Geochemical types of Volkhovites and possible diamond resource potential of areas occupied by Holocene fluidisites

Volkhovites—tektite-like glasses—have been detected in the Holocene glacial drift along the right bank of the Volkhov River. A cryptomagmatic model of their formation and pre-Holocene age of volkhovite melts, cinder, and frothed glasses has been suggested (Skublov et al., 2007). Four geochemical types of volkhovites are distinguished: (1) manganous (Mn, Fe, Cr, V, Si, Nb, Pb, H), (2) magnesian (Mg, Al, Ti, F, B), (3) potassic (K, Rb, Cs), and (4) calcic (Ca, REEs, Ba, U, Th, Ta, Hf, Y, Sc, Cl). In light of the geochemical data, volkhovites are regarded as natural silicate glasses of kimberlite-carbonatite composition. Their types are called kimberlitic (Mn type), kimberlitic-carbonatitic (Mg type), lamproitic-carbonatitic (K type), and carbonatitic (Ca type). Volkhovites are suggested to be indicators of undiscovered diamond mineralization of kimberlite or carbonatite (Chagatai) types.     

Kirishites—high-carbonaceous hairlike fibers associated with volkhovites

Kirishites are highly carbonaceous hairlike fibers 30–100 μm in thickness and 3–30 mm long, which jut out as bunches on the surface of cinder and shungite fragments associated with volkhovites (Holocene tectitelike glasses corresponding to the rocks of kimberlite-lamproite-carbonatite series in composition). Kirishite fibers are zonal. Their inner (axial) zone is composed of high-nitrogen proteinlike compounds, whereas the outer zone is essentially carbonaceous, with a high content of organoelemental complexes (Si, Fe) and numerous micrometer-sized anomalies of major, volatile, trace, and ore elements. Longitudinal zoning is established in aposhungite kirishites: the consecutive change of maximum concentrations—K, Na, Cl, C, Mn → C, S, V, Ni, Cu, Zn → S, N, Ba, Te, Pb, Bi, Nd—is traced from the roots of fibers to their ends. It is suggested that as volkhovites were forming, fragments of cinder and shungite underwent partial melting. The highly carbonaceous compounds released due decompression and explosion were squeezed out from fragments and solidified as fibers during fall of fragments on the Earth’s surface.     

Boron Isotope Analysis of Silicate Glass with Very Low Boron Concentrations by Secondary Ion Mass Spectrometry

We present an improved method for the determination of the boron isotopic composition of volcanic glasses with boron concentrations of as low as 0.4–2.5 μg g^?1, as is typical for mid‐ocean ridge basalt glasses. The analyses were completed by secondary ion mass spectrometry using a Cameca 1280 large‐radius ion microprobe. Transmission and stability of the instrument and analytical protocol were optimised, which led to an improvement of precision and reduction in surface contamination and analysis time compared with earlier studies. Accuracy, reproducibility (0.4–2.3‰, 2 RSD), measurement repeatability (2 RSE = 2.5–4.0‰ for a single spot with [B] = 1 μg g^?1), matrix effects (? 0.5‰ among komatiitic, dacitic and rhyolitic glass), machine drift (no internal drift; long‐term drift: ~ 0.1‰ hr^?1), contamination (~ 3–8 ng g^?1) and machine background (0.093 s^?1) were quantified and their influence on samples with low B concentrations was determined. The newly developed set‐up was capable of determining the B isotopic composition of basaltic glass with 1 μg g^?1 B with a precision and accuracy of ± 1.5‰ (2 RSE) by completing 4–5 consecutive spot analyses with a spatial resolution of 30 μm × 30 μm. Samples with slightly higher concentrations (≥ 2.5 μg g^?1) could be analysed with a precision of better than ± 2‰ (internal 2 RSE) with a single spot analysis, which took 32 min.     

Origin of rapidly solidified metal-troilite grains in chondrites and iron meteorites

