Selective excitation and detection of maximum quantum coherence of a group of scalar coupled protons in chiral molecules: an NMR experiment for enantiodiscrimination

The H-1 NMR spectroscopic discrimination of enantiomers in the solution state and the measurement of enantiomeric composition is most often hindered due to either very small chemical shift differences between the discriminated peaks or severe overlap of transitions from other chemically non-equivalent protons. In addition the use of chiral auxiliaries such as, crown ether and chiral lanthanide shift reagent may often cause enormous line broadening or give little degree of discrimination beyond the crown ether substrate ratio, hampering the discrimination. In circumventing such problems we are proposing the utilization of the difference in the additive values of all the chemical shifts of a scalar coupled spin system. The excitation and detection of appropriate highest quantum coherence yields the measurable difference in the frequencies between two transitions, one pertaining to each enantiomer in the maximum quantum dimension permitting their discrimination and the F-2 cross section at each of these frequencies yields an enantiopure spectrum. The advantage of the utility of the proposed method is demonstrated on several chiral compounds where the conventional one dimensional H-1 NMR spectra fail to differentiate the enantiomers.

Sharp raman anomalies and broken adiabaticity at a pressure induced transition from band to topological insulator in Sb2Se3

The nontrivial electronic topology of a topological insulator is thus far known to display signatures in a robust metallic state at the surface. Here, we establish vibrational anomalies in Raman spectra of the bulk that signify changes in electronic topology: an E-g(2) phonon softens unusually and its linewidth exhibits an asymmetric peak at the pressure induced electronic topological transition (ETT) in Sb2Se3 crystal. Our first-principles calculations confirm the electronic transition from band to topological insulating state with reversal of parity of electronic bands passing through a metallic state at the ETT, but do not capture the phonon anomalies which involve breakdown of adiabatic approximation due to strongly coupled dynamics of phonons and electrons. Treating this within a four-band model of topological insulators, we elucidate how nonadiabatic renormalization of phonons constitutes readily measurable bulk signatures of an ETT, which will facilitate efforts to develop topological insulators by modifying a band insulator. DOI: 10.1103/PhysRevLett.110.107401

Nonclassical Paths in Quantum Interference Experiments

In a double slit interference experiment, the wave function at the screen with both slits open is not exactly equal to the sum of the wave functions with the slits individually open one at a time. The three scenarios represent three different boundary conditions and as such, the superposition principle should not be applicable. However, most well-known text books in quantum mechanics implicitly and/or explicitly use this assumption that is only approximately true. In our present study, we have used the Feynman path integral formalism to quantify contributions from nonclassical paths in quantum interference experiments that provide a measurable deviation from a naive application of the superposition principle. A direct experimental demonstration for the existence of these nonclassical paths is difficult to present. We find that contributions from such paths can be significant and we propose simple three-slit interference experiments to directly confirm their existence.

A Kunitz-type serine protease inhibitor from Butea monosperma seed and its influence on developmental physiology of Helicoverpa armigera

A protease inhibitor from the seeds of Butea monosperma (BmPI) was purified, characterized and studied for its influence on developmental physiology of Helicover-pa armigera. BmPI on two-dimensional separations indicated the presence of a 14 kDa protein with an isoelectric point in the acidic region (pl 5.6). Multiple Sequence Analysis data suggested that the BmPI contains a sequence motif which is conserved in various trypsin and chymotrypsin inhibitors of Kunitz-type. The inhibitor exhibited trypsin inhibitory activity in a broad range of pH (4-10) and temperature (10-80 degrees C). The enzyme kinetic studies revealed BmPI as a competitive inhibitor with a K-i value of 1.2 x 10(-9) M. In vitro studies with BmPI indicated measurable inhibitory activity on total gut proteolytic enzymes of H. armigera (IC(50)2.0 mu g/ml) and bovine trypsin. BmPI supplemented artificial diet caused dose dependent mortality and reduction in growth and weight. The fertility and fecundity of H. armigera, declined whereas the larval-pupal duration of the insect life cycle extended. These detrimental effects on H. armigera suggest the usefulness of BmPl in insect pest management of food crops. (C) 2014 Elsevier Ltd. All rights reserved.

