The chemical composition of medieval wood ash glass from Central Europe     

Karl Hans Wedepohl  Klaus Simon 《Chemie der Erde / Geochemistry》2010,70(1):89-97

Medieval wood ash glass classified as 6 early medieval wood ash glasses, 17 wood ash glasses, 5 early wood ash lime glasses, 7 wood ash lime glasses and 9 mixed alkali glasses has been analyzed by microprobe and ICP-mass spectrometry on 61 elements. Their calcium oxide to potassium oxide ratio (CaO/K₂O) increases from early to late medieval glasses according to an increase of the proportion of twigs in the bulk amount of wood (logs plus twigs). Twigs because of their relatively large proportion of bark contain more calcium than wood logs. The ratio CaO/K₂O of the glasses from not yet evaluated excavations can be used for dating. The observation that the 25 minor elements Be, Sc, V, Cr, Ge, Y, Nb, REE (La to Lu), Ta, W and Bi occur in almost equal concentrations in the five subtypes of wood ash glass makes it highly probable that these elements were introduced into the starting mixtures of the glasses by means of quartz from quartz-rich sand with heavy minerals. The majorities of the wood ash glasses contain so-called europium anomalies within the group of rare-earth elements (REE). Their Eu concentrations normalized to those of the Continental Earth's Crust are lower than the normalized samarium and gadolinium concentrations. These Eu anomalies are apparently inherited from the granitic source of quartz in the upper Continental Earth's Crust. Soda ash and soda lime glass as the other major types in the history of glass contain no Eu anomaly. Therefore a different source of quartz has caused this important element constellation for these glass types. The elements K, Cu, Rb and S are physiologically separated from Ca, P, Mn, Sr and B during the growth of the wood and bark, respectively, in the trees. Different sources of the metals Cu and Co were used for colouring the glasses of our report.  相似文献   

Assessment of Nanosecond Laser Ablation Multi‐Collector Inductively Coupled Plasma‐Mass Spectrometry for Pb and Sr Isotopic Determination in Archaeological Glass: Mass Bias Correction Strategies and Results for Corning Glass Reference Materials          下载免费PDF全文

Alicia Van Ham‐Meert  Stepan M. Chernonozhkin  Stijn J.M. Van Malderen  Thibaut Van Acker  Frank Vanhaecke  Patrick Degryse 《Geostandards and Geoanalytical Research》2018,42(2):223-238

This work presents an evaluation of various methods for in situ high‐precision Sr and Pb isotopic determination in archaeological glass (containing 100–500 μg g^?1 target element) by nanosecond laser ablation multi‐collector‐inductively coupled plasma‐mass spectrometry (ns‐LA‐MC‐ICP‐MS). A set of four soda‐lime silicate glasses, Corning A–D, mimicking the composition of archaeological glass and produced by the Corning Museum of Glass (Corning, New York, USA), were investigated as candidates for matrix‐matched reference materials for use in the analysis of archaeological glass. Common geological reference materials with known isotopic compositions (USGS basalt glasses BHVO‐2G, GSE‐1G and NKT‐1G, soda‐lime silicate glass NIST SRM 610 and several archaeological glass samples with known Sr isotopic composition) were used to evaluate the ns‐LA‐MC‐ICP‐MS analytical procedures. When available, ns‐LA‐MC‐ICP‐MS results for the Corning glasses are reported. These were found to be in good agreement with results obtained via pneumatic nebulisation (pn) MC‐ICP‐MS after digestion of the glass matrix and target element isolation. The presence of potential spectral interference from doubly charged rare earth element (REE) ions affecting Sr isotopic determination was investigated by admixing Er and Yb aerosols by means of pneumatic nebulisation into the gas flow from the laser ablation system. It was shown that doubly charged REE ions affect the Sr isotope ratios, but that this could be circumvented by operating the instrument at higher mass resolution. Multiple strategies to correct for instrumental mass discrimination in ns‐LA‐MC‐ICP‐MS and the effects of relevant interferences were evaluated. Application of common glass reference materials with basaltic matrices for correction of ns‐LA‐MC‐ICP‐MS isotope data of archaeological glasses results in inaccurate Pb isotope ratios, rendering application of matrix‐matched reference materials indispensable. Correction for instrumental mass discrimination using the exponential law, with the application of Tl as an internal isotopic standard element introduced by pneumatic nebulisation and Corning D as bracketing isotopic calibrator, provided the most accurate results for Pb isotope ratio measurements in archaeological glass. Mass bias correction relying on the power law, combined with intra‐element internal correction, assuming a constant ⁸⁸Sr/⁸⁶Sr ratio, yielded the most accurate results for ⁸⁷Sr/⁸⁶Sr determination in archaeological glasses  相似文献   

Evolution of the trachydacite and pantellerite magmas of the bimodal volcanic association of Dzarta-Khuduk, Central Mongolia: Investigation of inclusions in minerals     