Inclusions of troilite and metallic Fe,Ni 0.2–4 mm in size with a dendritic or cellular texture were observed in 12 ordinary chondrites. Cooling rates in the interval 1400?950°C calculated from the spacing of secondary dendrite arms or cell widths and published experimental data range from 10^?7 to 10⁴°C/sec. In 8 of these chondrites, which are breccias containing some normal slow-cooled metal grains, the inclusions solidified before they were incorporated into the breccias. Their cooling rates of 1–300 °C/sec indicate cooling by radiation, or by conduction in contact with cold silicate or hot silicate volumes only 6–40 mm in size. This is quantitative evidence that these inclusions and their associated clasts were melted on the surface of a parent body (by impact), and were not formed at depth from an internally derived melt. In Ramsdorf, Rose City and Shaw, which show extensive reheating to ? 1000°C, Fe-FeS textures in melted areas are coarser and indicate cooling rates of 10^?1 to 10^?4°C/sec during solidification. This metal may have solidified inside hot silicate volumes that were 10–300 cm in size. As Shaw and Rose City are breccias of unmelted and melted material, their melted metal did not necessarily cool through 1000°C within a few m of the surface. Shock-melted, fine-grained, irregular intergrowths of metal and troilite formed in situ in many irons and some chondrites by rapid solidification at cooling rates of ? 10⁵°C/sec. Their kamacite and taenite compositions may result from annealing at ~250°C of metallic glass or exceedingly fine-grained quench products.     

A model for the dust envelope of the protoplanetary nebula LSIV-12°111

A model for the dust envelope of the protoplanetary nebula LSIV-12°111 is computed using measured fluxes of the object from the UV to the far-IR. It is assumed that the spherically symmetrical envelope is comprised of silicate particles with a standard MRN size distribution, whose number density varies inversely proportional to the square of the distance. The optical depth of the envelope, whose inner boundary is 5.6×10¹⁶ cm from the central star, is 0.072 at 0.55 µm. The temperature of the dust grains at the inner boundary of the envelope is 124 K. The estimated distance to LSIV-12°111 is 3.8 kpc. The current mass-loss rate of the object derived from a self-consistent solution for the radiative transport and motion of the dust in the envelope is 1.0×10^?5M_⊙/yr.     

Experimental modeling of platinum sorption on organic matter

In connection with the discovery of a new type of Pt deposit in low-rank brown coals and black shales, the interaction of Pt-bearing aqueous solutions with fractionated organic matter (asphaltenes and asphaltenic acids) was studied at 200–400°C and 1 kbar total pressure. It was found that chemical sorption onto the organic matter lowers Pt content in the aqueous solutions by about two orders of magnitude relative to organic-free systems. Thermal maturation of the asphaltenes leads to its aromatization and concomitant sorption of Pt from n×10⁻⁴ mPt (mol per kg of dry matter) at 200°C to n×10⁻² mPt at 400°C. Thus, the Pt chemisorption on activated carbonized organic matter may be an effective mechanism of Pt accumulation in C-bearing rocks.     

Structure of mineral glasses—I. The feldspar glasses NaAlSi3O8, KAlSi3O8, CaAl2Si2O8

The short range distribution of interatomic distances in three feldspar glasses has been determined by X-ray radial distribution analysis. The resulting radial distribution functions (RDF's) are interpreted by comparison with RDF's calculated for various quasi-crystalline models of the glass structure.The experimental RDF's of the alkali feldspar glasses were found to be inconsistent with the four-membered rings of tetrahedra associated with crystalline feldspars; the structures of these glasses are probably based on interconnected six-membered rings of the type found in tridymite, nepheline, or kalsilite. In contrast, the RDF of calcic feldspar glass is consistent with a four-membered ring structure of the type found in crystalline anorthite. T-O bond lengths (T = Si,Al) increase from 1.60 Å in SiO₂ glass [J. H. Konnert and J. Karle (1973) Acta Cryst.A29, 702–710] to 1.63 Å in the alkali feldspar glasses to 1.66 Å in the calcic feldspar glass due to the substitution of Al for Si in the tetrahedra] sites. The T-O-T bond angles inferred from the RDF peak positions are 151° in SiO₂ glass (see reference above), 146° in the alkali feldspar glasses, and 143° in the calcic feldspar glass. Detail in the RDF at distances greater than 5 Å suggests that the alkali feldspar glasses have a higher degree of long range order than the calcic feldspar glasses.Assuming that the structural details of our feldspar glasses are similar to those of the melts, the observed structural differences between the alkali feldspar and calcic feldspar glasses helps explain the differences in crystallization kinetics of anhydrous feldspar composition melts. Structural interpretations of some thermodynamic and rheologic phenomena associated with feldspar melts are also presented based on these results.     