Isolated singularities of polyharmonic operator in even dimension

We consider the equation Delta(2)u = g(x, u) >= 0 in the sense of distribution in Omega' = Omega\textbackslash {0} where u and -Delta u >= 0. Then it is known that u solves Delta(2)u = g(x, u) + alpha delta(0) - beta Delta delta(0), for some nonnegative constants alpha and beta. In this paper, we study the existence of singular solutions to Delta(2)u = a(x) f (u) + alpha delta(0) - beta Delta delta(0) in a domain Omega subset of R-4, a is a nonnegative measurable function in some Lebesgue space. If Delta(2)u = a(x) f (u) in Omega', then we find the growth of the nonlinearity f that determines alpha and beta to be 0. In case when alpha = beta = 0, we will establish regularity results when f (t) <= Ce-gamma t, for some C, gamma > 0. This paper extends the work of Soranzo (1997) where the author finds the barrier function in higher dimensions (N >= 5) with a specific weight function a(x) = |x|(sigma). Later, we discuss its analogous generalization for the polyharmonic operator.

Weakly corrected numerical solutions to stochastically driven nonlinear dynamical systems

A method to weakly correct the solutions of stochastically driven nonlinear dynamical systems, herein numerically approximated through the Eule-Maruyama (EM) time-marching map, is proposed. An essential feature of the method is a change of measures that aims at rendering the EM-approximated solution measurable with respect to the filtration generated by an appropriately defined error process. Using Ito's formula and adopting a Monte Carlo (MC) setup, it is shown that the correction term may be additively applied to the realizations of the numerically integrated trajectories. Numerical evidence, presently gathered via applications of the proposed method to a few nonlinear mechanical oscillators and a semi-discrete form of a 1-D Burger's equation, lends credence to the remarkably improved numerical accuracy of the corrected solutions even with relatively large time step sizes. (C) 2015 Elsevier Inc. All rights reserved.

Failure modes of doubly supported capacitive RF MEMS switches

For the design of radio frequency micro-electro-mechanical systems (RF MEMS) switches, the reliability issue becomes increasingly important. This paper represents some failure phenomena of doubly supported capacitive RF MEMS switches that include observable destruction failure and directly measurable parameter degradation obtained from the actuating-voltage testing and scanning electron microscope (SEM) observation. The relevant failure modes as well as their failure mechanisms are identified.

Enhanced virulence of Salmonella enterica serovar typhimurium after passage through mice.

The interaction between Salmonella enterica and the host immune system is complex. The outcome of an infection is the result of a balance between the in vivo environment where the bacteria survive and grow and the regulation of fitness genes at a level sufficient for the bacteria to retain their characteristic rate of growth in a given host. Using bacteriological counts from tissue homogenates and fluorescence microscopy to determine the spread, localization, and distribution of S. enterica in the tissues, we show that, during a systemic infection, S. enterica adapts to the in vivo environment. The adaptation becomes a measurable phenotype when bacteria that have resided in a donor animal are introduced into a recipient naïve animal. This adaptation does not confer increased resistance to early host killing mechanisms but can be detected as an enhancement in the bacterial net growth rate later in the infection. The enhanced growth rate is lost upon a single passage in vitro, and it is therefore transient and not due to selection of mutants. The adapted bacteria on average reach higher intracellular numbers in individual infected cells and therefore have patterns of organ spread different from those of nonadapted bacteria. These experiments help in developing an understanding of the influence of passage in a host on the fitness and virulence of S. enterica.

