Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (a_w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a_w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO₄·12H₂O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.     

Isotopic variability in the aragonite shells of freshwater gastropods living in springs with nearly constant temperature and isotopic composition

We conducted a year-long, intensive monitoring program of live aquatic gastropods (Helisoma duryi, Melanoides tuberculata, Physa virgata, Pyrgulopsis sp., and Tyronia sp.) and their host springs in the Ash Meadows National Wildlife Refuge of southern Nevada. Our purpose was to constrain the degree of natural variation in the isotopic values of shell aragonite for gastropods living in near-constant conditions. Inter- and intraspecies variations, as well as within-shell variations, of δ¹⁸O and δ¹³C values for all taxa were larger than predicted based on variations in environmental conditions alone. This result suggests that different organisms growing in identical or nearly identical environmental conditions may not produce shells with equilibrium isotopic compositions and that these offsets from equilibrium may differ by small, but statistically significant amounts. For the gill-breathing, fully aquatic gastropods M. tuberculata, Pyrgulopsis sp., and Tyronia sp., the deviation of measured isotopic values compared to predicted values based on average environmental conditions were consistent with differences between taxa in the seasonal timing of shell growth. Measured values for the lung-breathing gastropods H. duryi and P. virgata were higher for δ¹⁸O and lower for δ¹³C than predicted at isotopic equilibrium, even when accounting for seasonality effects. We suggest that explaining the differences between the shell isotopic composition of lung- and gill-breathing snails requires a combination of both behavioral and physiologic factors. Our results illustrate the potential complexities of interpreting stable isotopic data from fossil gastropod shells even when environmental conditions are nearly constant, and place limitations on the paleoenvironmental deductions that can be made from the isotopic measurements on fossil gastropods.     

“Extreme boiling” model for variable salinity of the Hokko low-sulfidation epithermal Au prospect, southwestern Hokkaido, Japan

The Hokko prospect is located in the Minamikayabe area southwestern Hokkaido, Japan, where gold-bearing quartz veins of Pliocene age are exposed at the surface. The alteration mineral assemblage is typical of low-sulfidation epithermal systems, with the quartz veins associated with adularia alteration overprinted on Late Miocene propylitic alteration. Fluid inclusion studies of the vein quartz reveal mean homogenization temperatures of approximately 220 °C, and the co-existence of low-salinity (<2 wt.% NaCl equivalent) and moderate salinity (2 to 12 wt.% NaCl equivalent) fluid inclusions within the same veins. The moderate salinity fluid inclusions (2–12 wt.% NaCl equivalent) typically have relatively low homogenization temperatures between 150° to 200 °C. The results obtained from stable isotope analysis of  δ¹⁸O in quartz vein material showed a gradual decrease in  δ¹⁸O signatures with increasing depth. The majority of the samples have calculated fluid source signatures (δ¹⁸O_H2O) between −8.0 and −10.0‰, but there is a significant change in the composition above 185 m drill depth. The shallower samples in particular show a wide range of oxygen isotope signatures that are associated with the moderate salinity fluid inclusions. We interpret that low-salinity inclusions within the Hokko system represent the composition of the liquid phase of the fluid, before boiling, and that the moderate-salinity inclusions are representative of the residual liquid phase, after extensive non-adiabatic boiling and vapor loss in an open system. This mechanism resulted in the entrapment of fluids with variable salinities at the same time, and in close proximity to each other. This is also reflected in the  δ¹⁸O_H2O values which become more variable and heavier where the moderate-salinity inclusions occur. Deposition of ore minerals within the Hokko vein system also occurred at this time as a result of boiling and gas loss. Received: 30 May 1997 / Accepted: 6 January 1998     

Chemical classification of iron meteorites—VIII. Groups IC. IIE,IIIF and 97 other irons

Concentrations of Ni, Ga, Ge and Ir in 106 iron meteorites are reported. Three new groups are defined: IC, IIE and IIIF containing 10, 12 and 5 members, respectively, raising the number of independent groups to 12. Group IC is a cohenite-rich group distantly related to IA. Group IIE consists of those irons previously designated Weekeroo Station type and five others having similar compositions though diverse structures. The IIE irons are compositionally similar to the mesosiderites and pallasites, and the three groups probably formed at similar heliocentric distances. The mixing of the globular IIE silicates with the metal probably occurred during shock events. Group IIIF is a well-defined group of low-Ni and low-Ge irons. The compositions of these groups are summarized as follows:

     

36.

