₂) was determined at 1 kbar water pressure and 750 900°C. Apatite saturation occurs at levels of dissolved P₂O₅ ranging between 0.04 (± 0.02) and 0.28 (± 0.13) wt%. with only 4 values outside the 0.09–0.20 wt% range.The results demonstrate not only that apatite is a common liquidus phase in felsic melts, but also that, under most circumstances, it remains in the residue during episodes of partial fusion of the crust. Given a solubility limit of 0.14 wt% dissolved P₂O₅ (the mean of the experimental values) a source containing as little as 0.05% P₂O₅ must be 35% melted before apatite is lost from the residue and no longer buffers the melt P₂O₅ concentration at the saturation value. Higher abundances of P₂O₅ in the source postpone the loss of residual apatite to still higher degrees of melting, and if the source P₂O₅ content exceeds 0.14 wt%, apatite must be residual for all degrees of melting, increasing in abundance as melting proceeds.The generally secondary influence of apatite on the rare earth element (REE) patterns of melt and residue is most apparent when garnet and/or amphibole is minor or lacking in the residue. Fractional crystallization of intermediate (e.g. andesitic) magmas toward felsic compositions invariably results in saturation in apatite and some consequent depletion of REE in the melt.     

Experimental determination of the spinel peridotite to garnet peridotite inversion at 900° C and 1,000° C in the system CaO-MgO-Al2O3-SiO2, and at 900° C with natural garnet and olivine

Hydrothermal experiments were carried out at 2 kbar water pressure, 700 °–800 ° C, with the objective of determining the level of dissolved Zr required for precipitation of zircon from melts in the system SiO₂-Al₂O₃-Na₂O-K₂O. The saturation level depends strongly upon molar (Na₂O + K₂O)/Al₂O₃ of the melts, with remarkably little sensitivity to temperature, SiO₂ concentration, or melt Na₂O/ K₂O. For peraluminous melts and melts lying in the quartz-orthoclase-albite composition plane, less than 100 ppm Zr is required for zircon saturation. In peralkaline melts, however, zircon solubility shows pronounced, apparently linear, dependence upon (Na₂O + K₂O)/Al₂O₃, with the amount of dissolvable Zr ranging up to 3.9 wt.% at (Na₂O + K₂O)/Al₂O₃ = 2.0. Small amounts (1 wt.% each) of dissolved CaO and Fe₂O₃ cause a 25% relative reduction of zircon solubility in peralkaline melts.The main conclusion regarding zirconium/zircon behavior in nature is that any felsic, non-peralkaline magma is likely to contain zircon crystals, because the saturation level is so low for these compositions. Zircon fractionation, and its consequences to REE, Th, and Ta abundances must, therefore, be considered in modelling the evolution of these magmas. Partial melting in any region of the Earth's crust that contains more than 100 ppm Zr will produce granitic magmas whose Zr contents are buffered at constant low (< 100 ppm) values; unmelted zircon in the residual rock of such a melting event will impart to the residue a characteristic U- or V-shaped REE abundance pattern. In peralkaline, felsic magmas such as those that form pantellerites and comendites, extreme Zr (and REE, Ta) enrichment is possible because the feldspar fractionation that produces these magmas from non-peralkaline predecessors does not drive the melt toward saturation in zircon.Zircon solubility in felsic melts appears to be controlled by the formation of alkali-zirconosilicate complexes of simple (2:1) alkali oxide: ZrO₂ stoichiometry.     