I. A. Andreeva  V. I. Kovalenko 《Petrology》2011,19(4):348-369

Using various methods of melt inclusion investigation, including electron and ion microprobe techniques, we estimated the composition, evolution, and formation conditions of melts producing the trachydacites and pantellerites of the Late Paleozoic bimodal volcanic association of Dzarta-Khuduk, Central Mongolia. Primary crystalline and melt inclusions were detected in anorthoclase from trachydacites and quartz from pantellerites and pantelleritic tuffs. Among the crystalline inclusions, we identified hedenbergite, fluorapatite, and pyrrhotite in the trachydacites and F-arfvedsonite, fluorite, ilmenite, and the rare REE diorthosilicate chevkinite in the pantellerites. Melt inclusions in anorthoclase from the trachydacites are composed of glass, a gas phase, and daughter minerals (F-arfvedsonite, fluorite, villiaumite, and anorthoclase rim on the inclusion wall). Melt inclusions in quartz from the pantellerites are composed of glass, a gas phase, and a fine-grained salt aggregate consisting of Li, Na, and Ca fluorides (griceite, villiaumite, and fluorite). Melt inclusions in quartz crystalloclasts from the pantelleritic tuffs are composed of homogeneous silicate glasses. The phenocrysts of the trachydacites and pantellerites crystallized at temperatures of 1060–1000°C. During thermometric experiments with quartz-hosted melt inclusions from the pantellerites, the formation of immiscible silicate and salt (fluoride) melts was observed at a temperature of 800°C. Homogeneous melt inclusions in anorthoclase from the trachydacites have both trachydacite and rhyolite compositions (wt %): 68–70 SiO₂, 12–13 Al₂O₃, 0.34–0.74 TiO₂, 5–7 FeO, 0.4–0.9 CaO, and 9–12 Na₂O + K₂O. The agpaitic index ranges from 0.92 to 1.24. The glasses of homogenized melt inclusions in quartz from the pantellerites and pantelleritic tuffs have rhyolitic compositions. Compared with the homogeneous glasses trapped in anorthoclase of the trachydacites, quartz-hosted inclusions from the pantellerites show higher SiO₂ (72–78 wt %) and lower Al₂O₃ contents (7.8–10.0 wt %). They also contain 0.14–0.26 wt % TiO₂, 2.5–4.9 wt % FeO, 9–11 wt % Na₂O + K₂O, and 0.9–0.15 wt % CaO and show an agpaitic index of 1.2–2.05. Homogeneous melt inclusions in quartz from the pantelleritic tuffs contain 69–72 wt % SiO₂. The contents of other major components, including TiO₂, Al₂O₃, FeO, and CaO, are close to those in the homogeneous glasses of quartzhosted melt inclusions in the pantellerites. The contents of Na₂O + K₂O are 4–10 wt %, and the agpaitic index is 1.0–1.6. The glasses of melt inclusions from each rock group show distinctive volatile compositions. The H₂O content is up to 0.08 wt % in anorthoclase of the trachydacites, 0.4–1.4 wt % in quartz of the pantellerites, and up to 5 wt % in quartz of the pantelleritic tuffs. The content of F in the glasses of melt inclusions in the phenocrysts of the trachydacites is no higher than 0.67 wt %, and up to 1.4–2.8 wt % in quartz from the pantellerites. The Cl content is up to 0.2 wt % in the glasses of melt inclusions in the minerals of the trachydacites and up to 0.5 wt % in the glasses of quartz-hosted melt inclusions from the pantellerites. The investigation of trace elements in the homogenized glasses of melt inclusions in minerals showed that the trachydacites and pantellerites were formed from strongly evolved rare-metal alkaline silicate melts with high contents of Li, Zr, Rb, Y, Hf, Th, U, and REE. The analysis of the composition of homogeneous melt inclusions in the minerals of the above rocks allowed us to distinguish magmatic processes resulting in the enrichment of these rocks in trace and rare earth elements. The most important processes are the crystallization differentiation and immiscible separation of silicate and fluoride salt melts. It was also shown that all the melts studied evolved in spatially separated magma chambers. This caused the differences in the character of melt evolution between the trachydacites and pantellerites. During the final stages of differentiation, when the magmatic system was saturated with respect to ore elements, Na-Ca fluoride melts were separated and extracted considerable amounts of Li.  相似文献   

Genesis and mechanisms of formation of rare-metal peralkaline granites of the Khaldzan Buregtey massif,Mongolia: Evidence from melt inclusions     

