Water in silicate glasses: An infrared spectroscopic study

Infrared and near-infrared transmission spectra have been taken on 19 volcanic and synthetic silicate glasses with known H₂O contents (0.06–6.9 wt. %). Absorption peaks were observed at wavelengths of 1.41 m, 1.91 m, 2.22 m, 2.53 m, and 2.8 m. These peaks have been attributed to the first overtone of the OH stretching vibration, the combination stretching+bending mode of H₂O molecules, the combination stretching+bending mode of X-OH groups, a combination mode of the fundamental OH stretch+a low energy lattice vibration, and the fundamental OH stretching mode, respectively. Molar absorptivities of the peaks have been determined to be 0.2, 1.8, 1.0, 0.9, and 67 l/mol-cm. These values apply over the full range of glass compositions studied (albite, rhyolite, basalt).Quantitative determinations of total H₂O contents and of the concentrations of molecular water and hydroxyl groups in silicate glasses are possible using these molar absorptivities, although they are limited in their accuracy by the accuracy of the reported water contents of the glasses used to calibrate these molar absorptivities. The most important uses of this technique may stem from its applicability to microsamples (100 m) and to the determination of the concentrations of hydroxyl groups and molecular water in quenched silicate melts.Hydroxyl groups are the dominant hydrogen-bearing species in water-bearing glasses at low total water contents, but molecular H₂O was detected in all samples with 0.5 weight percent total water. The concentration of hydroxyl groups increases rapidly with total water content at low total water contents, but more slowly at higher (>3 wt. %) total water contents; it may level off or even decrease at high total water contents. The concentration of molecular water increases slowly at low total water contents and more rapidly at high total water contents. More water is dissolved as molecular water than as hydroxyl groups at total water contents greater than 4 wt. %. Molecular water in these glasses is probably structurally bound rather than present as fluid inclusions as a separate phase, since ice bands were not observed in spectra taken at 78K and since samples were free of visible bubbles.It is proposed that the speciation of water in silicate glass formed by rapid quenching from melt equilibrated at high temperatures reflects that of the melt. According to this hypothesis, neither high water contents nor high pressures are needed to stabilize substantial quantities of molecular water in melts. This hypothesis, that water dissolves in silicate melts as both molecular water and hydroxyl groups in proportions similar to those measured in waterbearing glasses, can explain the variations in viscosity, electrical conductivity, diffusivity of water, diffusivity of cesium, and phase relationships that are observed in melts as functions of total water content. It also explains the observation that at vapor-saturation at high pressures, where most of the dissolved water is expected to be present as molecular water, water solubilities are similar for all melts but that at low pressures and water contents, where most dissolved water is present in dissociated form as hydroxyl groups, vapor-saturated water solubilities differ for different melt compositions. The linear relationship between water fugacity and the square of the mole fraction of total dissolved water observed for silicate melts at low water contents and the observed deviations from this linear relationship at high total water contents can be accounted for by this hypothesis.     

辽河三角洲翅碱蓬湿地不同植被覆盖度下的土壤对碳的扣留

为研究辽河三角洲湿地的固碳能力,2010年5月在辽河三角洲双台子河口东侧的两个翅碱蓬湿地区域采取7个柱状样,通过对样品的化学分析测试,并利用210Pb测年法确定的沉积速率研究了土壤对碳的扣留速率,其结果表明:有机碳浓度分别与各营养元素浓度间有显著的正相关关系(p0.01),指示沉积物中的有机物质对营养元素有很强的富集能力,同时营养元素促进植物的生长,从而影响土壤碳的加积速率。研究区总碳浓度范围为10.5~14.6 g/kg,其中约83%为有机碳,其相应的土壤对总碳和有机碳扣留速率分别为98.02~260.37 g/m2/a(均值171.84 g/m2/a)和81.17~229.98 g/m2/a(均值141.29 g/m2/a)。本研究区,土壤对碳的扣留速率主要受土壤的沉积速率控制,并与高程有显著的相关关系(p0.01)。土壤对碳扣留机制的研究有助于加深对全球碳循的理解。     