Petrography and geochemistry of granitoid and metamorphite pebbles from the early Archaean Moodies Group,Barberton Mountainland/South Africa

Pebbles of potassic granitoids and metamorphites constitute up to 5% of the basal conglomerate of the Moodies Group in a ratio of 2 : 1. The granitoid pebbles frequently show micrographic quartz–feldspar intergrowth, whereas the metamorphites—of a modal composition similar to that of the granitoids—are characterized by large quartz grains which could represent original quartz phenocrysts in felsic volcanic precursors.The granitoids show high K₂O, Sr, K₂O/Na₂O, and K/Rb, small enrichment of light REE, large negative Eu-anomalies, and slightly depleted and fractionated heavy REE. Compared to the granitoids the metamorphites show higher Fe₂O₃, TiO₂, and Cr concentrations, greater enrichment of light REE, and also large negative Eu-anomalies.There is little similarity between the Moodies pebbles and the majority of the rocks of the Ancient Gneiss Complex of Swaziland (AGC). There is only some similarity of the REE distribution patterns between the pebbles and the Mkhondo Metamorphic Suite, possibly an areally restricted phase of the AGC. The geochemical data, and especially the large negative Eu-anomalies suggest that the Moodies pebbles were derived from granites which represent residual magmas from which much plagioclase had been removed. The granites crystallized at depths of < 7 km from magmas with low H₂O-pressures in a rather thick sialic crust. It appears possible that the pre-Moodies granitoids originated through partial melting of low-Al₂O₃ siliceous gneisses of the AGC. A chronologic connection of the formation of the granitoids with the late Onverwacht Group volcanicity is possible.     

Models of basalt petrogenesis: Lower Keweenawan diabase dikes and middle Keweenawan Portage Lake Lavas,upper Michigan

Lower Keweenawan diabase dikes from Marquette-Baraga Counties, and middle Keweenawan Portage Lake Lavas from upper Michigan, can each be subdivided into two chemically distinct groups: a low TiO₂-P₂O₅ group characterized by higher A1₂O₃ content, higher Mg ratio, and lower total Fe and REE abundances than a high TiO₂-P₂O₅ group. Both groups, which are indistinguishable in the field, are enriched in the LREE relative to the HREE, and have similar normalized REE abundance patterns.The systematic variation of the REE's within the subgroups is consistent with a model of fractional crystallization of the observed phenocryst phases, olivine and plagioclase. The unique TiO₂/P₂O₅ content of the subgroups cannot be explained by magma mixing or fractionation from a single primary liquid. Thus, two mantle sources of differing depth and REE abundance are required to produce the TiO₂-P₂O₅ subgroups which are intercalated in the lava pile. Similar chemical trends within the dikes have been interpreted to mean that the same magmatic processes must have been operative during their emplacement in the early opening stages of the Keweenawan rift in Michigan.     

The role of P2O5 in silicate melts

Phase equilibria data in the systems SiO₂-P₂O₅, P₂O₅-M_xO_y, and P₂O₅-M_xO_y-SiO₂ are employed in conjunction with Chromatographic and spectral data to investigate the role of P₂O₅ in silicate melts. Such data indicate that the behavior of P₂O₅ is complex. P₂O₅ depolymerizes pure SiO₂ melts by entering the network as a four-fold coordinated cation, but polymerizes melts in which an additional metal cation other than silicon is present. The effect of this polymerization is apparent in the widening of the granite-ferrobasalt two-liquid solvus. In this complex system P₂O₅ acts to increase phase separation by further enrichment of the high charge density cations Ti, Fe, Mg, Mn, Ca, in the ferrobasaltic liquid. P₂O₅ also produces an increase in the ferrobasalt-granite REE liquid distribution coefficients. These distribution coefficients are close to 4 in P₂O₅-free melts, but close to 15 in P₂O₅-bearing melts.The dual behavior of P₂O₅ is explained in a model which requires complexing of phosphate anions (analogous to silicate anions) and metal cations in the melt. This interaction destroys Si-O-M-O-Si bonds polymerizing the melt. The higher concentration of Si-O-M-O-Si bond complexes in immiscible ferrobasaltic liquids relative to their conjugate immiscible granite liquids explains the partitioning of P₂O₅ into the ferrobasaltic liquid.     