Ecosystem Responses of a Tidal Freshwater Marsh Experiencing Saltwater Intrusion and Altered Hydrology   总被引：5，自引：0，他引：5  

Scott C. Neubauer 《Estuaries and Coasts》2013,36(3):491-507

Tidal freshwater marshes exist in a dynamic environment where plant productivity, subsurface biogeochemical processes, and soil elevation respond to hydrological fluctuations over tidal to multi-decadal time scales. The objective of this study was to determine ecosystem responses to elevated salinity and increased water inputs, which are likely as sea level rise accelerates and saltwater intrudes into freshwater habitats. Since June 2008, in situ manipulations in a Zizaniopsis miliacea (giant cutgrass)-dominated tidal freshwater marsh in South Carolina have raised porewater salinities from freshwater to oligohaline levels and/or subtly increased the amount of water flowing through the system. Ecosystem-level fluxes of CO₂ and CH₄ have been measured to quantify rates of production and respiration. During the first 20 months of the experiment, the major impact of elevated salinity was a depression of plant productivity, whereas increasing freshwater inputs had a greater effect on rates of ecosystem CO₂ emissions, primarily due to changes in soil processes. Net ecosystem production, the balance between gross ecosystem production and ecosystem respiration, decreased by 55% due to elevated salinity, increased by 75% when freshwater inputs were increased, and did not change when salinity and hydrology were both manipulated. These changes in net ecosystem production may impact the ability of marshes to keep up with rising sea levels since the accumulation of organic matter is critical in allowing tidal freshwater marshes to build soil volume. Thus, it is necessary to have regional-scale predictions of saltwater intrusion and water level changes relative to the marsh surface in order to accurately forecast the long-term sustainability of tidal freshwater marshes to future environmental change.     

37.

Two-stage collision-related extrusion of the western Dabie HP–UHP metamorphic terranes, central China: Evidence from quartz c-axis fabrics and structures     

Sanzhong Li  Timothy M. Kusky  Xiaochun Liu  Guowei Zhang  Guochun Zhao  Lu Wang  Yuejun Wang 《Gondwana Research》2009,16(2):294

The western Dabie orogen (also known as the Hong'an block) forms the western part of the Dabie–Sulu HP–UHP belt, central China. Rocks of this orogen have been subjected to pervasive ductile deformation, and include numerous quartz schists and felsic mylonites cropping out in ductile shear zones. Quartz textures in these mylonites contain important clues for understanding the movement sense of late-collisional extrusion and exhumation of high-pressure–ultrahigh-pressure (HP–UHP) rocks from the lower crustal level to the upper crustal level during Middle Triassic and Early Jurassic. The orientation and distribution of quartz crystallographic axes were used to confirm the regional shear sense across the orogen. The asymmetry of c-axis patterns consistently indicates top-to-the-southeast thrusting across the orogen in early structural stages. Later stages of deformation show different senses of movement in northern and southern parts of the orogen, with top-to-the-northwest sinistral shearing recorded in rocks north of the Xinxian HP–UHP eclogite-facies belt, and top-to-the-southeast dextral shearing south of the same unit.Based on our study on quartz c-axis fabrics and marco- to micro-scale structures, simultaneous southeastward shearing within a large part of the orogen and normal faulting north of the Xinxian HP–UHP unit is explained by upward extrusion in early stages of deformation. The extrusion process has been attributed to syn- and late-collisional processes, accounting for some earlier deformation in the western Dabie orogen such as metamorphic sequences around the core of the Xinxian HP–UHP eclogite-facies unit. Much higher pressure of deformation is also indicated in the aligned glaucophane and omphacite from blueschist and eclogite in the field. An orogen-parallel eastward extrusion of the Xinxian HP–UHP eclogite-facies unit, however, occurred diachronously in later stages of deformation. Therefore, a tectonic model combining an early upward extrusion with a later eastward extrusion is presented. Two different stages and types of extrusion for exhumation of HP–UHP rocks are suitable to all of east central China. Geochronological data shows that the first, upward extrusion occurred during Middle Triassic, the second, eastward extrusion occurred during Late Triassic to Early Jurassic. These two extrusions are correlative with two stages of rapid exhumation of the Dabie HP–UHP rocks, respectively. These two-stage late-collisional (Middle Triassic to Early Jurassic) extrusion events bridge the gap between syn-collisional (Early to Middle Triassic) vertical extrusion and post-collisional (Cretaceous) eastward-directed lateral escape and provide vital clues to understanding the more detailed processes of exhumation of HP–UHP rocks.     