Modal scattering at an impedance transition in a lined flow duct

An explicit Wiener-Hopf solution is derived to describe the scattering of duct modes at a hard-soft wall impedance transition in a circular duct with uniform mean flow. Specifically, we have a circular duct r = 1, - ∞ < x < ∞ with mean flow Mach number M > 0 and a hard wall along x < 0 and a wall of impedance Z along x > 0. A minimum edge condition at x = 0 requires a continuous wall streamline r = 1 + h(x, t), no more singular than h = Ο(x1/2) for x ↓ 0. A mode, incident from x < 0, scatters at x = 0 into a series of reflected modes and a series of transmitted modes. Of particular interest is the role of a possible instability along the lined wall in combination with the edge singularity. If one of the "upstream" running modes is to be interpreted as a downstream-running instability, we have an extra degree of freedom in the Wiener-Hopf analysis that can be resolved by application of some form of Kutta condition at x = 0, for example a more stringent edge condition where h = Ο(x3/2) at the downstream side. The question of the instability requires an investigation of the modes in the complex frequency plane and therefore depends on the chosen impedance model, since Z = Z (ω) is essentially frequency dependent. The usual causality condition by Briggs and Bers appears to be not applicable here because it requires a temporal growth rate bounded for all real axial wave numbers. The alternative Crighton-Leppington criterion, however, is applicable and confirms that the suspected mode is usually unstable. In general, the effect of this Kutta condition is significant, but it is particularly large for the plane wave at low frequencies and should therefore be easily measurable. For ω → 0, the modulus fends to |R001| → (1 + M)/(1 -M) without and to 1 with Kutta condition, while the end correction tends to ∞ without and to a finite value with Kutta condition. This is exactly the same behaviour as found for reflection at a pipe exit with flow, irrespective if this is uniform or jet flow.

A porous bulk metallic glass with unidirectional opening pores

Porous Zr-based bulk metallic glass (PMG) with unidirectional opening pores is prepared by electrochemical etching of tungsten wires of the W/bulk metallic glass (BMG) composites. The porosity and pore size can be controlled by adjusting the tungsten wires. The PMG showed no measurable loss in thermal stability as compared to the monolithic Zr-based BMG by water quenching and is more ductile and softer than the pore-free counterpart. The specific surface area of the PMGs is calculated to be 0.65, 3.96, and 10.54 m(2)/kg for 20, 60, and 80 vol % porosity, respectively. (c) 2007 The Electrochemical Society.

Chemical contaminants, pathogen exposure and general health status of live and beach-cast Washington sea otters (Enhydra lutris kenyoni)

Analyses of blood and liver samples from live captured sea otters and liver samples from beachcast sea otter carcasses off the remote Washington coast indicate relatively low exposure to contaminants, but suggest that even at the low levels measured, exposure may be indicated by biomarker response. Evidence of pathogen exposure is noteworthy - infectious disease presents a potential risk to Washington sea otters, particularly due to their small population size and limited distribution. During 2001 and 2002, 32 sea otters were captured, of which 28 were implanted with transmitters to track their movements and liver and blood samples were collected to evaluate contaminant and pathogen exposure. In addition, liver samples from fifteen beachcast animals that washed ashore between 1991 and 2002 were analyzed to provide historical information and a basis of reference for values obtained from live otters. The results indicate low levels of metals, butyltins, and organochlorine compounds in the blood samples, with many of the organochlorines not detected except polychlorinated biphenyls (PCBs), and a few aromatic hydrocarbons detected in the liver of the live captured animals. Aliphatic hydrocarbons were measurable in the liver from the live captured animals; however, some of these are likely from biogenic sources. A significant reduction of vitamin A storage in the liver was observed in relation to PCB, dibutyltin and octacosane concentration. A significant and strong positive correlation in vitamin A storage in the liver was observed for cadmium and several of the aliphatic hydrocarbons. Peripheral blood mononuclear cell (PBMC) cytochrome P450 induction was elevated in two of 16 animals and may be potentially related to aliphatic and aromatic hydrocarbon exposure. Mean concentration of total butyltin in the liver of the Washington beach-cast otters was more than 15 times lower than the mean concentration reported by Kannan et al. (1998) for Southern sea otters in California. Organochlorine compounds were evident in the liver of beach-cast animals, despite the lack of large human population centers and development along the Washington coast. Concentrations of PCBs and chlordanes (e.g., transchlordane, cis-chlordane, trans-nonachlor, cis-nonachlor and oxychlordane) in liver of Washington beach-cast sea otters were similar to those measured in Aleutian and California sea otters, excluding those from Monterey Bay, which were higher. Mean concentrations of 1,1,1,- trichloro-2,2-bis(p-chlorophyenyl)ethanes (DDTs) were lower, and mean concentrations of cyclohexanes (HCH, e.g., alpha BHC, beta BHC, delta BHC and gamma BHC) were slightly higher in Washington beach-cast otters versus those from California and the Aleutians. Epidemiologically, blood tests revealed that 80 percent of the otters tested positive for morbillivirus and 60 percent for Toxoplasma, the latter of which has been a significant cause of mortality in Southern sea otters in California. This is the first finding of positive morbillivirus titers in sea otters from the Northeast Pacific. Individual deaths may occur from these diseases, perhaps more so when animals are otherwise immuno-compromised or infected with multiple diseases, but a population-threatening die-off from these diseases singly is unlikely while population immunity remains high. The high frequency of detection of morbillivirus and Toxoplasma in the live otters corresponds well with the cause of death of stranded Washington sea otters reported herein, which has generally been attributable to infectious disease. Washington’s sea otter population continues to grow, with over 1100 animals currently inhabiting Washington waters; however, the rate of growth has slowed over recent years. The population has a limited distribution and has not yet reached its carrying capacity and as such, is still considered at high risk to catastrophic events. (PDF contains 189 pages)