Implications of liquid-liquid distribution coefficients to mineral-liquid partitioning

The effect of silicate liquid structure upon mineral-liquid partitioning has been investigated by determining element partitioning data for coexisting immiscible granitic and ferrobasaltic magmas. The resulting elemental distribution patterns may be interpreted in terms of the relative states of polymerization of the coexisting magmas. Highly charged cations (REE, Ti, Fe, Mn, etc.) are enriched in the ferrobasaltic melt. The ferrobasaltic melt is relatively depolymerized due to its low $\text{Si}\text{O}$ ratio. This allows highly charged cations to obtain stable coordination polyhedra of oxygen within the ferrobasaltic melt. The granitic melt is a highly polymerized network structure in which Al can occupy tetrahedral sites in copolymerization with Si. The substitution of Al⁺³ for Si⁺⁴ produces a local charge imbalance in the granitic melt which is satisfied by a coupled substitution of alkalis, thus explaining the enrichment of low charge density cations, the alkalis, in the granitic melt. P₂O₅ increases the width of the solvus and, therefore, the values of the distribution coefficients of the trace elements. This effect is attributed to complexing of metal cations with PO₄^?3 groups in the ferrobasaltic melt.The values of ferrobasalt-granite liquid distribution coefficients are reflected in distribution coefficients for a mineral and melts of different compositions. The mineral-liquid distribution coefficient for a highly charged cation is greater for a mineral coexisting with a highly polymerized melt (granite) than it is for that same mineral and a depolymerized melt (ferrobasalt). The opposite is true for low charge density cations. Mineralliquid and liquid-liquid distribution coefficients determined for the REE's indicate that fractionated REE patterns are due to mineral selectivity and not the state of polymerization of the melt.     

Rare Earth Element Enrichment in Late Archean Manganese Deposits from the Iron Ore Group,East India

The major, trace and rare earth element (REE) composition of Late Archean manganese, ferromanganese and iron ores from the Iron Ore Group (IOG) in Orissa, east India, was examined. Manganese deposits, occurring above the iron formations of the IOG, display massive, rhythmically laminated or botryoidal textures. The ores are composed primarily of iron and manganese, and are low in other major and trace elements such as SiO₂, Al₂O₃, P₂O₅ and Zr. The total REE concentration is as high as 975 ppm in manganese ores, whereas concentrations as high as 345 ppm and 211 ppm are found in ferromanganese and iron ores, respectively. Heavy REE (HREE) enrichments, negative Ce anomalies and positive Eu anomalies were observed in post‐Archean average shale (PAAS)‐normalized REE patterns of the IOG manganese and ferromanganese ores. The stratiform or stratabound shapes of ore bodies within the shale horizon, and REE geochemistry, suggest that the manganese and ferromanganese ores of the IOG were formed by iron and/or manganese precipitation from a submarine, hydrothermal solution under oxic conditions that occurred as a result of mixing with oxic seawater. While HREE concentrations in the Late Archean manganese and ferromanganese ores in the IOG are slightly less than those of the Phanerozoic ferromanganese ores in Japan, HREE resources in the IOG manganese deposits appear to be two orders of magnitude higher because of the large size of the deposits. Although a reliable, economic concentration technique for HREE from manganese and ferromanganese ores has not yet been developed, those ores could be an important future source of HREE.     

Partial fusion of basic granulites at 5 to 15 kbar: implications for the origin of TTG magmas

