Oxygen diffusion rates in quartz exchanged with CO2

Oxygen self diffusion rates were determined in quartz samples exchanged with¹⁸O-enriched CO₂ between 745 and 900°C and various pressures, and the diffusion profiles were measured using an ion microprobe. The activation energy (Q) and preexponential factor (D₀) at P(CO₂) = P(tot) = 100 bar, for diffusion parallel to the c-axis are 159 ( ± 13) kJ/g atom and 2.10 (+0.75/ −0.55) × 10⁻⁸ cm²/s. This rate is approximately 100 times slower than that obtained from hydrothermal experiments and 100 times faster than a previous 1-bar quartz-O₂ exchange experiment. The oxygen diffusion rate measured at 0.6 bar, 888°C, and at 900°C in vacuum is in agreement with the previous 1-bar exchange experiments with¹⁸O₂. The effect of higher CO₂ pressures is small. At 900°C, the diffusion rate exchanged with CO₂ is = 2.35 × 10⁻¹⁵ cm²/s at 100 bar, 2.24 × 10⁻¹⁵ cm²/s at 3.45 kbar and 8.13 × 10⁻¹⁵ cm²/s at 7.2 kbar.There is probably a diffusing species, other than oxygen, that enhances the oxygen diffusion rate in these quartz-CO₂ systems, relative to that occurring at very low pressures or in a vacuum. The effect of this diffusing species, however, is not as strong as that associated with H₂O. Preserved oxygen isotope fractionations between coexisting minerals in a slowly cooled, high-grade metamorphic terrane will vary depending upon whether a water-rich phase was present or not. Closure temperatures will be approximately 100°C higher in rocks where no water-rich phase was present during cooling. The measured fractionations between coexisting minerals in metamorphic rocks may potentially be used as a sensor of water presence during retrogression.     

Crustal neon: a striking uniformity

By combining data from a diverse suite of crustal fluid samples representing a broad geographical distribution, we have identified a well-defined nucleogenic (crustal) neon component. The neon is produced from (α, n) and (n, α) nuclear interactions involving nuclei of O, Mg, and F [1]. In the limiting case of ²⁰Ne/²²Ne = 0, the composition is: ²¹Ne/²²Ne = 0.47 ± 0.01 and ²¹Ne/⁴He = (0.46 ± 0.08) × 10⁻⁷. A crustal O/F ratio of 110 (atomic) calculated from the ²¹Ne/²²Ne ratio is 4–10 times less than the average crustal O/F ratio. The discrepancy can be accounted for by an enhanced O/F ratio within the 10–40 μm range of the U-Th-generated α-particles.     

O/O mapping and hydrogeology of a short-lived (≈10 years) fumarolic (>500°C) meteoric–hydrothermal event in the upper part of the 0.76 Ma Bishop Tuff outflow sheet, California

¹⁸O/¹⁶O data from the 200-m-thick, 0.76 Ma Bishop Tuff outflow sheet provide evidence for a vigorous, short-lived (≈10 years), high-temperature, fumarolic meteoric–hydrothermal event. This is proved by: (1) the juxtaposition in the upper, partially welded Bishop Tuff of low-¹⁸O groundmass/glass (δ¹⁸O=−5 to +3) with coexisting quartz and feldspar phenocrysts having magmatic δ¹⁸O values (+8.7±0.3; +7.5±0.3); and (2) the fact that these kinds of ¹⁸O/¹⁶O signatures correlate very well with morphological features and mapped zones of fumarolic activity. Profiles of δ¹⁸O with depth in the Bishop Tuff within the fumarole area define a 40- to 50-m-thick, low-¹⁸O, stratigraphic zone that is sandwiched between the essentially unwelded near-surface portion of the tuff and an underlying, densely welded black tuff that displays magmatic ¹⁸O/¹⁶O values. Shallow-dipping columnar joints and other fumarolic features (i.e., subhorizontal tubular conduits and steep fissures) correlate very well with these pervasively devitrified, low-¹⁸O zones. The base of the low-¹⁸O zone is extremely sharp (3‰ per meter) and is located directly above the transition from partially welded tuff to densely welded black tuff. The observed average whole-rock ¹⁸O-depletions within this low-¹⁸O zone are about 6–7‰, requiring meteoric water/rock ratios in excess of 0.24 in mass units. Rainfall on the surface of the tuff would not have been high enough to supply this much H₂O in the short lifetime of fumarolic activity, suggesting that some recharge must have been from groundwater flow through the upper part of the tuff, above the sloping (1°–5°) top of the impermeable lower zone. This is compatible with the observation that the fumarolic areas roughly correlate with the preeruptive regional drainage pattern. Some of this recharge may in part have been from the lake that filled Long Valley caldera, which was dammed by the Bishop Tuff up to the level of this boundary between the partially and densely welded zones (≈7000 ft, the elevation of the highest Long Valley Lake shorelines). Gazis et al. had previously shown that the 2.8-Ma intracaldera Chegem Tuff from the Caucasus Mountains exhibits exactly the same kind of ¹⁸O-signature that we have correlated with fossil fumaroles in the Bishop Tuff outflow sheet. Although not recognized as such by McConnell et al.; ¹⁸O/¹⁶O data from drill-hole samples from the intracaldera Bishop Tuff in Long Valley also display this characteristic ¹⁸O signature (i.e., analogous δ¹⁸O-depth profiles, as well as low-¹⁸O groundmass coexisting with high-¹⁸O feldspar phenocrysts). This fumarolic ¹⁸O/¹⁶O signature is observed to much greater depths (≈650–750 m) in the intracaldera tuffs (≈1500 m thick) than it is in the ≈200-m-thick Bishop Tuff outflow sheet (≈80 m depth).     

