Development of reaction models for ground-water systems

Methods are described for developing geochemical reaction models from the observed chemical compositions of ground water along a hydrologic flow path. The roles of thermodynamic speciation programs, mass balance calculations, and reaction-path simulations in developing and testing reaction models are contrasted. Electron transfer is included in the mass balance equations to properly account for redox reactions in ground water. The mass balance calculations determine net mass transfer models which must be checked against the thermodynamic calculations of speciation and reaction-path programs. Although reaction-path simulations of ground-water chemistry are thermodynamically valid, they must be checked against the net mass transfer defined by the mass balance calculations. An example is given testing multiple reaction hypotheses along a flow path in the Floridan aquifer where several reaction models are eliminated. Use of carbon and sulfur isotopic data with mass balance calculations indicates a net reaction of incongruent dissolution of dolomite (dolomite dissolution with calcite precipitation) driven irreversibly by gypsum dissolution, accompanied by minor sulfate reduction, ferric hydroxide dissolution, and pyrite precipitation in central Florida. Along the flow path, the aquifer appears to be open to CO₂ initially, and open to organic carbon at more distant points down gradient.     

Knowledge gaps in tropical Southeast Asian seagrass systems

Seagrasses are habitats with significant ecological and economic functions but we have limited knowledge of seagrasses in Southeast Asia, the hypothesized centre-of-origin for tropical seagrasses. There have been only 62 ISI-cited publications on the seagrasses of Southeast Asia in the last three decades and most work has been in few sites such as Northwest Luzon in the Philippines and South Sulawesi in Indonesia. Our understanding of the processes driving spatial and temporal distributions of seagrass species here has focussed primarily on backreef and estuarine seagrass meadows, with little work on forereef systems. We used Pulau Tinggi, an island off the southeast coast of Peninsular Malaysia, as an example of a subtidal forereef system. It is characterized by a community of small and fast growing species such as Halophila ovalis (mean shoot density 1454.6 ± 145.1 m⁻²) and Halodule uninervis (mean shoot density 861.7 ± 372.0 m⁻²) growing in relatively low light conditions (mean PAR 162.1 ± 35.0 μmol m⁻² s⁻¹ at 10 m depth to 405.8 ± 99.0 μmol m⁻² s⁻¹ at 3 m water depth) on sediment with low carbonate (mean 9.24 ± 1.74 percentage dry weight), organic matter (mean 2.56 ± 0.35 percentage dry weight) and silt-clay content (mean 2.28 ± 2.43 percentage dry weight). The literature reveals that there is a range of drivers operating in Southeast Asian seagrass systems and we suggest that this is because there are various types of seagrass habitats in this region, i.e. backreef, forereef and estuary, each of which has site characteristics and ecological drivers unique to it. Based on our case study of Pulau Tinggi, we suggest that seagrasses in forereef systems are more widespread in Southeast Asia than is reflected in the literature and that they are likely to be driven by recurring disturbance events such as monsoons, sediment burial and herbivory.     

Structural and nonstructural performance of a seismically isolated building using stable unbonded fiber‐reinforced elastomeric isolators

Stable unbonded fiber‐reinforced elastomeric isolators (SU‐FREIs) exhibit a characteristic horizontal softening and stiffening response, similar to other adaptive devices such as the triple friction pendulum and sliding systems with variable curvature. The transition between the softening and stiffening occurs at a displacement corresponding to a unique deformation known as full rollover. In this paper, the full rollover displacement of SU‐FREIs is altered by using modified support geometry (MSG), a geometric modification of the upper and lower supports applied to tailor the hysteresis loops of the isolator. Experimental results are used to calibrate a numerical model of a base‐isolated structure. The model demonstrates that the stiffening regime provides minimal restraint against displacements during events that meet or exceed the maximum considered earthquake. A parametric study revealed that the level of stiffening required to restrain displacements during large events is significant. This increase in stiffness is reflected in an increase in the response of the structure and light nonstructural components. Full rollover and MSG is considered advantageous to maintain horizontal stability and provide control over the stiffening of SU‐FREIs. Copyright © 2015 John Wiley & Sons, Ltd.     

Origin of halite brine in the Onondaga Trough near Syracuse,New York State,USA: modeling geochemistry and variable-density flow

Halite brine (saturation ranging from 45 to 80%) lies within glacial sediments that fill the Onondaga Trough, a bedrock valley deepened by Pleistocene glaciation near Syracuse, New York State, USA. The most concentrated brine occupies the northern end of the trough, about 10 km downgradient of the northern limit of halite beds in the Silurian Salina Group, the assumed source of salt. The chemical composition of the brine and its radiocarbon age suggest that the brine originally formed about 16,700  years ago through dissolution of halite by glacial melt water and later mixed with saline bedrock water. Two hypotheses regarding the formation of the brine pool were tested through variable-density flow simulations using SEAWAT. Simulation results supported the first hypothesis that the brine pool was derived from a source in the glacial sediments and then migrated to its current position, where it has persisted for over 16,000  years. A second hypothesis that the brine pool formed through steady accumulation of brine from upward flow of a source in the underlying bedrock was not supported by simulation results, because the simulated age distribution was much younger than the age estimated from geochemical modeling.     