Partial fusion experiments with basic granulites (S6, S37) believed to represent the lower crust beneath the Eifel region (Germany) were performed at pressures from 5 to 15 kbar. Water-undersaturated experiments were carried out in the presence of 1 wt% H₂O plus 2.44 or 0.81 wt% CO₂ equivalent to mole fractions of H₂O/(H₂O + CO₂) of 0.5 and 0.75, respectively, of the volatile components added. At temperatures from 850 to 1100 °C the weight proportions of melt range from 7 to 30 %. Melt compositions change from trondhjemitic over tonalitic to dioritic with increasing degree of partial melting. Crystalline residua are plagioclase/pyroxene dominated at 5 kbar to garnet/pyroxene dominated at 15␣kbar. Dehydration melting was studied in granulite S35 similar in composition to S6. The magmatic precursors of the granulite xenoliths used in this study had geochemical characteristics of cumulate gabbro (metagabbro S37) and evolved melts (metabasalts S6, S35), respectively. Melts from granulite S37 match the major element compositions of natural trondhjemites and tonalites. At 5 kbar, their Al₂O₃ is relatively low, similar to tonalites from ophiolites. At 15 kbar, Al₂O₃ in the melts is high due to the near absence of plagioclase in the crystalline residua. The Al₂O₃ concentrations in 15 kbar melts from S6 (˜20 wt%) are higher than in natural tonalites. Depth constraints on the formation of tonalitic magmas in the continental crust are provided by REE (rare earth element) patterns of the synthetic melts calculated from the known REE abundances in metagabbro S37 and metabasalt S6 assuming batch melting and using partition coefficients from the literature. The REE patterns of tonalites from active continental margins and Archean trondhjemite-tonalite-granodiorite␣associations low in REE with La_N (chondrite normalised) from 10 to 30 and Yb_N from 1 to 2 are reproduced at pressures of 10 and 12.5 kbar from metagabbro S37 which displays a slightly L(light)REE enriched pattern with La_N = 8 and Yb_N = 3. Natural tonalites with La_N from 30 to 100 require a source richer in REE than granulite S37. At 15 kbar, H(heavy)REE_N in melts from granulite S37 are depressed below the level observed in natural tonalites due to the high proportion of garnet (>30 wt%) in the residue. Melts from metabasalt S6 (enriched in REE with La_N = 38 and Yb_N = 16) do not match the REE characteristics of natural tonalites under any conditions. Received: 1 July 1994 / Accepted: 11 September 1996     

A comparative study of Pleistocene phosphorites from the continental slope off western India

Two types of phosphorite recovered from the continental slope off western India are described. The first type, phosphorite 1, comprises a hard, grey nodule composed of carbonate fluorapatite (CFA) and calcite as major minerals. The phosphorite consists of light‐brown microcrystalline apatite containing a few skeletal fragments and planktonic foraminifera. Scanning electron microscope (SEM) studies show evidence of dissolution of skeletal calcite and filling of the resulting cavities by phosphate composed of ovoid to rod‐shaped apatite microparticles. Apatite also occurs as coatings on these particles. The P₂O₅ content of the phosphorite is 29%, and the CO₂ content of the CFA is about 4·5%. The rare‐earth element (REE) abundance (ΣREE=2·02 μg g^–1) is lower than in other modern phosphorites. The ⁸⁷Sr/⁸⁶Sr ratio and ?Nd value of this sample are 0·70921 and –9·9 respectively. The ¹⁴C age found through accelerator mass spectrometry (AMS) dating (18 720 ± 120 years BP) is much younger than that determined by the U‐series method (100 ka). The second type, phosphorite 2, comprises a friable, light‐brown nodule consisting of CFA as the only major mineral, with a CO₂ content of the CFA of 4·5%. In thin section, the phosphate is light brown and homogeneous, and a few bone fragments are present. The P₂O₅ content is 33%, and REE contents (ΣREE = 0·18 μg g^–1) are lower than in phosphorite 1. The age of phosphorite 2 is >300 ka. Phosphorite 1 appears to have formed during the late Pleistocene through replacement of carbonate by phosphate; phosphorite 2 is also of Pleistocene age but is much older than phosphorite 1. The initial substrate for phosphorite 2 was a fish coprolite, which was subsequently phosphatized during slow sedimentation under low‐energy conditions. Microbial mediation is evident in both phosphorites. The colour, density and P₂O₅ content of the phosphorites are found to be dependent on the nature of the initial substrates and physico‐chemical conditions during phosphatization. The CO₂ content of the CFA is not related to the precursor carbonate phase. The nature of sediments, rates of sedimentation and the time spent undergoing phosphogenesis at the sediment–water interface may control REE concentrations in phosphorites.     