Changes in the size structure of the yellowfin tuna population of the tropical eastern Pacific Ocean from 1947 to 1955

ENGLISH: Morphometric studies by Godsil (1948), Godsil and Greenhood (1951), Royce (1953) and Schaefer (1952, 1955) have indicated that the yellowfin tuna of the Eastern Pacific are distinct from those of the Central Pacific. Tagging of yellowfin tuna by the California Department of Fish and Game, and by the Inter-American Tropical Tuna Commission in the Eastern Pacific, and by the Pacific Oceanic Fishery Investigations in the Central Pacific, have not yet revealed any migrations between these areas. Shimada and Schaefer (1956) have compared changes in population abundance and fishing intensity, considering the population in the Eastern Pacific as a separate entity. They conclude " ... the amount of fishing has had a real effect upon the stock of Eastern Pacific yellowfin tuna, taken in the aggregate, over the period studied. The evidence suggests also that for this species the intensity of fishing in some recent years has reached and might have even exceeded the level corresponding to the maximum equilibrium yield." Tagging experiments by the California Department of Fish and Game and by the Inter-American Tropical Tuna Commission have yielded returns in the order of one to five percent (Roedel 1954, and unpublished data of both agencies), a level much lower than that at which fishing intensity would be expected to noticeably affect the population size. These results are probably a reflection of the inadequacies of the present tagging methods, but they could lend doubt to the conclusions of Shimada and Schaefer. It is desirable, therefore, to examine other, independent, evidence as to the effects of fishing on the population. At the high levels of fishing intensity suggested by Shimada and Schaefer, in addition to changes in quantity, measurable changes would be expected to have occurred in the quality of the yellowfin tuna stocks, because the average age and size of the fish would have been reduced by the high mortality rates accompanying high fishing intensities. A continuing regular program of sampling catches and determining their length composition, to assess changes in the size composition of the stocks, was initiated by the Commission in 1954 but direct measurements are not available for the earlier, more dynamic period of growth of the fishery. Consequently, other, more general indications of possible changes in the size composition were sought. SPANISH: Los estudios morfométricos efectudos por Godsil (1948), Godsil y Greenhood (1951), Royce (1953) y Schaefer (1952, 1955), han demostrado que el atún aleta amarilla del Pacífico Oriental es distinto del que habita el PacÍfico Central. Los experimentos del Departamento de Pesca y Caza de California y de la Comisión Interamericana del Atún Tropical en el Pacífico Oriental, así como los de las Investigaciones Pesqueras del Océano Pacífico en el Pacífico Central,consistentes en la marcación de atunes aleta amarilla, aún no han puesto de manifiesto movimientos migratorios entre dichas áreas. Shimada y Schaefer (1956) han hecho estudios comparativos sobre la abundancia de la población y la intensidad de la pesca, considerando a la población del Pacífico Oriental como una entidad separada. Su conclusión es que " ... la intensidad de la pesca ha tenido un definido efecto sobre la población del atún aleta amarilla del Pacífico Oriental, tomada en conjunto, a lo largo del período estudiado. La evidencia de que se dispone sugiere así mismo que, por lo que hace a esta especie, la intensidad de la pesca en los últimos años ha alcanzado y quizás aún sobrepasado el nivel correspondiente a la máxima pesca de equilibrio". Los experimentos de mar•cación del Departamento de Pesca y Caza de California y de la Comisión Interamericana del Atún Tropical han producido recuperaciones ,entre el uno y el cinco por ciento (Roedel 1954 y datos inéditos de ambos organismos), lo que constituye un nivel mucho más bajo de aquél en que la intensidad de la pesca podría considerarse que afectaría notablemente el tamaño de la población. Estos resultados reflejan probablemente lo inadecuados que son aún los métodos de marcación, pero ellos podrían, quizá, poner en tela de juicio las conclusiones de Shimada y Schaefer. Por lo tanto,es deseable examinar otras fuentes de evidencia independientes, relacionadas con el efecto que la pesca tiene sobre la población. En efecto, si los altos índices de pesca sugeridos por Shimada y Schaefer son correctos, es de esperar que, además de los cambios en la magnitud de la población, se hayan producido otros, concomitantes y sensibles, en la calidad de los stocks de atún aleta amarilla, puesto que tanto el promedio de edad como el de tamaño de los individuos habrían disminuído debido a las elevadas tasas de mortalidad inherentes a las altas intensidades de pesca. En 1954 la Comisión inició un programa ininterrumpido para tomar muestras y determinar en ellas las frecuencias de tallas y evaluar de este modo los cambios correlativos que tuvieran lugar en los stocks pero, infortunadamente, este sistema de evaluación directa no fué practicado en el período anterior, que fué precisamente el de rápida expansión de la pesquería. En tal virtud, hubo de ser necesario buscar indicios más generales referentes a los cambios posibles en la composición de tamaños. (PDF contains 20 pages.)