I. A. Andreeva 《Petrology》2016,24(5):462-476

Melt inclusions were studied by various methods, including electron and ion microprobe analysis, to determine the compositions of melts and mechanisms of formation of rare-metal peralkaline granites of the Khaldzan Buregtey massif in Mongolia. Primary crystalline and coexisting melt inclusions were found in quartz from the rare-metal granites of intrusive phase V. Among the crystalline inclusions, we identified potassium feldspar, albite, tuhualite, titanite, fluorite, and diverse rare-metal phases, including minerals of zirconium (zircon and gittinsite), niobium (pyrochlore), and rare earth elements (parisite). The observed crystalline inclusions reproduce almost the whole suite of major and accessory minerals of the rare-metal granites, which supports the possibility of their crystallization from a magmatic melt. Melt inclusions in quartz from these rocks are completely crystallized. Their daughter mineral assemblage includes quartz, microcline, aegirine, arfvedsonite, polylithionite, a zirconosilicate, pyrochlore, and a rare-earth fluorocarbonate. The melt inclusions were homogenized in an internally heated gas vessel at a temperature of 850°C and a pressure of 3 kbar. After the experiments, many inclusions were homogeneous and consisted of silicate glass. In addition to silicate glass, some inclusions contained tiny quench zircon crystals confined to the boundary of inclusions, which indicates that the melts were saturated in zircon. In a few inclusions, glass coexisted with a CO₂ phase. This allowed us to estimate the content of CO₂ in the inclusion as 1.5 wt %. The composition of glasses from the homogeneous melt inclusions is similar to the composition of the rare-metal granites, in particular, with respect to SiO₂ (68–74 wt %), TiO₂ (0.5–0.9 wt %), FeO (2.2–4.6 wt %), MgO (0.02 wt %), and Na₂O + K₂O (up to 8.5 wt %). On the other hand, the glasses of melt inclusions appeared to be strongly depleted compared with the rocks in CaO (0.22 and 4 wt %, respectively) and Al₂O₃ (5.5–7.0 and 9.6 wt %, respectively). The agpaitic index is 1.1–1.7. The melts contain up to 3 wt % H₂O and 2–4 wt % F. The trace element analysis of glasses from homogenized melt inclusions in quartz showed that the rare-metal granites were formed from extensively evolved rare-metal alkaline melts with high contents of Zr, Nb, Th, U, Ta, Hf, Rb, Pb, Y, and REE, which reflects the metallogenic signature of the Khaldzan Buregtey deposit. The development of unique rare metal Zr–Nb–REE mineralization in these rocks is related to the prolonged crystallization differentiation of melts and assimilation of enclosing carbonate rocks.  相似文献   

Standard chemical‐based tephra extraction methods significantly alter the geochemistry of volcanic glass shards     

Claire L. Cooper  Ivan P. Savov  Graeme T. Swindles 《第四纪科学杂志》2019,34(8):697-707

The chemical compositions of tephra shards are widely utilised in a myriad of disciplines, including volcanology, petrology, tephrochronology, palaeoecology and climate studies. Previous research has raised concerns over the possible chemical alteration of microscopic (<100 µm) volcanic glass shards through standard extraction procedures, such as the widely used acid digestion method. This study subjects 10 samples of well‐characterised volcanic glasses ranging from basalt to rhyolite to three common methods used in the extraction of volcanic material from lake sediments and peats. The major element geochemistry of each sample was analysed and compared with a control group. The results of this test indicate that basaltic and andesitic glasses are highly susceptible to chemical alteration, particularly to the concentrated corrosive materials used in acid and base digestion techniques. PERMANOVA analysis of the variation within groups suggests that the oxides most susceptible to variation are alkalis from groups I and II (K₂O, Na₂O, CaO, MgO) and SiO₂, and the most stable oxides are Al₂O₃ and FeO. Felsic glasses are considerably less susceptible to alteration by both acidic (HCl, HNO₃, H₂SO₄) and alkaline (KOH) digestions. Our findings have important implications for interpreting the geochemistry of volcanic glasses. Copyright © 2019 John Wiley & Sons, Ltd.  相似文献   

Transition from I‐type to A‐type magmatism in the Sanandaj–Sirjan Zone,NW Iran: an extensional intra‐continental arc     

Fatemeh Sarjoughian  Ali Kananian  Michael Haschke  Jamshid Ahmadian 《Geological Journal》2016,51(3):387-404

The South Dehgolan pluton, in NW Iran was emplaced into the Sanandaj–Sirjan magmatic–metamorphic zone. This composite intrusion comprises three main groups: (1) monzogabbro–monzodiorite rocks, (2) quartz monzonite–syenite rocks, and (3) a granite suite which crops out in most of the area. The granites generally show high SiO₂ content from 72.1%–77.6 wt.% with diagnostic mineralogy consisting of biotite and amphibole along the boundaries of feldspar–quartz crystals which implies anhydrous primary magma compositions. The granite suite is metaluminous and distinguished by high FeOt/MgO ratios (av. 9.6 wt.%), typical of ferroan compositions with a pronounced A‐type affinity with high Na₂O + K₂O contents, high Ga/Al ratios, enrichment in Zr, Nb, REE, and depletion in Eu. The quartz monzonite–syenites show intermediate SiO₂ levels (59.8%–64.5 wt.%) with metaluminous, magnesian to ferroan characteristics, intermediate Na₂O + K₂O contents, enrichment in Zr, Nb, REE, Ga/Al, and depletion in Eu. The monzogabbro–monzodiorites show overall lower SiO₂ content (48.5%–55.9 wt.%) with metaluminous and calc‐alkaline compositions, relatively lower Na₂O + K₂O contents, low Ga/Al ratios, and FeOt/MgO (av. 1.6 wt.%) ratios, low abundances of Zr, Nb, and lower REE element concentrations relative to the granites and quartz monzonite–syenites. These geochemical differences among the three different rocks suites are likely to indicate different melt origins. We suggest that the South Dehgolan pluton resulted from a change in the geodynamic regime, from compression to extension in the Sanandaj–Sirjan zone during Mesozoic subduction of the Neo‐Tethys oceanic crust beneath the Central Iranian microcontinent. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