Geochemical comparison between Archaean and Proterozoic orthogneisses from the Nagssugtoqidian orogen,West Greenland

In the Palaeoproterozoic Nagssugtoqidian orogen of West Greenland reworked Archaean and juvenile Proterozoic orthogneisses occur side by side and are difficult to differentiate in the field. Archaean gneisses have tonalitic to trondhjemitic compositions with relatively low Al₂O₃ and Sr, and may have been derived from magmas formed by melting of basaltic or amphibolitic rocks at moderate pressures. The Proterozoic rocks are on average more mafic, and it is likely that they crystallised from mantle-derived magmas. Felsic varieties of the Proterozoic igneous suite probably formed from the original magma by fractional crystallisation, in which hornblende played an important role, and at SiO₂ > 65% Archaean and Proterozoic rocks have very similar major and trace element compositions (including REE), illustrating that different modes of origin may lead to very similar results.     

The behavior of chlorine and sulfur during differentiation of the Mt. Somma-Vesuvius magmatic system

Summary Reheated silicate melt inclusions in volcanic rock samples from Mt. Somma-Vesuvius, Italy, have been analyzed for 29 constituents including H₂O, S, Cl, F, B, and P₂O₅. This composite volcano consists of the older Mt. Somma caldera, formed between 14 and 3.55 ka before present, and the younger Vesuvius cone. The melt inclusion compositions provide important constraints on pre-eruptive magma geochemistry, identify relationships that relate to eruption behavior and magma evolution, and provide extensive evidence for magmatic fluid exsolution well before eruption. The melt inclusion data have been categorized by groups that reflect magma compositions, age, and style of eruptions. The data show distinct differences in composition for eruptive products older than 14.0 ka (pre-caldera rocks) versus eruptive products younger than 3.55 ka. Moreover, pre-caldera eruptions were associated with magmas relatively enriched in SiO₂, whereas eruptions younger than 3.55 ka (i.e., the syn- and post-caldera magmas which generated the Somma caldera and the Vesuvius cone) were derived from magmas comparatively enriched in S, Cl, CaO, MgO, P₂O₅, F, and many lithophile trace elements. Melt inclusion data indicate that eruptive behavior at Vesuvius correlates with pre-eruptive volatile enrichments. Most magmas associated with explosive plinian and subplinian events younger than 3.55 ka contained more H₂O, contained significantly more S, and exhibited higher (S/Cl) ratios than syn- and post-caldera magmas which erupted during relatively passive interplinian volcanic phenomena. Received January 10, 2000 Revised version accepted July 17, 2000     

The origin of island arc high-alumina basalts

A detailed examination of the hypothesis that high-alumina basalts (HAB) in island arcs are primary magmas derived by 50–60% partial melting of subducted ocean crust eclogite shows that this model is unlikely to be viable. Evidence suggests that the overwhelming majority of arc HAB are porphyritic lavas, enriched in Al₂O₃ either by protracted prior crystallization of olivine and clinopyroxene, or by plagioclase phenocryst accumulation in magmas of basaltic andesite to dacite composition. Experimentally-determined phase relationships of such plagioclase-enriched (non-liquid) compositions have little bearing on the petrogenesis of arc magmas, and do not rule out the possibility that arc HAB can be derived by fractionation of more primitive arc lavas. Although models invoking eclogite-melting can match typical arc HAB REE patterns, calculations indicate that the Ni and Cr contents of proposed Aleutian primary HAB are many times lower than such models predict. In contrast, Ni vs Sc and Cr vs Sc trends for arc HAB are readily explained by olivine (+Cr-sp) and clinopyroxene-dominated fractionation from more primitive arc magmas. GENMIX major element modelling of several HAB compositions as partial melts of MORB eclogite, using appropriate experimentally (26–34 kb)-determined garnet and omphacite compositions yields exceptionally poor matches, especially for CaO, Na₂O, MgO and Al₂O₃. These mismatches are easily explained if the HAB are plagioclase-accumulative. Groundmasses of arc HAB are shown to vary from basaltic andesite to dacite in composition. Crystal fractionation driving liquid compositions toward dacite involves important plagioclase separation, resulting in development of significant negative Eu anomalies in more evolved lavas. Plagioclase accumulation in such evolved liquids tends to diminish or eliminate negative Eu anomalies. Therefore, the absence of positive Eu anomaly in a plagioclase-phyric HAB does not indicate that plagioclase has not accumulated in that lava. In addition, we show that plagioclase phenocrysts in arc HAB are not in equilibrium with the liquids in which they were carried (groundmass). Exceptional volumes of picrite and olivine basalt occur in the Solomons and Vanuatu arcs; the presence in lavas from these and other arcs (Aleutian, Tonga) of olivine phenocrysts to Fo₉₄, finds no ready explanation in the primary eclogite-derived HAB model. We suggest that most lavas in intra-oceanic arcs are derived from parental magmas with >10% MgO; fractionation of olivine (+Cr-sp) and clinopyroxene drives liquids to basalt compositions with <7% MgO, but plagioclase nucleation is delayed by their low but significant (<1%?) H₂O contents. Thus evolved liquid compositions in the basaltic andesite—andesite range may achieve relatively high Al₂O₃ contents (<17.5%). The majority of arc basalts, however, have Al₂O₃ contents in excess of 18%, reflecting plagioclase accumulation. We give new experimental data to show that HAB liquids may be generated by anhydrous, low-degree (<10%) partial melting of peridotite at P<18 kb. Relative to arc HAB, these experimental melts have notably higher Mg#(69–72) and are in equilibrium with olivine Fo_87–89. Only further detailed trace element modelling will show if they might be parental magmas for some arc HAB.     