The solubilities of calcite,aragonite and vaterite in CO2-H2O solutions between 0 and 90°C,and an evaluation of the aqueous model for the system CaCO3-CO2-H2O

Calculations based on approximately 350 new measurements (Ca_T-PCO₂) of the solubilities of calcite, aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants K_C, K_A, and K_V respectively, for the reaction CaCO₃(s) = Ca²⁺ + CO^2?₃: $\text{Log K}{}_{\mathrm{C}}\text{= ?171.9065 ? 0.077993T +}\text{2839.319}\text{T}\text{+ 71.595 log T}$$\text{Log K}{}_{\mathrm{A}}\text{= ?171.9773 ? 0.077993T +}\text{2903.293}\text{T}\text{+71.595 log T}$$\text{Log K}{}_{\mathrm{V}}\text{= ?172.1295 ? 0.077993T +}\text{3074.688}\text{T}\text{+ 71.595 log T}$ where T is in ^oK. At 25°C the logarithms of the equilibrium constants are ?8.480 ± 0.020, ?8.336 ± 0.020 and ?7.913 ± 0.020 for calcite, aragonite and vaterite, respectively.The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO⁺₃ and CaCO⁰₃ ion pairs, revised analytical expressions for CO₂-H₂O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO₂-dependence if the CaHCO⁺₃ association constant is between 0 and 90°C, corresponding to the value logK_Cahco⁺3 = 1.11 ± 0.07 at 25°C. The CaCO⁰₃ association constant was measured potentiometrically to be between 5 and 80°C, yielding logK_CaCO⁰3 = 3.22 ± 0.14 at 25°C.The CO₂-H₂O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of K_H, K₁ and K₂ are $\text{log K}{}_{\mathrm{H}}\text{= 108.3865 + 0.01985076T ?}\text{6919.53}\text{T}\text{? 40.45154 log T +}\text{669365.}\text{T}{}^2$, $\text{log K}{}_1\text{= ?356.3094 ? 0.06091964T +}\text{21834.37}\text{T}\text{+ 126.8339 log T —}\text{1684915.}\text{T}{}^2$ and logK₂ = ?107.8871 ? 0.03252849T + 5151.79/T + 38.92561 logT ? 563713.9/T² which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures.Extensive measurements of the pH of Ca-HCO₃ solutions at 25°C and 0.956 atm PCO₂ using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH.Earlier arguments suggesting that the CaHCO⁺₃ ion pair should not be included in the CaCO₃-CO₂-H₂O aqueous model were based on less accurate calcite solubility data. The CaHCO⁺₃ ion pair must be included in the aqueous model to account for the observed PCO₂-dependence of aragonite solubility between 317 ppm CO₂ and 100% CO₂.Previous literature on the solubility of CaCO₃ polymorphs have been critically evaluated using the aqueous model and the results are compared.     

Hydrochemical tracers in the middle Rio Grande Basin,USA: 1. Conceptualization of groundwater flow

Chemical and isotopic data for groundwater from throughout the Middle Rio Grande Basin, central New Mexico, USA, were used to identify and map groundwater flow from 12 sources of water to the basin, evaluate radiocarbon ages, and refine the conceptual model of the Santa Fe Group aquifer system.Hydrochemical zones, representing groundwater flow over thousands to tens of thousands of years, can be traced over large distances through the primarily siliciclastic aquifer system. The locations of the hydrochemical zones mostly reflect the modern predevelopment hydraulic-head distribution, but are inconsistent with a trough in predevelopment water levels in the west-central part of the basin, indicating that this trough is a transient rather than a long-term feature of the aquifer system. Radiocarbon ages adjusted for geochemical reactions, mixing, and evapotranspiration/dilution processes in the aquifer system were nearly identical to the unadjusted radiocarbon ages, and ranged from modern to more than 30 ka. Age gradients from piezometer nests ranged from 0.1 to 2 year cm^–1 and indicate a recharge rate of about 3 cm year^–1 for recharge along the eastern mountain front and infiltration from the Rio Grande near Albuquerque. There has been appreciably less recharge along the eastern mountain front north and south of Albuquerque.