Phosphate: a neglected argument in studies of ancient glass technology     

Willem B. Stern 《Swiss Journal of Geoscience》2017,110(3):725-740

The phosphate content of ancient alkali-glass has been tested as an indicator for biogenic ash, used in glass production. The living tissue of plants and vertebrates accumulates phosphate that remains in native ash as a main component (1 to over 10 wt%) forming together with biologically essential element oxides a complex chemical fingerprint that characterises any glass made with it. If, instead of native plant ash its alkali extract is used, soluble oxides are concentrated in the extract whilst insoluble oxides get depleted, leading to a different elemental fingerprint of the glass. Geogenic raw-materials for glass production like quartz-rich sand, evaporitic natron, or limestone are virtually phosphate free (below detection limit up to ≈0.15 wt%). Several collections of ancient glass stemming from different archaeological excavations, regions and times have been analysed by instrumental methods (WD-XFA, ED-XFA, thermal techniques), i.e. flat- and hollow K–Ca glass dated 1699/1714 N = 340, Na–Ca glass 13th/14th cy N = 94, Na–Ca glass 7th/9th cy N = 110, and alkali-Ca glass La Tène N = 395. Although the phosphate content of native alkali plant ash gets diluted with quartz sand by a factor of roughly two in glass production, it remains a main component of the product glass. Wood-ash glass contains 1–3 wt% phosphate, whilst glass manufactured from halophyte ash contains around 0.2–1 wt%. When processed wood-ash is used, the phosphate content in glass sinks below 1 wt%, the depletion factor amounting to roughly 8–15. Glass made from evaporitic soda displays phosphate contents below 0.2 wt% in the cases examined. The phosphate content of ancient alkali glass thus indicates whether virtually phosphate-free evaporitic soda has been used as a flux, or native ash of halophile plants. Ternary melting diagrams reveal at least three groups of alkali glass: Naturally coloured forest glass displays a broad distributional pattern with minimum melting temperatures ranging from 1200 to ≥1450 °C, colourless potash-extract glass from 900 to ≈1200 °C, and the typical, tight cluster of Roman sodium-calcium glass ranges from 800 to ≈900 °C. The wide-spread sodium-lime glass made with native halophytic ash, contains besides Na₂O as the chemical main component always some K₂O, and melting temperatures range from 800 to ≈1000 °C.  相似文献   

Chemical characteristics (REE,etc.) of Paleozoic and Mesozoic graywackes and sandstones from Central Europe     

Karl?Hans?Wedepohl  Klaus?SimonEmail author 《Contributions to Mineralogy and Petrology》2012,164(4):693-696

During the Variscan orogeny in Central Europe, partial melting in the lower continental crust formed granitic magmas, which intruded into the upper crust and left compounds of Ca (plus Eu²⁺), Mg, etc. in the lower crust. From the late Paleozoic decomposition of the tonalitic upper crust, sedimentary graywackes were produced reflecting the composition of this crust. The repeated reworking of the sedimentary cover caused the formation of sands. Sandstones as their products of consolidation contain increasing fractions of quartz and decreasing feldspar from Carboniferous and Triassic to Cretaceous age. A distinct negative Eu anomaly characterizes the majority of these rocks. The latter is imprinted by the Variscan magmatism. Quartz as used for numerous Medieval wood ash glasses is marked for its Central European origin by a distinct negative Eu anomaly in contrast to many soda glasses produced outside Germany mostly with a small or none Eu anomaly.  相似文献   

Alteration of basaltic glass: Mechanisms and significance for the oceanic crust-seawater budget   总被引：1，自引：0，他引：1  

Hubert Staudigel  Stanley R. Hart 《Geochimica et cosmochimica acta》1983,47(3):337-350