Mass transfer and REE mobility during fenitization at Alnö, Sweden

The Precambrian migmatitic gneisses at Alnö have been altered to fenite by fluids emanating from alkaline and carbonatitic magmas intruded during early to middle Cambrian times. Fenitization, related to carbonatitic sources, was promoted by peralkaline, carbonate-rich fluids, in which the main chemical components and REE were mobile. Composition-volume relationships of progressively fenitized protolith suggest mainly isovolumetric equilibration, but a modest decrease of volume (6%) did occur in the highest grade of the process. The fenitizing fluids introduced essentially CaO, CO₂, Na₂O, and K₂O while removing SiO₂ and Al₂O₃. Different trends of fenitization, defined as sodic, potassic and intermediate, show differing REE distribution and abundance patterns. The sodic carbonate-rich fluid introduced all the REE, but the La/Lu ratio was high. The extreme REE enrichments of high-grade fenites are associated with the widespread formation of calcite, apatite and possibly titanite. The potassic carbonaterich fluid introduced essentially light REE, but produced also the redistribution of heavy REE in the high-grade fenites. REE distribution patterns of intermediate fenites suggest the re-equilibration of fenite with a highly oxidizing alkaline fluorine-rich fluid, possibly in a later post-magmatic episode.     

湖南常宁县康家湾铅锌金矿硅化角砾岩岩石地球化学特征

湖南常宁县康家湾铅锌金矿床硅化角砾岩带由未硅化角砾岩—极弱硅化角砾岩—硅化角砾岩—强硅化角砾岩(似硅质岩)组成,产于侏罗系与下伏二叠系间的不整合面附近,角砾成份复杂,充填物和胶结物类型多样。随着硅化程度的加强,硅化角砾岩带SiO₂含量变化大,最高可达95.34%,而Al₂O₃、MgO、FeO、K₂O、Na₂O、CaO、CO₂和P₂O₅含量特别是MgO、CaO、CO₂和P₂O₅含量明显降低,且K₂O>Na₂O,TiO₂的含量显著偏低。硅化角砾岩带LREE/HREE比值为1.95～4.93,Ce(δCe=0.44～0.81)和Eu(δEu=0.58～0.89)均为弱负异常,属轻稀土富集型,但随硅化程度增高稀土元素含量显著减少:未硅化和弱硅化角砾岩稀土元素总量较高,为(176.82～318.93)×10^-10,与当冲组泥质岩配分曲线相似;硅化强烈的角砾岩稀土元素总量低,为(7.71～65.95)×10^-10,与下伏栖霞组灰岩稀土元素配分曲线极为相似。结合微量元素F、Ba、Cl、Cr、Ni、Sr、V研究结果及硅化角砾岩带自底部至顶部特有的下粗上细的韵律性层理构造,认为康家湾铅锌金矿床硅化角砾岩带是在地台体制向地洼体制转变期的大地构造环境下,由于地壳快速隆升,二叠纪灰岩、泥质岩、石英砂岩等岩石剥蚀,在古河流环境下搬运、沉积形成的。此     