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Resumen Se utilizaron datos químicos e isotópicos de agua subterránea a lo largo de la cuenca central del río Grande, Nuevo México, EEUU, para identificar y mapear el flujo de agua subterránea de 12 fuentes de agua a la cuenca para evaluar edades por medio de radio carbon y para refinar el modelo conceptual del sistema acuífero del Grupo Santa Fé. Se puede establecer zonas hidrotérmicas que representan el flujo de agua subterránea a lo largo de miles a miles de decenas de años en grandes distancias a través del sistema acuífero principalmente siliclástico. Las ubicaciones de las zonas hidroquímicas mayormente reflejan la distribucion de la cabeza hidráulica pre-desarollo moderna pero son inconsistentes con una depresión en los niveles de agua pre-desarollo en la zona central oeste de la cuenca. Esto indica que esta depresión es un rasgo transitorio y no un rasgo de largo plazo del sistema acuífero. Las edades de radio carbon ajustadas para los procesos de reaciones geoquímicas, de mezclado y de evapotranspiración-dilución son casi idénticas a los edades de radio carbon no ajustadas oscilan en un rango desde la modernidad a 30 mil años. Las gradientes de edad de nidos de piezometros van de 0.1 a 2 años cm^–1 e indican un sitio de recarga de aproximadamente 3 cm/yr para la recarga a lo largo del frente montañoso oriental e infiltración del río Grande cerca de Albuquerque. Se aprecia una recarga menor a lo largo del frente oriental de montañas al norte y al sur de Albuquerque.

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Résumé Des données sur les éléments chimiques et les isotopes présents dans leau souterraine prélevée à divers endroits dans le bassin moyen du Rio Grande, au centre du Nouveau-Mexique (É-U), ont permis de déterminer lexistence et létendue de douze sources deau régionales dans le bassin, dévaluer les âges radiocarbones et de raffiner le modèle conceptuel du système aquifère du groupe de Santa Fe. Des zones hydro-chimiques qui représentent lécoulement de leau souterraine depuis des dizaines de milliers dannées peuvent être suivies sur de longues distances à travers laquifère principalement siliclastique. La position des zones hydro-chimiques reflète principalement la distribution moderne des charges hydrauliques mais est incohérente avec une dépression dans le niveau deau dans la partie centre-ouest du bassin, ce qui indique que cette dépression est un élément transitoire du système aquifère plutôt quun élément à long terme. Les âges radiocarbones ajustés aux réactions géochimiques et aux processus de mélange et dévapotranspiration/dilution qui ont lieu dans laquifère sont presque identiques aux âges non ajustés et varient de la période moderne jusquà 30 ka. Les gradients dâge établis à partir des nids de piézomètres sétendent de 0.1 à 2 a cm^–1 et suggèrent un taux de recharge denviron 3 cm a^–1 le long du front des montagnes à lest et pour linfiltration provenant du Rio Grande près dAlbuquerque. Il y a eu substantiellement moins de recharge le long du front des montagnes à lest, au nord et au sud dAlbuquerque.

     

Ulysses observations of cosmic gamma-ray bursts

We review the current status of the Ulysses mission and summarize the results to date of the GRB experiment. This instrument detects bursts at the rate of about one every 3.5 days, and the localization data are being disseminated rapidly via the BACO-DINE and NMSU networks. The mission should operate through 2001, and future missions to Mars starting in 1996 will complete the 3rd Interplanetary Network.     

Solar hard X-ray and γ-ray bursts observed by the sigma anti-coincidence shield aboard granat

The anti-coincidence shield of the SIGMA telescope aboard GRANAT provides observations of solar X-ray and -ray bursts in the energy range 200 keV–15 MeV. The characteristics of the experiment are presented here as well as the observations of the solar bursts detected during the first year of operation. Among these events, two of these bursts associated respectively with a limb and a disk flare were observed with significant flux above 10 MeV. Advantage is taken of the experiment large detector area to examine fine time structures even at high energies ( 10 MeV).     

The November 22, 1977 solar flare: Evidence for 2.23 and 4.43 MeV line emission from the signe 2MP experiment

The November 22, 1977 solar flare was observed at energies up to 4.9 MeV by French-built gamma ray detectors aboard the Soviet Prognoz-6 satellite. The data show evidence for 2.23 and 4.43 MeV line emission, with the 2.23 MeV emission occurring about 3 min after the flare onset in hard X-rays. The line intensities, 0.11 cm^–2s^–1 and 0.06 cm^–2s^–1 for the 2.23 and 4.43 lines, respectively, are roughly comparable to intensities observed in other events. Particle detectors aboard the Prognoz-6 satellite, however, recorded a proton flux much lower than that observed for the 4 August 1972 event. It is shown that this may be taken as evidence for a thick target interpretation of the proton interactions in the solar atmosphere.     

High-resolution stratigraphy and turbidite processes in the Seine Abyssal Plain, northwest Africa

 Seine Abyssal Plain sediments consist of turbidites interbedded with pelagic oozes, marls, and clays. The pelagics produce a high-resolution integrated stratigraphy combining oxygen isotope, carbonate curves, palaeotemperature analyses, and nannofossil acme zone stratigraphy. Individual turbidites could then be correlated. Isogram and isopach maps of the turbidites maximum median grain size and thickness, respectively, were used to identify turbidity current pathways and study their depositional processes. Nannofossil fingerprints were used to study possible sedimentary links between the Seine and Madeira abyssal plains. Received: 8 February 1996 / Revision received: 9 May 1996