Microanalysis of colloids and suspended particles from nuclear waste glass alteration

Fully radioactive and non-radioactive Savannah River Laboratory (SRL) borosilicate glasses were reacted with water under static conditions at glass surface area to leachant volume (S/V) ratios of 340 m⁻¹, 2000 m⁻¹, and 20 000 m⁻¹ for times varying from several days to several years at 90°C. A radioactive SRL 200 glass was also reacted under intermittent flow conditions at 90°C. Colloidal and suspended glass alteration particles present in the leachates of these tests were examined with analytical transmission electron microscopy (AEM). The major colloidal phase identified in all tests was partially crystalline dioctahedral smectite clay. At 20 000 m⁻¹, the clay colloids flocculate and sediment, becoming attached to available surfaces when the ionic strength reached a value of about 0.3–0.5 mol·kg⁻¹. Clay colloids remained stable in the solution for the duration of the experiment in tests conducted at S/V values of 2000 m⁻¹ and 340 m⁻¹. Calcite, dolomite, and transition metal oxide particles were more common in the intermittent flow tests but were also found in the static tests. Layered, Mn-bearing minerals, birnessite and asbolane, were found exclusively in the intermittent flow tests. Weeksite and a U-Ti phase were found exclusively in the static tests. Partially crystalline rare earth-bearing calcium phosphate colloids, structurally related to rhabdophane, were found in both types of tests. These particles exhibited a negative Ce anomaly. The affinity of phosphate for Pu was investigated through geochemical modeling. The results from this study and others were used to form a picture of colloidal development in the leachate from waste glass testing.     

Evidence for extensive diagenesis,Madagascar Basin,Deep Sea Drilling Site 245

Deep Sea Drilling Hole 245 (31°32′S, 52° 18′E) in the southwest Indian Ocean shows pronounced linear concentration-depth gradients in interstitial dissolved Ca, Mg and Sr. Electrical conductivity tests enable us to make the estimate of a constant diffusion coefficient with depth of about 2 × 10^?6 cm²/sec. The shapes of the concentration-depth gradients suggest that the major reaction sites in this hole are situated in the basal sediments and/or underlying basalts. It is proposed that observed interstitial water concentration changes in Ca and Mg are related to alteration of basaltic material, whereas those in Sr are due to calcium carbonate recrystallization processes. Support for the basaltic material alteration hypothesis comes from petrochemical and mineralogical data. Geochemical data also indicate that the high contents in Fe and Mn of the basal sediments can be related to low temperature alteration of basaltic glass and not necessarily to ‘hydrothermal’ activity.     

Argon retention properties of silicate glasses and implications for <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar age and noble gas diffusion studies

Sized aggregates of glasses (47–84 wt% SiO₂) were fused from igneous-derived cohesive fault rock and igneous rock, and step-heated from ~400 to >1,200 °C to obtain their ³⁹Ar diffusion properties (average E=33,400 cal mol^?1; D _o=4.63×10^?3 cm² s^?1). At T<~1,000 °C, glasses containing <~69 wt% SiO₂ and abundant network-forming cations (Ca, Fe, Mg) reveal moderate to strong non-linear increases in D and E, reflecting structural modifications as the solid transitions to melt. Extrapolation of these Arrhenius properties down to typical geologic T-t conditions could result in a 1.5 log₁₀ unit underestimation in the diffusion rate of Ar in similar materials. Numerical simulations based upon the diffusion results caution that some common geologic glasses will likely yield ⁴⁰Ar/³⁹Ar cooling ages rather than formation ages. However, if cooling rates are sufficiently high, ambient temperatures are sufficiently low (e.g., <65–175 °C), and coarse particles (e.g., radius (r) >~1 mm) are analyzed, glasses with compositions similar to ours may preserve their formation ages.     

1.0 GPa、高温下岩石熔融玻璃的弹性波速测量及其地球物理意义

利用超声波反射法,在1.0GPa、最高温度分别达900℃和730℃条件下,测量了岩石成分从酸性到基性的7种熔融玻璃的纵波波速(vp)和横波波速(vs)随温度的变化。实验过程证明,高压下升温过程中样品被压缩导致了样品中弹性波走时减少,而降温过程中样品长度基本保持不变。结果显示,1.0GPa下,随实验温度升高,不同成分玻璃的vp首先以-0.2×10-3km.s-1.℃-1到-0.7×10-3km.s-1.℃-1不等的速率缓慢降低,而其vs多以-0.1×10-3km.s-1.℃-1速率随温度升高而降低。当温度高于玻璃转变温度(Tg)后,玻璃的vp开始以-0.8×10-3km.s-1.℃-1到-3.6×10-3km.s-1.℃-1不等的速率快速下降。根据玻璃vp随温度变化速率的改变,拟合出这几种玻璃的转变温度从584℃到654℃。由实验获得的玻璃波速,利用Voigt-Reuss-Hill(VRH)平均计算出下地壳岩石中玻璃的存在将降低岩石的波速,并由此为下地壳低速层提出一种新的解释,即非晶质体的存在可能在下地壳形成地震波低速层。     