38.

Volcano monitoring in NZ and links to SW Pacific via the Wellington VAAC   总被引：1，自引：0，他引：1  

Bradley J. Scott  James Travers 《Natural Hazards》2009,51(2):263-273

Monitoring for natural hazards like earthquakes, volcanic eruptions and landslides in New Zealand is under taken by GNS Science through the GeoNet project, funded by the Earthquake Commission (EQC). The volcano monitoring function, which includes seismograph and GPS networks, visual observations, webcams, deformation, gas and chemical measurements, assesses the status of New Zealand’s 12 active volcanoes and disseminates warnings as necessary. Interaction with the Wellington VAAC addresses aviation concerns. Near-real-time data is obtained from the monitoring networks and processed via two data centres, with two Duty Officers who respond to pager alerts. Through the National Civil Defence Plan, the volcano monitoring function is delegated to GNS Science, which is responsible for setting the volcanic alert level at each volcano. The Alert level is then used by responding agencies, industries, utility providers and the public to set their response. The New Zealand alert level system is based on the current status of the volcano, and is not necessarily predictive. The aviation industry is one of these responding industries. As a consequence of the 1995 and 1996 eruptions of Ruapehu volcano, it became apparent that the aviation industry required more information than the standard VAAC data and an additional service known as VAAS (NZ Volcanic Ash Advisory System) was established by MetService NZ and GNS Science. This arrangement provides enhanced services to the airlines and ensures rapid dissemination and quantification of information like SIGMET and NOTAM. GNS Science has informal relationships with similar geological based organisations in SW Pacific countries, especially Vanuatu and the Solomon Islands, and is able to quantify information about eruptions in those countries. Similarly, MetService NZ has relationships and is able to obtain pilot reports and updates from the meteorological and air traffic control organisations.     

39.

Salinity stratification in a river-dominated estuary   总被引：1，自引：0，他引：1  

William W. Schroeder  Scott P. Dinnel  William J. Wiseman 《Estuaries and Coasts》1990,13(2):145-154

Analysis of salinity data from Mobile Bay indicates that stratification-destratification events within this broad, shallow estuary are not uncommon. These events are related to the strength of the winds, through their influence on wave generation and subsequent bottom drag coefficient increases, and to the strength of river discharge. They do not appear to be due to the strength of tidal currents, as has been observed elsewhere. Furthermore, river flow appears to be the dominant control, the winds being important only in the absence of large freshwater discharges. The annual spring freshet can flush most of the salt from the bay. During other times of the year the relative strengths of river discharge and wind stress change the bay from highly stratified to nearly homogeneous and back on a variety of time scales ranging from daily to seasonal.     

40.

RAGLAND,AN LL3.4 CHONDRITE FIND FROM NEW MEXICO     

S.I. Recca  E.R.D. Scott  K. Keil  R.N. Clayton  T.K. Mayeda  G.I Huss  E. Jarosewich  K.S. Weeks  F.A. Hasan  D.W.G. Sears  R. Wieler  P. Signer 《Meteoritics & planetary science》1986,21(2):217-229

The Ragland, New Mexico chondrite was found in 1978, and consists of a single stone of 12.16 kg that broke into three pieces. The stone is moderately weathered and has a pronounced chondritic texture. Bulk composition favors an LL classification, and modal analysis and oxygen isotopic composition are consistent with this. The thermoluminescence sensitivity of 0.056 ± 0.020 normalized to Dhajala, compositional variability of olivine (mean Fa 18.3, σ = 10.1) and low-Ca pyroxene (mean Fs 14.6, σ = 6.7), and Ca concentrations in olivine indicate metamorphic subtype 3.4 ± 0.1. The isotopically heavy oxygen composition, which is characteristic of subtypes 3.0–3.1, may be a primary characteristic and not a result of weathering. Low concentrations of radiogenic ⁴⁰Ar and planetary ³⁶Ar suggest noble gas loss.     