Alteration of basaltic glass to palagonite is characterized by a nearly isomolar exchange of SiO₂, Al₂O₃, MnO, MgO, CaO, Na₂O, P₂O₅, Zn, Cu, Ni, Cr, Hf, Sc, Co and REE for H₂O and K₂O, whilst TiO₂ and FeO are passively accumulated during removal of the remaining cations. The network forming cations Al and Si are removed from the glass in proportion to the gain in Ti and Fe, whilst the other cations do not show a significant relationship to the amount of Ti and Fe accumulation. Sr isotopic data show that during palagonite formation approximately 85% of the basaltic Sr is lost to the hydrous solutions and 40% of seawater Sr is added to the glass, yielding an average loss of the same order of magnitude as of the network forming cations. Losses and gains of oxides yield an average increase of +105% TiO₂.K, Rb, and Cs show high increases, but $\text{K}\text{Rb}$ and $\text{K}\text{Cs}$ ratios indicate two different alteration processes: (1) formation of palagonite involves a drastic decrease in these ratios, indicating structural similarities between palagonite and smectite; (2) surface alteration of glass is characterized by an increase in $\text{K}\text{Rb}$ and $\text{K}\text{Cs}$ ratios, probably best interpreted as sorption of alkalies in ratios approximating those of seawater.The total fluxes involved in alteration of glass in the upper portion of the oceanic crust are estimated from the modal abundance of palagonite in the oceanic crust and the abundance of the vein materials smectite and carbonate. Smectite and carbonates act as a sink for a significant portion of the elements liberated up during alteration of basaltic glass except for Na and Al, which are probably taken up by zeolites and/or albite, possibly hidden in the macroscopic estimate of carbonate. Formation of the observed quantity of secondary phases requires additional sources for Si, Fe. Ca and K. K is provided in excess from the inflowing seawater at reasonable water/rock ratios. The remaining excess Ca, Si and Fe required may be derived by alteration of interstitial glass and breakdown of anorthite rich plagioclase and titano-magnetite, and/or by supply of deeper seated metamorphic reactions.  相似文献   

Evidence of deep fluid explosions in products of the Bityuk-Tyube independent eruption center (Western Cis-Elbrus Region)     

N. V. Koronovskii  L. I. Demina  M. Yu. Promyslova  M. S. Myshenkova 《Moscow University Geology Bulletin》2013,68(2):61-71

Four glass types, which sharply differ in terms of their silica content and the K₂O/Na₂O ratio are found in the earliest eruption products of the Bityuk-Tyube independent eruption center in the Western Cis-Elbrus Region. In addition to this, two monomineral glasses, which are close to monomineral plagioclase and quartz types, are identified. Such a composition of initial melts was produced by deep fluid explosions. It is shown that deep fluid explosions, on the one hand, initiate substrate melting and, on the other hand, prepare and develop channels for the further eruption of igneous material.  相似文献   

Compositions of early Islamic glass along the Iranian Silk Road     

《Chemie der Erde / Geochemistry》2022,82(4):125903

The composition of archaeological glass reflects the geochemical nature of its raw materials. To determine the origins and distribution of early Islamic glasses from Iran, a set of 169 glass samples from five different sites was analysed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of 58 elements. The glasses were classified into six different plant ash glass groups, three of which were attributed to a Mesopotamian origin, while three further groups are presumed to represent regional Iranian productions. The ratios of MgO/CaO and K₂O/P₂O₅ of the different groups reflect variations in the plant ash component. Minor elements Cr, Ti, Zr, La and Th and their ratios proved effective in distinguishing the base glass types. Mapping their frequency across the Iranian plateau revealed the relative movement of glass and likely source areas. The decline in the frequency of glass types with elevated Cr/La ratios east of the Zagros Mountain range confirms that elevated Cr/La ratios together with an augmentation of the magnesium levels are features of Mesopotamian glass production apparently inherited from the geochemical environment of the Euphrates and Tigris river valleys. Some exceptionally clean Mesopotamian glasses made from a quartz-rich silica with low levels of accessory minerals are consistent with ninth-century glass from Samarra, which was evidently traded widely along the Silk Road network. No evidence of local glass production was detected in Nishapur. The Iranian groups were produced from a quartz-rich silica source, high in thorium but with different zirconium contents resulting in different Th/Zr ratios. Aluminium concentrations tend to increase from west to east, with the highest values found among glass assemblages from Central Asia.  相似文献   

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

Thomas O. Reimer  Kent C. Condie  Gabriele Schneider  Angelika Georgi 《Precambrian Research》1985,29(4):383-404

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.  相似文献   

Effects of the degree of polymerization on the structure of sodium silicate and aluminosilicate glasses and melts: An O NMR study     

Sung Keun Lee  Jonathan F. Stebbins 《Geochimica et cosmochimica acta》2009,73(4):1109-2191