Mg,Ca and O18O16 exchange in the sediment-pore water system,hole 149, DSDP

The diagenesis and geochemical evolution of deep-sea sediments are controlled by the interaction between sediments and their associated pore waters. With increasing depth, the pore water of Hole 149 (DSDP) exhibits a strong depletion in Mg and a corresponding enrichment in Ca, while the alkalinity remains relatively constant. Dissolved SiO₂ is nearly constant in the upper 100 m of sediment, but is highly enriched in the deepest pore waters. The pore waters exhibit a depletion in K with increasing depth, and $\text{O}{}^{18}\text{O}{}^{16}$ pore water ratios also decrease.The sediment section has three zones of sedimentary regimes with increasing depth in the drill hole: an upper 100 m section of detrital clays, a middle section enriched in calc-akalic volcanics which have undergone submarine weathering to a smectite phase, and a lower section of siliceous ooze which still has a diagenetic smectite phase. The quartz-feldspar ratios and $\text{O}{}^{18}\text{O}{}^{16}$ composition of the silicate phases are in agreement with these interpretations.The submarine weathering of volcanics to a smectite can account for the observed pore water gradients. Volcanics release Ca and Mg to the pore waters causing the alkalinity values to increase. Smectite is formed, depletes the pore waters in Mg and O¹⁸ and causes the alkalinity to decrease. The net reaction allows for the observed relationship between pore water Ca and Mg gradients with little net change in alkalinity. Given the abundance of volcanics in many deep-sea sediments, especially in lower sections which often form near ridge crests, the submarine formation of smectite may be an additional oceanic Mg sink which has not yet been fully considered.     

Low molecular weight α-hydroxy carboxylic and dicarboxylic acids in reducing marine sediments

The occurrence and distribution of low molecular weight α-hydroxy carboxylic and dicarboxylic acids was studied in reducing marine sediments collected in the Santa Barbara Basin and the Cariaco Trench. Four compounds were found to occur in both basin sediments: glycolic, lactic, oxalic and succinic acids. In general concentrations were low (? 1 μmol/g for the hydroxy acids and ? 100μmol/g for the dicarboxylic acids), and generally decreased with depth. Subsurface maxima were observed for lactate and succinate in the Santa Barbara Basin. Both the vertical profiles and lactate enantiomer ratios suggested microbial origin and control for the distribution of these compounds. A preliminary model for the microbial mediation of the early diagenesis of organic compounds in reducing marine sediments is presented.     

The Kalatongke magmatic Ni–Cu deposits in the Central Asian Orogenic Belt, NW China: product of slab window magmatism?

The Permian Kalatongke Ni–Cu deposits in the Central Asian Orogenic Belt are among the most important Ni–Cu deposits in northern Xinjiang, western China. The deposits are hosted by three small mafic intrusions comprising mainly norite and diorite. Its tectonic context, petrogenesis, and ore genesis have been highly contested. In this paper, we present a new model involving slab window magmatism for the Kalatongke intrusions. The origin of the associated sulfide ores is explained in the context of this new model. Minor amounts of olivine in the intrusions have Fo contents varying between 71 and 81.5?mol%, which are similar to the predicted values for olivine crystallizing from coeval basalts in the region. Analytic modeling based on major element concentrations suggests that the parental magma of the Kalatongke intrusions and the coeval basalts represent fractionated liquids produced by ～15% of olivine crystallization from a primary magma, itself produced by 7–8% partial melting of depleted mantle peridotite. Positive ε _Nd values (+4 to +10) and significant negative Nb anomalies for both intrusive and extrusive rocks can be explained by the mixing of magma derived from depleted mantle with 6–18% of a partial melt derived from the lower part of a juvenile arc crust with a composition similar to coeval A-type granites in the region, plus up to 10% contamination with the upper continental crust. Our model suggests that a slab window was created due to slab break-off during a transition from oceanic subduction to arc–arc or arc–continent collision in the region in the Early Permian. Decompression melting in the upwelling oceanic asthenosphere produced the primary magma. When this magma ascended to pond in the lower parts of a juvenile arc crust, it underwent olivine crystallization and at the same time triggered partial melting of the arc crust. Mixing between these two magmas followed by contamination with the upper crust after the magma ascended to higher crustal levels formed the parental magma of the Kalatongke intrusions. The parental magma of the Kalatongke intrusions was saturated with sulfide upon arrival primarily due to olivine fractional crystallization and selective assimilation of crustal sulfur. Sulfide mineralization in the Kalatongke intrusions can be explained by accumulation of immiscible sulfide droplets by flow differentiation, gravitational settling, and downward percolation which operated in different parts of the intrusions. Platinum-group element (PGE) depletion in the bulk sulfide ores of the Kalatongke deposits was due to depletion in the parental magma which in turn was likely due to depletion in the primary magma. PGE depletion in the primary magma can be explained by a relatively low degree of partial melting of the mantle and retention of coexisting sulfide liquid in the mantle.     

10Be exposure age constraints on the Late Weichselian ice‐sheet geometry and dynamics in inter‐ice‐stream areas,western Svalbard

The Late Weichselian ice sheet of western Svalbard was characterized by ice streams and inter‐ice‐stream areas. To reconstruct its geometry and dynamics we investigated the glacial geology of two areas on the island of Prins Karls Forland and the Mitrahalvøya peninsula. Cosmogenic ¹⁰Be surface exposure dating of glacial erratics and bedrock was used to constrain past ice thickness, providing minimum estimates in both areas. Contrary to previous studies, we found that Prins Karls Forland experienced a westward ice flux from Spitsbergen. Ice thickness reached >470 m a.s.l., and warm‐based conditions occurred periodically. Local deglaciation took place between 16 and 13 ka. At Mitrahalvøya, glacier ice draining the Krossfjorden basin reached >300 m a.s.l., and local deglaciation occurred at c. 13 ka. We propose the following succession of events for the last deglaciation. After the maximum glacier extent, ice streams in the cross‐shelf troughs and fjords retreated, tributary ice streams formed in Forlandsundet and Krossfjorden, and, finally, local ice caps were isolated over both Prins Karls Forland and Mitrahalvøya and their adjacent shelves.     