Influence of the Azores high on sea level pressure and wind, and on precipitation, in the Eastern Tropical Pacific Ocean

ENGLISH: Intensification of the Azores high pressure cell in mid-year, with concomitant air flow from the Caribbean into the Pacific, is shown to be responsible for a secondary minimum of precipitation observed along the tropical Pacific coast of the Americas, and to have a measurable effect on wind and precipitation several hundred kilometers offshore. SPANISH: La intensificación de la célula de alta presión de las Azores a mediados del año, y la corriente de aire concomitante que entra al Pacífico procedente del Caribe, se demuestra que es la causante de un mínimo secundario de precipitación observado a lo largo de la costa tropical de las Américas en el Pacífico y que tiene un efecto mensurable sobre el viento y la precipitación varios cientos de kilómetros mar afuera. (PDF contains 23 pages.)

Population dynamics of the skipjack tuna (Katsuwonus pelamis) of the Eastern Pacific Ocean

ENGLISH: Catches of skipjack tuna supporting major fisheries in parts of the western, central and eastern Pacific Ocean have increased in recent years; thus, it is important to examine the dynamics of the fishery to determine man's effect on the abundance of the stocks. A general linear hypothesis model was developed to standardize fishing effort to a single vessel size and gear type. Standardized effort was then used to compute an index of abundance which accounts for seasonal variability in the fishing area. The indices of abundance were highly variable from year to year in both the northern and southern areas of the fishery but indicated a generally higher abundance in the south. Data from 438 fish tagged and recovered in the eastern Pacific Ocean were used to compute growth curves. A least-squares technique was used to estimate the parameters of the von Bertalanffy growth function. Two estimates of the parameters were made by analyzing the same data in different ways. For the first set of estimates, K= 0.819 on an annual instantaneous basis and L= 729 mm; for the second, K = 0.431 and L=881. These compared well with estimates derived using the Chapman-Richards growth function, which includes the von Bertalanffy function as a special case. It was concluded that the latter function provided an adequate empirical fit to the skipjack data since the more complicated function did not significantly improve the fit. Tagging data from three cruises involving 8852 releases and 1777 returns were used to compute mortality rates during the time the fish were in the fishery. Two models were used in the analyses. The best estimates of the catchability coefficient (q) in the north and south were 8.4 X 10- 4 and 5.0 X 10- 5 respectively. The other loss rate (X), which included losses due to emigration, natural mortality and mortality due to carrying a tag, was 0.14 on an annual instantaneous basis for both areas. To detect the possible effect of fishing on abundance and total yield, the relation between abundance and effort and between total catch and effort was examined. It was found that at levels of intensity observed in the fishery, fishing does not appear to have had any measurable effect on the stocks. It was concluded therefore that the total catch could probably be increased by substantially increasing total effort beyond the present level, and that the fluctuations in abundance are fishery-independent. The estimates of growth, mortality and fishing effort were used to compute yield-per-recruitment isopleths for skipjack in both the northern and southern areas. For a size at first entry of about 425 mm, the yield per recruitment was calculated at 3 pounds in the north and 1.5 pounds in the south. In both areas it would be possible to increase the yield per recruitment by increasing fishing effort. It was not possible to