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Group	Ni (%)	Ga (ppm)	Ge (ppm)	Ir (ppm)
IC	6.1–6.8	42–54	85–250	0.07–10
IIE	7.5–9.7	21–28	62–75	0.5–8
IIIF	6.8–7.8	6.3–7.2	0.7–1.1	1.3–7.9

Ecosystem Responses of a Tidal Freshwater Marsh Experiencing Saltwater Intrusion and Altered Hydrology

Tidal freshwater marshes exist in a dynamic environment where plant productivity, subsurface biogeochemical processes, and soil elevation respond to hydrological fluctuations over tidal to multi-decadal time scales. The objective of this study was to determine ecosystem responses to elevated salinity and increased water inputs, which are likely as sea level rise accelerates and saltwater intrudes into freshwater habitats. Since June 2008, in situ manipulations in a Zizaniopsis miliacea (giant cutgrass)-dominated tidal freshwater marsh in South Carolina have raised porewater salinities from freshwater to oligohaline levels and/or subtly increased the amount of water flowing through the system. Ecosystem-level fluxes of CO₂ and CH₄ have been measured to quantify rates of production and respiration. During the first 20 months of the experiment, the major impact of elevated salinity was a depression of plant productivity, whereas increasing freshwater inputs had a greater effect on rates of ecosystem CO₂ emissions, primarily due to changes in soil processes. Net ecosystem production, the balance between gross ecosystem production and ecosystem respiration, decreased by 55% due to elevated salinity, increased by 75% when freshwater inputs were increased, and did not change when salinity and hydrology were both manipulated. These changes in net ecosystem production may impact the ability of marshes to keep up with rising sea levels since the accumulation of organic matter is critical in allowing tidal freshwater marshes to build soil volume. Thus, it is necessary to have regional-scale predictions of saltwater intrusion and water level changes relative to the marsh surface in order to accurately forecast the long-term sustainability of tidal freshwater marshes to future environmental change.     

Two-stage collision-related extrusion of the western Dabie HP–UHP metamorphic terranes, central China: Evidence from quartz c-axis fabrics and structures

The western Dabie orogen (also known as the Hong'an block) forms the western part of the Dabie–Sulu HP–UHP belt, central China. Rocks of this orogen have been subjected to pervasive ductile deformation, and include numerous quartz schists and felsic mylonites cropping out in ductile shear zones. Quartz textures in these mylonites contain important clues for understanding the movement sense of late-collisional extrusion and exhumation of high-pressure–ultrahigh-pressure (HP–UHP) rocks from the lower crustal level to the upper crustal level during Middle Triassic and Early Jurassic. The orientation and distribution of quartz crystallographic axes were used to confirm the regional shear sense across the orogen. The asymmetry of c-axis patterns consistently indicates top-to-the-southeast thrusting across the orogen in early structural stages. Later stages of deformation show different senses of movement in northern and southern parts of the orogen, with top-to-the-northwest sinistral shearing recorded in rocks north of the Xinxian HP–UHP eclogite-facies belt, and top-to-the-southeast dextral shearing south of the same unit.Based on our study on quartz c-axis fabrics and marco- to micro-scale structures, simultaneous southeastward shearing within a large part of the orogen and normal faulting north of the Xinxian HP–UHP unit is explained by upward extrusion in early stages of deformation. The extrusion process has been attributed to syn- and late-collisional processes, accounting for some earlier deformation in the western Dabie orogen such as metamorphic sequences around the core of the Xinxian HP–UHP eclogite-facies unit. Much higher pressure of deformation is also indicated in the aligned glaucophane and omphacite from blueschist and eclogite in the field. An orogen-parallel eastward extrusion of the Xinxian HP–UHP eclogite-facies unit, however, occurred diachronously in later stages of deformation. Therefore, a tectonic model combining an early upward extrusion with a later eastward extrusion is presented. Two different stages and types of extrusion for exhumation of HP–UHP rocks are suitable to all of east central China. Geochronological data shows that the first, upward extrusion occurred during Middle Triassic, the second, eastward extrusion occurred during Late Triassic to Early Jurassic. These two extrusions are correlative with two stages of rapid exhumation of the Dabie HP–UHP rocks, respectively. These two-stage late-collisional (Middle Triassic to Early Jurassic) extrusion events bridge the gap between syn-collisional (Early to Middle Triassic) vertical extrusion and post-collisional (Cretaceous) eastward-directed lateral escape and provide vital clues to understanding the more detailed processes of exhumation of HP–UHP rocks.     