Geochemical, mineralogical and isotopic signatures of the Semikan, West Kasrık “Turkish” phosphorites from the Derik–Mazıdağı–Mardin area, SE Anatolia

The geochemistry and mineralogy of a condensed section, ~6 m thick of the West Kasrik member (Coniacian–Santonian) near the uplifted northern flank of the Mardin–Derik anticline (south-eastern Turkey) was studied. The only deposit exploited in Turkey is found in this area. The sediment textures as well as the mineralogical and the geochemical results collectively suggest that these recycled phosphorites accumulated in areas of intensive very early diagenesis of the sediments in highly oxic bottom waters, and almost no detrital apport. The total concentration of redox-sensitive trace metals is very low (<600 μg/g); in addition the structural CO₂ and F/P₂O₅ are unusually high (~5 wt % and 0.14, respectively). REE distribution shows a clear “seawater” pattern with a strongly negative Ce-anomaly (0.20 ± 0.02) and heavy REE enrichment (Lu_N/La_N = 1.50 ± 0.12), however their total concentration is very low. The low REE contents, quite unexpected in recycled phosphorites, are explained by the scarcity of terrigenous components which leads to minimal incorporation of REEs from detrital clastic phases in the CFA fraction. Weathering previously suggested as responsible for the high P enrichment of the Mazidagi phosphorites is rather improbable in the samples we studied, in view of their high structural CO₂, high F/P₂O₅, high (La/Nd)_N and (La/Sm)_N ratios, and high Sr/P and Ca/P of separated CFA fractions that all negate post-depositional weathering. More likely, the high P enrichment of some rocks (P₂O₅ content reaches 34%) was produced by sedimentary and early diagenetic processes acting in oxygenated areas of starved sedimentation on and around tectonic highs.     

Behavior of REE Fractionation during Weathering of Dolomite Regolith Profile in Southwest China

<正>REE fractionation during the weathering of dolomite has been recognized for decades.A regolith profile on dolomite in southwest Yunnan of China was selected to investigate the behaviors of REE during weathering.The weathering of dolomite is divided into two stages:the pedogenesis stage and soil evolution stage,corresponding to the saprolites and soils respectively in the regolith profile. SiO_2,TiO_2,P_2O_5,Zr,Hf,Nb and Ta were immobile components during the weathering by and large, while Al_2O_3,K_2O and Fe_2O_3 were lost during the soil evolution stage in the physical form(clay minerals probably).REE were fractionated during the whole weathering of dolomite.The field weathering profile and the lab acid-leaching experiments on dolomite indicate that MREE were enriched clearly relative to other REE during the pedogenesis stage in a "capillary ascending-adsorption" mechanism, but they did not fractionate clearly in the soil evolution stage.REE were lost and accumulated in the weathering front of dolomite during the soil evolution stage in a "physical-chemical leaching" mechanism.     