Oxygen isotope evidence for past and present hydrothermal regimes of Long Valley caldera, California

Whole-rock oxygen isotope compositions of cores and cuttings from Long Valley exploration wells show that the Bishop Tuff has been an important reservoir for both fossil and active geothermal systems within the caldera. The deep Clay Pit-1 and Mammoth-1 wells on the resurgent dome penetrate mildly to strongly altered Bishop Tuff with δ¹⁸O_WR values as low as −2.6% (vs V-SMOW). The idfu 44-16 well intercepts a thinner Bishop Tuff section with δ¹⁸O_WR values of +0.4 to +2.3%. in the western caldera moat, where milder and more sporadic ¹⁸O depletions occur in Tertiary volcanic rocks of the western caldera floor (δ¹⁸O_WR = +2.2 to +6.4‰). Bishop Tuff samples from deeper parts of the 715 m rdo-8 (Shady Rest) well in the SW moat are also strongly depleted in ¹⁸O (δ¹⁸O_WR = −1.5 to +0.6‰). Four shallow thermal gradient wells (469–715 m td drilled in the western moat did not penetrate Bishop Tuff, but Early Rhyolites from two of these holes are depleted in ¹⁸O (δ¹⁸O_WR = −1.2 to +6.0‰ inplv-1 +4.6 to +5.3%. inmlgrap-1), compared to lithologic equivalents from the other two holes (δ¹⁸O_WR = +6.3 to +8.0‰ inplv-2 andmlgrap-2).Whole-rock oxygen isotope profiles for the resurgent dome wells are unlike profiles calculated assuming alkali feldspar-H₂O fractionation behavior and total O-isotopic equilibration with −14.3‰ fluids at measured temperatures. The sense of this divergence implies an earlier hydrothermal episode within the central caldera driven by one or more shallow intrusions. Geochemical similarities between an intrusive granophyre at the bottom of the Clay Pit-1 well and a nearby Moat Rhyolite dome with a K/Ar cooling age of 0.5 Ma suggest that vigorous hydrothermal activity beneath the central resurgent dome may have occurred as much as 0.5 m.y. ago. Calculated and measured O-isotope profiles are similar for deep wells that penetrate the western moat of the caldera, where steep temperature gradients and low δ¹⁸O_WR values in Early Rhyolites from plv-1 are attributed to an active hydrothermal aquifer that has descended slightly from earlier, shallower elevations. Similarly, severe ¹⁸O depletions in Bishop Tuff samples from the idfu 44-16 and rdo-8 wells reflect active convection beneath the western moat, whereas milder ¹⁸O depletions in Early Rhyolites from mlgrap-1 were apparently caused by hydrothermal alteration at lower temperatures. The O-isotope profiles imply that surface discharge within and around the resurgent dome results from shallow, eastward-directed outflow from a zone of higher enthalpy hydrothermal upflow beneath the western caldera moat. Intrusive magmatic heat source(s) are inferred to exist beneath the western moat, perhaps beneath Mammoth Mountain.     