Revealing the atomic structure and disorder in oxide glasses, including sodium silicates and aluminosilicates, with varying degrees of polymerization, is a challenging problem in high-temperature geochemistry as well as glass science. Here, we report ¹⁷O MAS and 3QMAS NMR spectra for binary sodium silicate and ternary sodium aluminosilicate glasses with varying degrees of polymerization (Na₂O/SiO₂ ratio and Na₂O/Al₂O₃ ratio), revealing in detail the extent of disorder (network connectivity and topological disorder) and variations of NMR parameters with the glass composition. In binary sodium silicate glasses [Na₂O-k(SiO₂)], the fraction of non-bridging oxygens (NBOs, Na-O-Si) increases with the Na₂O/SiO₂ ratio (k), as predicted from the composition. The ¹⁷O isotropic chemical shifts (¹⁷O δ_iso) for both bridging oxygen (BO) and NBO increase by about 10-15 ppm with the SiO₂ content (for k = 1-3). The quadrupolar coupling products of BOs and NBOs also increase with the SiO₂ content. These trends suggest that both NBOs and BOs strongly interact with Na; therefore, the Na distributions around BOs and NBOs are likely to be relatively homogenous for the glass compositions studied here, placing some qualitative limits on the extent of segregation of alkali channels from silica-enriched regions as suggested by modified random-network models. The peak width (in the isotropic dimension) and thus bond angle and length distributions of Si-O-Si and Na-O-Si increase with the SiO₂ content, indicating an increase in the topological disorder with the degree of polymerization. In the ternary aluminosilicate glasses [Na₂O]_x[Al₂O₃]_1−xSiO₂, the NBO fraction decreases while the Al-O-Si and Al-O-Al fractions apparently increase with increasing Al₂O₃ content. The variation of oxygen cluster populations suggests that deviation from “Al avoidance” is more apparent near the charge-balanced join (Na/Al = 1). The Si-O-Si fraction, which is closely related to the activity coefficient of silica, would decrease with increasing Al₂O₃ content at a constant mole fraction of SiO₂. Therefore, the activity of silica may decrease from depolymerized binary silicates to fully polymerized sodium aluminosilicate glasses at a constant mole fraction of SiO₂.  相似文献   

Composition of Li-F granite melt and its evolution during the formation of the ore-bearing Orlovka massif in Eastern Transbaikalia     

E. V. Badanina  L. F. Syritso  E. V. Volkova  R. Thomas  R. B. Trumbull 《Petrology》2010,18(2):131-157

By the example of the Orlovka massif of Li-F granites in Eastern Transbaikalia, the major- and trace-element (Li, Be, B, Ta, Nb, W, REE, Y, Zr, and Hf) compositions of the parental melt and the character of its variations during the formation of the differentiated rock series were quantitatively estimated for the first time on the basis of electron and ion microprobe analysis and Raman spectroscopy of rehomogenized glasses of melt inclusions in quartz. It was shown that the composition of the Orlovka melt corresponded to a strongly evolved alumina-saturated granitoid magma (A/CNK = 1.12–1.55) rich in normative albite, poor in normative quartz, and similar to ongonite melts. This magma was strongly enriched in water (up to 9.9 ± 1.1 wt %) and fluorine (up to 2.8 wt %). Most importantly, this massif provided the first evidence for high B₂O₃ contents in melts (up to 2.09 wt %). The highest contents of trace elements were observed in the melt from pegmatoid bodies in the amazonite granites of the border zone: up to 5077 ppm Li, 6397 ppm Rb, 313 ppm Cs, 62 ppm Ta, 116 ppm Nb, and 62 ppm W. Compared with the daughter rock, the Orlovka melt was depleted at all stages of formation in SiO₂ (by up to 6 wt %), Na₂O (by up to 2.5 wt %), and, to a smaller extent, in Ti, Fe, Mg, Sr, and Ba, but was enriched in Mn, Rb, F, B, and H₂O.  相似文献   

Chemical analyses of Bosumtwi crater target rocks compared with the Ivory Coast tektites     

W.B Jones 《Geochimica et cosmochimica acta》1985,49(12):2569-2576

The Bosumtwi crater, Ghana, was excavated in phyllites and greywackes with subordinate microgranite dykes and quartz veins of the 2000 Ma old Lower Birimian System with a granodiorite intrusion at Pepiakese on its northeastern side. New major and trace element analyses are presented for 7 phyllites, 5 greywackes, 2 microgranites, 3 Pepiakese intrusion rocks and 1 suevite using XRF and INNA.Means and standard deviations were calculated using all available modern analyses for each element in the Bosumtwi target rocks, Bosumtwi suevite glasses and Ivory Coast tektites. Good agreements between the means were found for the three groups with the suevite glasses and tektites having more limited compositional ranges than the target rocks. Least squares mixing between target rock types shows that the best fits to the tektite and suevite glass compositions require components of about a third or a quarter from the Pepiakese intrusion and some extra silica, derived from quartz veins, as well as the metasediments.The new data provide evidence for vapour phase fractionation of P₂O₅ and Na₂O in the tektites in addition to the previously reported Pb and Rb. Evidence for a meteoritic component in the tektites was found to be equivocal since the target rocks are probably a sufficient source of the meteorite indicator elements Ni and Ir.  相似文献   

A study on the preparation of fine and low soda alumina     

Yi Yong Park  Suong Oh Lee  Tam Tran  Seong Jun Kim  Myong Jun Kim   《International Journal of Mineral Processing》2006,80(2-4):126-132

A simple process to produce fine and low soda α-alumina (α-Al₂O₃) from a commercial grade aluminium trihydroxide (gibbsite, Al(OH)₃) produced by KC Corporation Ltd was developed. There are two options for this process with the first one producing low soda α-alumina (< 0.05% Na₂O) having a mean particle size of 50 μm. The second option yields a fine product with a mean size of less than 10 μm. In the first option, a plant aluminium trihydroxide containing 0.20% Na₂O was first fluidized with nitrogen at 400–600 °C to yield an amorphous activated alumina. This intermediate product was then treated with acetic or oxalic acid, washed with water and heated to 1200 °C to form calcined α-alumina, having a Na₂O content of less than 0.05%. A 20 min leaching using 0.2 M acetic or oxalic acid could yield an alumina product containing 0.04% Na₂O. In the second option, a new technique for the preparation of fine and low soda α-alumina was evaluated using an attrition mill working also as a leaching vessel at 80 °C. Fine (< 10 μm in mean particle size) and low soda (< 0.04% Na₂O) alumina was produced by a 20 min leaching step with 0.2 M acetic acid and concurrent attrition milling.  相似文献   