Volcano monitoring in NZ and links to SW Pacific via the Wellington VAAC

Monitoring for natural hazards like earthquakes, volcanic eruptions and landslides in New Zealand is under taken by GNS Science through the GeoNet project, funded by the Earthquake Commission (EQC). The volcano monitoring function, which includes seismograph and GPS networks, visual observations, webcams, deformation, gas and chemical measurements, assesses the status of New Zealand’s 12 active volcanoes and disseminates warnings as necessary. Interaction with the Wellington VAAC addresses aviation concerns. Near-real-time data is obtained from the monitoring networks and processed via two data centres, with two Duty Officers who respond to pager alerts. Through the National Civil Defence Plan, the volcano monitoring function is delegated to GNS Science, which is responsible for setting the volcanic alert level at each volcano. The Alert level is then used by responding agencies, industries, utility providers and the public to set their response. The New Zealand alert level system is based on the current status of the volcano, and is not necessarily predictive. The aviation industry is one of these responding industries. As a consequence of the 1995 and 1996 eruptions of Ruapehu volcano, it became apparent that the aviation industry required more information than the standard VAAC data and an additional service known as VAAS (NZ Volcanic Ash Advisory System) was established by MetService NZ and GNS Science. This arrangement provides enhanced services to the airlines and ensures rapid dissemination and quantification of information like SIGMET and NOTAM. GNS Science has informal relationships with similar geological based organisations in SW Pacific countries, especially Vanuatu and the Solomon Islands, and is able to quantify information about eruptions in those countries. Similarly, MetService NZ has relationships and is able to obtain pilot reports and updates from the meteorological and air traffic control organisations.     

Salinity stratification in a river-dominated estuary

Analysis of salinity data from Mobile Bay indicates that stratification-destratification events within this broad, shallow estuary are not uncommon. These events are related to the strength of the winds, through their influence on wave generation and subsequent bottom drag coefficient increases, and to the strength of river discharge. They do not appear to be due to the strength of tidal currents, as has been observed elsewhere. Furthermore, river flow appears to be the dominant control, the winds being important only in the absence of large freshwater discharges. The annual spring freshet can flush most of the salt from the bay. During other times of the year the relative strengths of river discharge and wind stress change the bay from highly stratified to nearly homogeneous and back on a variety of time scales ranging from daily to seasonal.     

RAGLAND,AN LL3.4 CHONDRITE FIND FROM NEW MEXICO

The Ragland, New Mexico chondrite was found in 1978, and consists of a single stone of 12.16 kg that broke into three pieces. The stone is moderately weathered and has a pronounced chondritic texture. Bulk composition favors an LL classification, and modal analysis and oxygen isotopic composition are consistent with this. The thermoluminescence sensitivity of 0.056 ± 0.020 normalized to Dhajala, compositional variability of olivine (mean Fa 18.3, σ = 10.1) and low-Ca pyroxene (mean Fs 14.6, σ = 6.7), and Ca concentrations in olivine indicate metamorphic subtype 3.4 ± 0.1. The isotopically heavy oxygen composition, which is characteristic of subtypes 3.0–3.1, may be a primary characteristic and not a result of weathering. Low concentrations of radiogenic ⁴⁰Ar and planetary ³⁶Ar suggest noble gas loss.