Isotope geochemistry of minerals and fluids from Newberry volcano, Oregon

Isotopic compositions were determined for hydrothermal quartz, calcite, and siderite from core samples of the Newberry 2 drill hole, Oregon. The δ¹⁵O values for these minerals decrease with increasing temperatures. The values indicate that these hydrothermal minerals precipitated in isotopic equilibrium with water currently present in the reservoirs. The δ¹⁸O values of quartz and calcite from the andesite and basalt flows (700–932 m) have isotopic values which require that the equilibrated water δ¹⁸O values increase slightly (− 11.3 to −9.2‰) with increasing measured temperatures (150–265°C). The lithic tuffs and brecciated lava flows (300–700 m) contain widespread siderite. Calculated oxygen isotopic compositions of waters in equilibrium with siderite generally increase with increasing temperatures (76–100°C). The δ¹⁸O values of siderite probably result from precipitation in water produced by mixing various amounts of the deep hydrothermal water (− 10.5 ‰) with meteoric water (− 15.5 ‰) recharged within the caldera. The δ¹³C values of calcite and siderite decrease with increasing temperatures and show that these minerals precipitated in isotopic equilibrium with CO₂ of about −8 ‰.The δ¹⁸O values of weakly altered (<5% alteration of plagioclase) whole-rock samples decrease with increasing temperatures above 100°C, indicating that exchange between water and rock is kinetically controlled. The water/rock mass ratios decrease with decreasing temperatures. The δ¹⁸O values of rocks from the bottom of Newberry 2 show about 40% isotopic exchange with the reservoir water.The calculated δ¹⁸O and δD values of bottom hole water determined from the fluid produced during the 20 hour flow test are −10.2 and −109‰, respectively. The δD value of the hydrothermal water indicates recharge from outside the caldera.     

Diffusion of osmium in pyrrhotite and pyrite: implications for closure of the Re–Os isotopic system

In order to better constrain the extent to which common sulfide minerals will retain their osmium isotopic composition subsequent to crystallization, we have conducted experiments to quantify the diffusion behavior of osmium in pyrite and pyrrhotite. Experiments consisted of either (1) isothermal soaking of diffusion couples consisting of natural pyrite or pyrrhotite crystals packed against powdered Os-bearing Fe-sulfide or (2) ‘relaxation’ of initially high near-surface osmium concentrations produced in the latter experiments (pyrite only). Osmium penetration into samples was characterized by depth profiling using Rutherford backscattering spectroscopy (RBS) (pyrite) or electron microprobe analyses across sectioned run products (pyrrhotite). Results of the first type of diffusion experiment involving pyrite show only limited osmium penetration into sample surfaces, with the extent of penetration uncorrelated with run duration. Images of pyrite samples using atomic force microscopy show roughening of initially smooth surfaces as a consequence of step formation and suggest that osmium incorporation into the near-surface occurred by solute uptake during step growth and not by volume diffusion. Prolonged (1000⁺ h) ‘relaxation’ experiments revealed no additional osmium penetration into pyrite surfaces and based on the depth resolution for RBS, a maximum diffusion coefficient of 2.5×10⁻²³ m²/s at 500°C was calculated. Experiments involving pyrrhotite over the temperature range of 950–1100°C showed extensive osmium uptake and osmium concentration gradients that conform with Fickian diffusion behavior. We found that pyrrhotite Fe/S could be varied by changes in the composition of the starting material and osmium source and over the range of Fe/S produced in experiments (molar Fe/S=0.83–0.90), we observed no systematic variation in the osmium diffusion coefficient. Diffusion coefficients measured parallel to the a crystallographic axis were on average 1.4× higher than values measured parallel to c and regression of the c-axis data yielded the Arrhenius relation:

The application of these diffusion data to simple models of diffusive exchange during static or polythermal time–temperature histories is used to assess the conditions under which radiogenic osmium will be retained. During isothermal annealing, calculations indicate that the cores of millimeter-sized spherical pyrrhotite crystals undergoing diffusive exchange with an external osmium reservoir will have their initial compositions perturbed in ≤0.5 Ma at temperatures exceeding 400°C. Pyrite undergoing the same process at 500°C requires in excess of 10 Ma before crystal cores are affected. The relatively short ‘core retention’ time-scales for pyrrhotite indicates that this mineral may be prone to isotopic resetting following relatively brief crustal thermal events, thus possibly accounting for the scatter that commonly occurs in Re–Os isochrons generated from massive sulfide samples. Calculated closure temperatures (T_c) for osmium exchange in pyrrhotite yielded values of 300–400°C for grain sizes ranging from 10 to 1000 μm. These values of T_c are similar to those calculated for Ar retention in biotite, and considerably lower than for Sr in apatite and plagioclase, for example. Such low closure temperatures for pyrrhotite suggest this mineral will date the final stage in the cooling of a magmatic system and possibly be susceptible to open system osmium exchange in the presence of late-stage hydrothermal fluids. This latter result infers that caution be applied when interpreting elevated initial osmium isotopic ratios as a product of crustal assimilation at the magmatic stage.     