东天山寨北山铜矿区钠质火山岩年代学、地球化学特征及其成因   总被引：2，自引：1，他引：1       下载免费PDF全文

孙志远  龙灵利  王玉往  罗照华  赵路通  解洪晶 《中国地质》2018,45(5):943-962

寨北山矿区海相火山岩为一套富钠的玄武安山玢岩、安山岩、英安岩、流纹岩组合,属于钙碱性系列岩石,具有低MgO（0.51%~5.93%,平均2.54%）、FeO（0.54%~6.39%,平均2.84%）和钛（TiO₂=0.09%~1.10%,平均0.58%）,富铝（Al₂O₃=12.23%~17.75%,平均15.20%,A/CNK=0.79~1.42,平均1.11）以及富钠（Na₂O/K₂O平均为7.30）、富水的特征。火山岩中斜长石主要为钠长石,少量更长石。轻、重稀土分馏较明显（（LREE/HREE）_N=3.68~9.00）,微量元素显示大离子亲石元素（如Th、U、Rb）、轻稀土的富集和高场强元素（如Nb、Ta、Ti、P）相对亏损的特征。获得矿区雅满苏组钠质玄武安山玢岩SHRIMP锆石U-Pb谐和年龄为（337.6±3.3）Ma,为早石炭世火山活动的产物。火山岩岩石学及地球化学特征表明研究区钠质火山岩可能形成于俯冲带近大陆方向的岛弧构造环境,是早石炭世洋壳俯冲熔融产生的岩浆在海底喷发过程中与海水相互反应后,经低变质相作用产生的。成矿元素在钠长石化过程中可能被淋滤出来进入含矿热液,后期在适当的温压等条件下沉淀形成本区的矿床。  相似文献   

Provenance and Tectonic Setting of the Metasedimentary Rocks of the Neoproterozoic Adola Belt of Southern Ethiopia     

Bisrat Yibas   《Gondwana Research》1999,2(3):377

The Metasedimentary rocks from the Adola metamorphic belt has been analysed for major, minor, and trace elements, including REEs, in order to investigate the provenance and tectonic setting of these rocks.On the basis of filed work, petrographic data and major element geochemistry the Adola sedimentary rocks are essentially greywackes with subordinate lithic arenite. Among the 27 samples analysed, only two samples are quartz arenite with SiO₂ values above 89%. CaO-Na₂O-K₂O diagrams showed that most sample cluster around the average plots of granites and granodiorites. In order to determine the tectonic setting and provenance of the rocks, the samples are plotted on various binary and ternary diagrams. The plots on Fe₂O₃T+MgO versus TiO₂, K₂O/Na₂O, Al₂O₃/SiO₂ and Al₂O₃/(CaO+Na₂O) plots show that the Adola sediments have Oceanic Island Arc(OIC), Continental Island Arc(CIA), Active Continental Margin(ACM) and Passive Margin(PM) characteristics. Most samples, however, show island arc affinity. Only two samples (the quartz arenites) fall in the Passive Margin (PM) field.The trace element characteristics of these rocks discriminate the rocks only into oceanic and continental arc fields. The relatively high abundance of the transition metals, mainly Co, Ni, Cr and the low concentration of TiO₂ correlates well with the previously determined geochemical affinity of the basic rocks of Adola suggesting the dominance of the low- Ti oceanic tholeiites and even boninites in the source region.The REE patterns show three distinct groupings; a)With strong LREE enrichment, flat HREE and with out Eu anomaly, shows similar patterns with that of the oceanic island arc rocks; b) samples with strong Light REE enrichment, flat HREE pattern and strong negative Eu anomaly showing similar patterns to the Andean type andesites, probably derived from granitic gneisses and are affiliated to Active Continental Margin settings; c) this group is represented by a single plot having an enriched LREE pattern, flat HREE pattern and strong positive Eu anomaly. It is most likely that this pattern is related to a high normative plagioclase content due to local accumulation of feldspar during sedimentation rather than representing excessive Eu content of the precursor rock. The REE pattern represented by this sample is roughly similar to that of the Devonian greywackes of Australia.In conclusion, the use of geochemical characteristics of the sediments coupled with the geological information from the area strengthens the suprasubduction zone (SSZ) ophiolitic tectonic setting interpretation suggested (Yibas 1993) for the Adola belt. The trace element plots and their absolute abundance, and the REE patterns strongly constrain the tectonic setting and the provenance of the metasediments to an arc related setting.  相似文献   