assess potential production of the skipjack stocks fished in the eastern Pacific, except to note that the fishery had not affected their abundance and that they were certainly under-exploited. It was concluded that the northern and southern stocks could support increased harvests, especially the latter. SPANISH: Las capturas de atún barrilete que sostienen las pesquerías principales de la parte occidental, central y oriental del Océano Pacífico han aumentado en los últimos años; así que es importante examinar la dinámica de la pesquería para determinar el efecto que pueda tener sobre la abundancia de los stocks. Se desarrolló un modelo hipotético, lineal para standardizar el esfuerzo de pesca a un solo tamaño de barco y tipo de arte. Luego se usó el esfuerzo standardizado para computar un índice de la abundancia que pueda dar razón de la variabilidad estacional en el área de pesca. Los índices de la abundancia variaron mucho de un año a otro tanto en el área septentrional como en el área meridional de la pesquería, pero indicaron una abundancia generalmente superior en el sur. Se emplearon los datos de 438 peces marcados y recuperados en el Océano Pacífico oriental para computar las curvas de crecimiento. Una técnica de mínimos cuadrados fue usada para estimar los parámetros de la función de crecimiento de van Bertalanffy. Se hicieron dos estimativos de los parámetros mediante el análisis de los mismos datos, de diferente manera. Para el primer juego de estimativos, K=0.819 sobre una base anual instantánea y L∞=729 mm; para el segundo, K=0.431 y L∞=881. Estos se correlacionaron bien con los estimativos obtenidos usando la función de crecimiento de Chapman-Richards, que incluye la de von Bertalanffy como un caso especial. Se decidió que la última función proveía un ajuste empírico, adecuado a los datos del barrilete, ya que la función más complicada no mejoró significativamente el ajuste. Los datos de marcación de tres cruceros incluyendo 8852 liberaciones y 1777 retornos, fueron usados para computar las tasas de mortalidad durante el tiempo en que los peces estuvieron en la pesquería. Se usaron dos modelos en los análisis. Los mejores estimativos del coeficiente de capturabilidad (q) en el norte y en el sur fueron 8.4 X 10-4 y 5.0 X 10-5 , respectivamente. La otra tasa de pérdida (X), la cual incluyó pérdidas debidas a la emigración, mortalidad natural y mortalidad debida a llevar una marca, fue 0.14 sobre una base anual instantánea para las dos áreas. Con el fin de descubrir el efecto que posiblemente pueda tener la pesca sobre la abundancia y el rendimiento total, se examinó la relación entre la abundancia y el esfuerzo y entre la captura total y el esfuerzo. Se encontró que a los niveles de la intensidad observada en la pesquería, la pesca no parece haber tenido ningún efecto perceptible en los stocks. Por lo tanto se decidió que mediante un aumento substancial del esfuerzo total, más allá del nivel actual, la captura total probablemente podría aumentarse, y que las fluctuaciones de la abundancia son independientes de la pesquería. Los estimativos del crecimiento, mortalidad y esfuerzo de pesca fueron usados para computar las isopletas del rendimiento por recluta del barrilete, tanto en las áreas del norte como del sur. Para una talla de primera entrada de unos 425 mm, el rendimiento por recluta fue calculado en 3 libras en el norte y 1.5 libras en el sur. En ambas áreas sería posible aumentar el rendimiento por recluta mediante un aumento del esfuerzo de pesca. No fue posible determinar la producción potencial de los stocks del barrilete pescado en el Pacífico oriental, excepto para observar que la pesquería no ha afectado su abundancia y que ciertamente se encuentran subexplotados. Se concluyó que los stocks norte y sur pueden soportar un aumento en el rendimiento, especialmente este último. (PDF contains 274 pages.)