Geochemical evolution of Jurassic diorites from the Bristol Lake region,California, USA,and the role of assimilation

Late Jurassic dioritic plutons from the Bristol Lake region of the eastern Mojave Desert share several geochemical attributes with high-alumina basalts, continental hawaiite basalts, and high-K are andesites including: high K₂O concentrations; high Al₂O₃ (16–19 weight %); elevated Zr/TiO₂; LREE (light-rare-earth-element) enrichment (La/Yb_CN=6.3–13.3); and high Nb. Pearce element ratio analysis supported by petrographic relations demonstrates that P, Hf, and Zr were conserved during differentiation. Abundances of conserved elements suggest that dioritic plutons from neighboring ranges were derived from similar parental melts. In the most voluminous suite, correlated variations in elemental concentrations and (⁸⁷Sr/⁸⁶Sr)_i indicate differentiation by fractional crystallization of hornblende and plagioclase combined with assimilation of a component characterized by abundant radiogenic Sr. Levenberg-Marquardt and Monte Carlo techniques were used to obtain optimal solutions to non-linear inverse models for fractional crystallization-assimilation processes. Results show that the assimilated material was chemically analogous to lower crustal mafic granulites and that the mass ratio of contaminant to parental magma was on the order of 0.1. Lack of enrichment in ¹⁸O with differentiation is consistent with the model results. Elemental concentrations and O, Sr, and Nd isotopic data point to a hydrous REE-enriched subcontinental lithospheric source similar to that which produced some Cenozoic continental hawaiites from the southern Cordillera. Isotopic compositions of associated granitoids suggest that partial melting of this subcontinental lithosphere may have been an important process in the development of the Late Jurassic plutonic arc of the eastern Mojave Desert.     

Effect of silica concentration on the diopsidic pyroxenes in the system diopside-CaTiAl2O6SiO2

The effect of silica concentration on the solubility of Al and Ti in diopsidic pyroxenes has been investigated at one atmosphere in the system diopside-CaTiAl₂O₆-SiO₂ at temperatures between 1150–1420° C. The composition of pyroxene in the system diopside-CaTiAl₂O₆-SiO₂ is influenced by the total SiO₂ content. Near the join diopside-CaTiAl₂O₆, the pyroxene forms a solid solution with the CaTiAl₂O₆ molecule, and co-exists with perovskite for compositions greater than 11 weight percent CaTiAl₂O₆. Anorthite is an accompanying phase. With increasing total SiO₂ content a series of mineralogical changes involving Ti-bearing phases occur. Sphene solid solution co-exists with diopside solid solution, anorthite, and perovskite in a small compositional range near the diopside-CaTiAl₂O₆ join. Additional total SiO₂ results in the elimination of perovskite and a decrease of solid solution in the pyroxenes. With further increase in SiO₂ content, tridymite appears and the pyroxene is approximately pure diopside. Rutile joins diopside, anorthite, sphene solid solution and tridymite over a broad compositional range in the Ti, Si-rich part of the system. These results demonstrate that increased silica concentration decreases the solubility of Al and Ti in diopsidic pyroxenes and controls the stability of co-existing Ti-bearing phases.     

Elemental abundances in Green River oil shale

Spark-source mass spectrometric analysis of pyrolyzed Green River oil shale for trace element distribution showed enhanced concentrations for only lithium and beryllium. In general, trace elemental concentrations were found to be below anticipated crustal amounts. There appears to be no promise of any substantial accumulation of any trace elements within the organic matrix of Green River oil shale.     

The question of Eaton: terrestrial versus meteoritic copper

The Eaton ‘meteorite’ contains roughly 66 per cent Cu, 33 per cent Zn and <0.1 per cent Ni. In contrast, native Cu from other meteorites contains >90 per cent Cu, <5 per cent Zn and in those samples in which it could be measured, 0.4–2.4 per cent Ni. The major phases and inclusions of Eaton closely resemble those in commercial yellow brass. Eaton contains α and β Cu-Zn, small Pb inclusions around the Cu-Zn crystals and larger Ca aluminosilicate inclusions similar to those from sand casting molds. Based on these data Eaton does not appear to be a meteorite.Both meteoritic and terrestrial native copper are striking for their relatively high purity. Meteoritic Cu appears to be distinguishable from terrestrial material by its higher Ni contents.