Typology of Natural Hazards and Assessment of Associated Risks in the Mount Bambouto Caldera (Cameroon Line,West Cameroon)

Abstract: Mount Bambouto is a polygenic stratovolcano of the Cameroon Volcanic Line, built between 21?Ma and 4.5?Ma. It is situated approximately 200?km NE of Mount Cameroon, between 09°55′ and 10°15′ longitude east and, 05°25′ and 05°50′ latitude north. The volcano covers an area of 500?km2 and culminates at 2740?m at Mélétan dome and bears a collapsed caldera at the summit (13?×?8?km). Mount Bambouto is characterized by several natural hazards of different origins: meteorological, such as landslides and rock falls; anthropogenic, such as bushfires, tribal wars and deforestation; and volcanological, such as volcanic eruption. The thematic map shows that 55–60% of the caldera has high probability of occurrence of mass movement. The caldera has a high population density (3000 inhabitants), which increases the level of risk, evaluated at approximately $US3.8 million for patrimony, 3000 civilian deaths and destruction of biodiversity.     

Himalayan uplift and osmium isotopes in oceans and rivers

Previous studies have shown that ¹⁸⁷Os/¹⁸⁸Os in seawater has become increasingly radiogenic over the last 40 Ma in a manner analogous to strontium. This rapid rise in the marine ¹⁸⁷Os/¹⁸⁸Os over the last 17 Ma has been attributed to an increase in the bulk silicate weathering rates resulting from the rise of the Himalayas and/or selective weathering and erosion of highly radiogenic organic rich ancient sediments. The key test of this hypothesis is the ¹⁸⁷Os/¹⁸⁸Os and the total osmium concentration of the Himalayan rivers. We report the concentration and isotopic composition of osmium in the Ganges, the Brahmaputra, and the Indus rivers. The ¹⁸⁷Os/¹⁸⁸Os of the Ganges close to its source (at Kaudiyal, 30°05′N, 78°50′E) is 2.65 and [Os] = 45 fM/kg. A second sample of the lower reaches of the Ganges at Patna (25°30′N, 85°10′E) gives ¹⁸⁷Os/¹⁸⁸Os =1.59 and [Os] = 171 fM/kg. The ¹⁸⁷Os/¹⁸⁸Os of the Brahmaputra at Guwahati (26°10′N, 91°58′E) is 1.07 and [Os] = 52 fM/kg. A sample of the Indus (Besham, 34°55′N, 72°51′E) has a ¹⁸⁷Os/¹⁸⁸Os of 1.2 and [Os] = 59 fM/kg. We infer that the Himalayas do not provide either a high flow of osmium or a highly radiogenic osmium component to the oceans. The overall trend for osmium and strontium could be explained by a regularly increasing input of global continental weathering sources but the Himalayas themselves appear not to be the dominant source.     

Static breakage of granitic detritus by ice and water in comparison with breakage by flowing water

Temperature cycling between ?4·5±1·0°C and 13·0±2·0°C in the presence of added water caused significant breakage of granitic detritus. Because cycling with only adsorbed water present also caused breakage, fragmentation is attributed to both the combined action of ice and adsorbed water and to the latter acting alone. Breakage evidently resulted from the gradual tensile opening of pre-existing cracks, weakening then splitting grains. Surviving unbroken grains show evidence of a fatigue effect. Quartz split dominantly along pre-existing subplanar microfractures whereas feldspar and biotite split along crystal cleavages. Degree of breakage and product size distribution depend on the crystalline nature of the parent material, its previous history, and the nature and duration of the breakage process. With the first two factors the same, size distributions from adsorbed water breakage alone and from that due to adsorbed water plus ice differ slightly. Both contrast strongly with those of simulated fluviatile breakage. Whereas the latter preferentially produced 2–20 μm particles (probably debris of inter-particle collisions), static breakage split coarser grains wherever major weaknesses occurred, producing less selective product size distributions with greater proportions of loess-sized material (about 20--60 μ). Characteristic inflections in the size distribution curves of our experimentally produced debris are also shown by samples from the sola of some frost-affected soils. Partially healed microfractures in plutonic quartz are normally spaced at about 1–10 μ—approaching the downward asymptotic comminution limit for brittle solids (about 1 μ). Surficial physical processes are capable of reducing only a small proportion of plutonic quartz to this size before its storage in sediments.     