The mineral chemistry of new titanates from the jagersfontein kimberlite,South Africa: Implications for metasomatism in the upper mantle

New members of the crichtonite mineral series are described in which K, Ba, Ca and REE are in significant concentrations (5 wt% oxides) filling the A formula position in AM₂₁O₃₈. These phases are chromium (16 wt% Cr₂O₃) titanates (58 wt% TiO₂) enriched in ZrO₂ (5 wt%) and constitute a mineral repository for refractory and large ion lithophile elements in the upper mantle. The mineral senes coexists with Mg-Cr-ilmenite, Nb-Cr-rutile, and Ca-Cr (NbZr) armalcolite that have equally unusual chemistries. Kimberlitic crichtonites are depleted in the intermediate lanthanides but highly enriched in LREE and HREE with chondrite normalized abundances of 10³ to 10⁵. Crichtonite, armalcolite, and Nb-Cr-rutile occupy a compositional range in TiO₂ contents bridging the gap between ilmenite and rutile, two minerals having a widespread distribution in kimberlites and mantle-derived nodule suites.In common with other associations, and based on similarities in mineral chemistry, it is concluded that these minerals formed at P = 20–30 kb, 900–1100°C by reaction of peridotite with metasomatizing fluids. Kimberlitic crichtonite may be expressed as spinel + Cr-ferropseudobrookite, and armalcolite is equivalent to Cr-geikielite + rutile in the system (FeMg)-TiO₂-Cr₂O₃. This system contains a number of Cr-Ti compounds not found as minerals but it is proposed that the ubiquitous occurrence of ilmenite intergrowths in kimberlitic rutile results from decomposition of high pressure αPbO₂-type crystallographic shear structures. The new minerals have exotic chemistries and the high K-affinities broaden the scope for the origin of alkalic rocks, the generation of highly potassic magmas in the upper mantle, and suggest that alkali metasomatism may be pervasive.     

Geochemical characteristics and geological significance of the Neoproterozoic carbonates from northern Anhui Province,China

Petrographical and geochemical studies were carried out of the Neoproterozoic carbonates from northern Anhui Province, China. These carbonates can be subdivided into two types, including purified limestone (PL) and mixed limestone and siliclastic rocks (MLS). PLs are low in Si, Al, Zr and total REE but high in CaO compared with MLSs. Correlations between Zr, Fe2O3, P2O5 and total REE are also less remarkable, indicating that they were not obviously contaminated by continental materials but directly precipitated from seawater. So they can be used for the inversion of paleo-seawater REE patterns. The inversed results indicated that the REE pattern of Neoproterozoic seawater was similar to that of the modern seawater except for the lack of Ce depletion, which was probably affected by the reduced hydrothermal solution. In combination with previous studies, the geochemical trending of these carbonatic samples towards the continental arc in the La- Th-Sc and Th-Sc-Zr/10 diagrams is interpreted as the contamination of arc volcanism. The tectonic background of the southern margin of the North China Craton in the Neoproterozoic was probably related to the Grenville orogeny during the convergence of the Rodinia supercontinent, rather than an intra-plate environment.     

贵州省松桃县道坨超大型锰矿床的发现及其成因探讨

贵州省松桃县道坨锰矿床是新发现的一个超大型全隐伏锰碳酸盐矿床。文章阐述了该矿床的发现概况及基本的地质和地球化学特征,并应用锰矿石和含锰黑色页岩的元素和碳同位素地球化学特征对菱锰矿的形成机制提出了制约。道坨超大型锰矿床的发现是填图及对区域地质资料综合分析的结果。该矿床具有品位高、厚度大、呈层性好及展布广等特点。其锰矿石的主量元素特征为Al2O3、TiO2、Fe2O3含量较低,P2O5中等程度富集,MnO、MgO含量相对较高,Fe/Mn比值低。在微量元素方面,锰矿石显示出较为明显的Co富集,含锰黑色页岩则显示出较为明显的Co、Mo富集;在稀土元素方面,锰矿石具有较高的稀土元素总量,轻微的"帽式"稀土元素PAAS标准化配分模式及明显的Ce正异常,含锰黑色页岩的稀土元素总量与PAAS接近,其稀土元素PAAS标准化配分模式较为平坦,无Ce异常。碳同位素测试结果显示出菱锰矿富集碳的轻同位素,表明在菱锰矿形成过程中存在有机碳的参与。文章表明,道坨锰矿床内的锰是以氧化物或氢氧化物的形式沉淀,菱锰矿是在缺氧且富含有机物质的成岩环境中转化而成。