Water in silicate glasses

The speciation of water in a variety of hydrous silicate glasses, including simple and rhyolitic compositions, synthesized over a range of experimental conditions with up to 11 weight percent water has been determined using infrared spectroscopy. This technique has been calibrated with a series of standard glasses and provides a precise and accurate method for determining the concentrations of molecular water and hydroxyl groups in these glasses.

For all the compositions studied, most of the water is dissolved as hydroxyl groups at total water contents less than 3-4 weight percent; at higher total water contents, molecular water becomes the dominant species. For total water contents above 3-4 weight percent, the amount of water dissolved as hydroxyl groups is approximately constant at about 2 weight percent and additional water is incorporated as molecular water. Although there are small but measurable differences in the ratio of molecular water to hydroxyl groups at a given total water content among these silicate glasses, the speciation of water is similar over this range of composition. The trends in the concentrations of the H-bearing species in the hydrous glasses included in this study are similar to those observed in other silicate glasses using either infrared or NMR spectroscopy.

The effects of pressure and temperature on the speciation of water in albitic glasses have been investigated. The ratio of molecular water to hydroxyl groups at a given total water content is independent of the pressure and temperature of equilibration for albitic glasses synthesized in rapidly quenching piston cylinder apparatus at temperatures greater than 1000°C and pressures greater than 8 kbar. For hydrous glasses quenched from melts cooled at slower rates (i.e., in internally heated or in air-quench cold seal pressure vessels), there is an increase in the ratio of molecular water to hydroxyl group content that probably reflects reequilibration of the melt to lower temperatures during slow cooling.

Molecular water and hydroxyl group concentrations in glasses provide information on the dissolution mechanisms of water in silicate liquids. Several mixing models involving homogeneous equilibria of the form H_2O + O = 20H among melt species have been explored for albitic melts. These models can account for the measured species concentrations if the effects of non-ideal behavior or mixing of polymerized units are included, or by allowing for the presence of several different types of anhydrous species.

A thermodynamic model for hydrous albitic melts has been developed based on the assumption that the activity of water in the melt is equal to the mole fraction of molecular water determined by infrared spectroscopy. This model can account for the position of the watersaturated solidus of crystalline albite, the pressure and temperature dependence of the solubility of water in albitic melt, and the volumes of hydrous albitic melts. To the extent that it is successful, this approach provides a direct link between measured species concentrations in hydrous albitic glasses and the macroscopic thermodynamic properties of the albite-water system.

The approach taken in modelling the thermodynamics of hydrous albitic melts has been generalized to other silicate compositions. Spectroscopic measurements of species concentrations in rhyolitic and simple silicate glasses quenched from melts equilibrated with water vapor provide important constraints on the thermodynamic properties of these melt-water systems. In particular, the assumption that the activity of water is equal to the mole fraction of molecular water has been tested in detail and shown to be a valid approximation for a range of hydrous silicate melts and the partial molar volume of water in these systems has been constrained. Thus, the results of this study provide a useful thermodynamic description of hydrous melts that can be readily applied to other melt-water systems for which spectroscopic measurements of the H-bearing species are available.