Magma degassing during 7600 14C Kurile Lake caldera-forming eruption and its climatic impact

The main goal of this investigation is estimating volume of volatile emission, atmospheric and climatic impact of the Kurile Lake caldera-forming eruption, one of the Earth’s largest Holocene explosive eruptions. The volatile content of magma before the eruption was estimated by comparing H₂O, S, Cl and F contents in natural quenched glassy melt inclusions trapped by plagioclase phenocrysts. The volatile content of igneous rocks after eruption was estimated by comparing concentrations of degassed matrix glasses. As a result of KO-eruption not more than (3.7–4.2) × 10¹² kg of water, (4.3–4.9) × 10¹⁰ kg of chlorine, (8.6–9.8) × 10⁹ kg of fluorine and (2.6–2.9) × 10¹⁰ kg of sulphur were injected into the atmosphere. This eruption had to produce an important climatic impact.     

Cooling rate variation in natural volcanic glasses from Tenerife,Canary Islands

 Silicate melts form glasses in a variety of geological environments. The relaxation (equilibration) of the frozen glass structure provides a means of investigating the quench rates of natural glasses, and this cooling history provides an important constraint for models of melt dynamics. Phonolite glasses from the central volcanic edifice of Tenerife, Canary Islands indicate a range of five orders of magnitude cooling rate, determined by modeling the relaxation of the structure-dependent property, enthalpy (H) across the glass transition. The relaxation of enthalpy is determined by heat capacity (c _p = ΔH/ΔT) measurement of natural glass samples by differential scanning calorimetry (DSC). Upon heating, the heat capacity curve in the vicinity of the glass transition has a geometry characteristic of the previous cooling rate. A series of thermal treatments applied to each individual sample results in a set of sample-specific parameters which are used to model the heat capacity curve of the naturally cooled glass. The cooling rate is then derived. The equivalence of shear and enthalpic relaxation enables the relaxation of enthalpy for these volcanic samples to be described by a general term for the evolution of fictive temperature. Quench rates for thirty-one glasses are calculated to be within the range 10°C s^–1 to 7°C per day. The cooling rates quoted are linear approximations across the glass transition. Within different volcanic facies cooling rates depend on several factors. The most rapidly cooled glasses occur where samples lose heat by radiation from the surface. Our analyses indicate that in certain environments, a natural annealing process results in slow quench rates. This is interpreted as either a slow initial cooling process or the reheating of a glass to an annealing temperature within the glass transition interval. The latter results in relaxation to a lower temperature structure. Controls on these processes include the initial temperature and dissipation of thermal energy from the volcanic body. Our results are consistent with an influence of volatiles on quench rates in volcanic bombs where glass adjacent to vesicular layers is relatively rapidly quenched. We interpret this as a rapid quench rate frozen into the glass resulting from a change in viscosity due to volatile degassing. In lava flows, the conduction of heat from the hot flow interior controls the cooling process and diminishes the effect of volatile exsolution. Relaxation geospeedometry can be applied to glass samples from a variety of geological environments where cooling rates cannot be measured directly. Such measurements provide a means of determining cooling rates for a variety of volcanic processes, an independent calibration for existing temperature and time data and a means for testing cooling-rate-dependent models. Received: 9 January 1996 / Accepted: 13 May 1996     

First U–Pb isotopic data on zircon from andesite of the Saf’yanovka Cu-bearing massive sulfide deposit (Middle Urals)

New results of U–Pb LA ICP–MS dating of zircon from andesite samples cropping out on the western wall of the Saf’yanovka quarry (57°22′58.88″ N, 61°31′50.85″ E) in the synonymous Cu–Zn-bearing massive sulfide deposit of the Urals type are considered. The position of data points of the U–Pb systematics in the ²⁰⁷Pb/²³⁵U–²⁰⁶Pb/²³⁸U plot determines a cluster practically corresponding to the concordant U–Pb age: 422.8 ± 2.0 Ma. This date indicates for the first time the presence of Pridolian volcanogenic rocks in the East Urals megazone of the Middle Urals.     