Petrochemistry and petrology of I-type granitoids in an arc setting: the composite Torul pluton, Eastern Pontides, NE Turkey   总被引：3，自引：0，他引：3  

Abdullah Kaygusuz  Wolfgang Siebel  Cüneyt Şen  Muharrem Satir 《International Journal of Earth Sciences》2008,97(4):739-764

The Upper Cretaceous Torul pluton, located in the Eastern Pontides, is of sub-alkaline affinity and displays features typical of volcanic arc granitoids. It is a composite pluton consisting of granodiorite, biotite hornblende monzogranite, quartz monzodiorite, quartz monzonite and hornblende biotite monzogranite. The oldest syenogranite (77.9 ± 0.3 Ma) and the youngest quartz diorite form small stocks within the pluton. Samples from the granodiorites, biotite hornblende monzogranites, quartz monzodiorites, quartz monzonites and hornblende biotite monzogranites have SiO₂ between 57 and 68 wt% and display high-K calc-alkaline, metaluminous to peraluminous characteristics. Chondrite-normalized REE patterns are fractionated (La_cn/Lu_cn = 6.0?14.2) with pronounced negative Eu anomalies (Eu/Eu* = 0.59–0.84). Initial ?_Nd(i) values vary between ?3.1 and ?4.1, initial ⁸⁷Sr/⁸⁶Sr values between 0.7058 and 0.7072, and δ¹⁸O values between +4.4 and +7.3‰. The quartz diorites are characterized by relatively high Mg-number of 36–38, low contents of Na₂O (2.3–2.5 wt%) and SiO₂ (52–55 wt%) and medium-K calc-alkaline, metaluminous composition. Chondrite-normalized REE patterns are relatively flat [(La/Yb)_cn =  2.8–3.3; (Tb/Yb)_cn =  1.2] and show small negative Eu anomalies (Eu/Eu* = 0.74–0.76). Compared to the other rock types, radiogenic isotope signatures of the quartz diorites show higher ⁸⁷Sr/⁸⁶Sr (0.7075–0.7079) and lower ?_Nd(i) (–4.5 to –5.3). The syenogranites have high SiO₂ (70–74 wt%) and display high-K calc-alkaline, peraluminous characteristics. Their REE patterns are characterized by higher La_cn/Lu_cn (12.9) and Eu/Eu* (0.76–0.77) values compared to the quartz diorites. Isotopic signatures of these rocks [?_Nd(i) =  ?4.0 to ?3.3; ⁸⁷Sr/⁸⁶Sr_(i) =  0.7034?0.7060; δ¹⁸ O =  + 4.9 to + 8.2] are largely similar to the other rock types but differ from that of the quartz diorites. Fractionation of plagioclase, hornblende, pyroxene and Fe–Ti oxides played an important role in the evolution of Torul granitoids. The crystallization temperatures of the melts ranged from 800 to 900°C as determined from zircon and apatite saturation thermometry. All these characteristics, combined with low K₂O/Na₂O, low Al₂O₃/(FeO_T + MgO + TiO₂), and low (Na₂O + K₂O)/(FeO_T + MgO + TiO₂) ratios suggest an origin through dehydration melting of mafic lower crustal source rocks.  相似文献   

Geochemistry and evolution of the South Platte granite-pegmatite system,Jefferson County,Colorado     

《Geochimica et cosmochimica acta》1987,51(3):455-471

The South Platte pegmatite district is well known for its significant enrichment in the rare earth elements (REE), Y, Nb, F, and for the exceptionally well-developed internal zonation of the complex pegmatites located within a reversely zoned portion of the Pikes Peak batholith. Chemical trends both within and between pegmatites define the behavior of major and trace elements and the role of F in the fractionation of the granitic magma and pegmatitic fluids, suggesting a new model for the evolution of the granite-pegmatite system.Whole-rock XRF and INAA analyses of the host Pikes Peak granite and quartz monzonite and pegmatite wall zones provide strong evidence that all three are related by differentiation. With increasing SiO₂, there is systematic enrichment in K₂O, Na₂O, and Rb, and depletion in CaO, MgO, FeO1, TiO₂, P₂O₅, Ba, Sr, and Sc. REE, Y, Zr, and Th were strongly partitioned out of the wall zone into the final residual fluids where they were concentrated up to an order of magnitude over levels in the granite.Within the district, there is also chemical zonation of F, Nb, Th, U, and REE between groups of pegmatites. Polyzonal quartz-core types typically contain more fluorite, samarskite, HREE-zircon, and yttrian-fluorite than their bizonal composite-core counterparts, which contain only sparse fluorite and allanite.The sequence of magmatic evolution involved: (1) a process of diffusive differentiation and fractional crystallization which produced a chemically stratified magma chamber with a hotter more mafic quartz monzonitic base and a more felsic, granitic top enriched in H₂O, F, HREE, Nb, and Y; (2) resurgence of the more mafic lower level crystal mush in to the upper more felsic part of the pluton; and (3) separation of pegmatitic fluids from the juxtaposed magmas giving rise to two compositionally distinct groups of pegmatites.  相似文献