Aerosol particle behavior during Dust Storm and Diwali over an urban location in north western India

In this study, the aerosol behavior during two contradictory events, i.e., dust storm (DS) and Diwali (DW) has been studied over Jaipur. The aerosol particle number concentration shows distinct features between DS and DW events. The total ANC was found minimum during DS while maximum during DW. The 24 h mean of total ANC was 9.15 × 10⁴ (±7.71 × 10⁴) and 5.38 × 10⁵ (±3.73 × 10⁵ particles/l) during DS and DW, respectively. The total ANC increases from 7.78 × 10⁴ to 5.32 × 10⁵ and 3.52 × 10⁵ to 1.70 × 10⁶ particles/l in 24 h during DS and DW, respectively. In DS, the ANC in coarse mode (2 < particle diameter < 20 μm) is significantly high while in DW, the ANC in fine mode (0.3 < particle diameter < 2 μm) exhibits higher concentration. During dust episode, a significant change in ANC (3.0 × 10³ to 1.12 × 10⁵ particles/l) was observed for the particle of size range in 2.0–20 μm with a slight increase in particles number concentration (7.48 × 10⁴ to 4.20 × 10⁵ particles/l) in 0.3–2.0 μm range is also observed. During DS, the fine and coarse mode particles increased 4.61 and 36.44 times while during DW, it increased 3.83 and 0.95 times, respectively. The relatively high particle levels during DW are attributed for two reasons: local emissions due to burning of fire crackers and meteorological conditions, i.e., low wind speeds and low mixing-layer heights lead to relatively high particle concentrations.

     

The chemical durability of tektites—A laboratory study and correlation with long-term corrosion behavior

Leach tests carried out on tektite specimens (indochinites and australites) under high-dilution conditions show a common behavior characterized by low leach rates (1.8 × 10^?5g · m^?2 · d^?1or 7.2 × 10^?12m · d^?1 at 23°C) and an activation energy of (79.6 ± 0.7) × 10³J · mol^?1. The extent of selective leaching is very small, of the order of 10^?8 m. Extrapolation of test results over the lifetime of the tektites gives an excellent agreement with field observations on the extent of corrosion, and this is an important step in establishing the validity of laboratory tests as a basis for the development of models and predictions concerning long-term durabilities at least in the limiting case of high dilution or rapid flow. The results are also shown to be in agreement with various previous observations on the corrosion resistance of tektites. The chemical durability of tektites is observed to be consistent with their composition, highlighting requirements for high corrosion resistance in glasses; these requirements include a silica content in excess of 67 mol%, an extremely low water content and an alkali content which is low both absolutely and relative to the di- and poly-valent metal oxide levels. It is shown that artificial glasses which fulfil these criteria are no less corrosion-resistant than the corresponding natural glasses. These conclusions have bearing on the development as well as on the evaluation of glasses intended for very long service, such as radioactive waste vitrification media.     

The temperature dependence of the speciation of water in NaAlSi3O8-KAlSi3O8 melts: an application of fictive temperatures derived from synthetic fluid-inclusions

 The speciation of water dissolved in glasses along the join NaAlSi₃O₈-KAlSi₃O₈ has been investigated using infrared spectroscopy. Hydrous melts have been hydrothermally synthesized by chemical equilibration of cylinders of bubble-free anhydrous start glasses with water at 1040^° C and 2 kbar. These melts have been isobarically and rapidly (200^° C/s) “drop”-quenched to room temperature and then subsequently depressurized. The speciation of water in the quenched glasses reflects the state of water speciation at a temperature (the so-called fictive temperature) where the quenched-in structure of the glasses closely corresponds to the melt structure at equilibrium. This fictive temperature is detectable as the macroscopically measureable glass transition temperature of these melt compositions. A separate set of experiments using vesicular samples of the same chemistry has precisely defined the glass transition temperature of these melts (±5^° C) on the basis of homogenization temperatures for water-filled fluid inclusions (Romano et al. 1994). The spectroscopic data on the speciation of water in these quenched glasses has been quantified using experimentally determined absorptivities for OH and H₂O for each individual melt composition. The knowledge of glass transition temperatures, together with quantitative speciation data permits an analysis of the temperature dependence of the water speciation over the 113^° C range of fictive temperatures obtained for these water-saturated melts. The variation of water speciation, cast as the equilibrium constant K where K = [H₂O] [O _m ]/[OH]² is plotted versus the fictive temperature of the melt to obtain the temperature dependence of speciation. Such a plot describes a single linear trend of the logarithm of the equilibrium constant versus reciprocal temperature, implying that the exchange of K for Na has little influence on melt speciation of water. The enthalpy derived from temperature dependence is 36.5(±5) kJ/mol. The results indicate a large variation in speciation with temperature and an insensitivity of the speciation to the K–Na exchange. Received: 8 March 1995/Accepted: 6 June 1995