Earthquake-induced variations in the composition of the water in the geothermal reservoir at Vulcano Island, Italy

During 1979–1989, variations were observed in the oxygen composition of the water contained in the geothermal reservoir at Vulcano Island, Italy.The reservoir water, that has a magmatic origin, showed an oxygen composition of +1.0±0.5‰ δ¹⁸O during periods without local tectonic earthquakes, and an oxygen composition of +3.4±0.5‰ δ¹⁸O after the highest-energy seismic activity that occurred recently near the island. A slight increase of the δ¹⁸O value in the reservoir water was also observed after a low-energy sequence of tectonic earthquakes that occurred at very shallow depth just beneath Vulcano Island. These ¹⁸O variations in the reservoir water are consistent with earthquake-induced increases in the contribution from high-temperature δ¹⁸O-rich magmatic condensate to the geothermal reservoir, and with subsequent decreases in the δ¹⁸O value due to ¹⁸O exchanges at the temporarily increased reservoir temperature during reactions between the highly reactive magmatic condensate and the local rocks.Only minor changes in the deuterium composition of the reservoir water occurred with time, as the δD value in the magmatic condensate released from the magma after major local earthquakes quickly approached the δD value of the water contained in the geothermal reservoir.Also the chloride concentration in the reservoir water appears to be linked to the contribution from the magmatic fluid. This chloride content seems not to have undergone major changes with time, as it may be buffered by temporary increases in the reservoir temperature up to values >300°C induced by major local earthquakes. This mechanism may possibly occur also in other magmatic–hydrothermal systems.     

An anomalous subauroral red arc on 4 August, 1972: comparison of ISIS-2 satellite data with numerical calculations

This study compares the Isis II satellite measurements of the electron density and temperature, the integral airglow intensity and volume emission rate at 630 nm in the SAR arc region, observed at dusk on 4 August, 1972, in the Southern Hemisphere, during the main phase of the geomagnetic storm. The model results were obtained using the time dependent one-dimensional mathematical model of the Earth’s ionosphere and plasmasphere (the IZMIRAN model). The major enhancement to the IZMIRAN model developed in this study to explain the two component 630 nm emission observed is the analytical yield spectrum approach to calculate the fluxes of precipitating electrons and the additional production rates of N⁺₂, O⁺₂, O⁺(⁴S), O⁺(²D), O⁻(²P), and O⁺(²P) ions, and O(¹D) in the SAR arc regions in the Northern and Southern Hemispheres. In order to bring the measured and modelled electron temperatures into agreement, the additional heating electron rate of 1.05 eV cm⁻³ s⁻¹ was added in the energy balance equation of electrons at altitudes above 5000 km during the main phase of the geomagnetic storm. This additional heating electron rate determines the thermally excited 630 nm emission observed. The IZMIRAN model calculates a 630 nm integral intensity above 350 km of 4.1 kR and a total 630 nm integral intensity of 8.1 kR, values which are slightly lower compared to the observed 4.7 kR and 10.6 kR. We conclude that the 630 nm emission observed can be explained considering both the soft energy electron excited component and the thermally excited component. It is found that the inclusion of N₂(v > 0) and O₂(v > 0) in the calculations of the O⁺(⁴S) loss rate improves the agreement between the calculated N_e and the data on 4 August, 1972. The N₂(v > 0) and O₂(v > 0) effects are enough to explain the electron density depression in the SAR arc F-region and above F2 peak altitude. Our calculations show that the increase in the O⁺ + N₂ rate factor due to the vibrationally excited nitrogen produces the 5–19% reductions in the calculated quiet daytime peak density and the 16–24% decrease in NmF2 in the SAR arc region. The increase in the O⁺ + N₂ loss rate due to vibrationally excited O₂ produces the 7–26% decrease in the calculated quiet daytime peak density and the 12–26% decrease in NmF2 in the SAR arc region. We evaluated the role of the electron cooling rates by low-lying electronic excitation of O₂(a¹δ_g) and O₂(b¹σ_g⁺), and rotational excitation of O₂, and found that the effect of these cooling rates on T_e can be considered negligible during the quiet and geomagnetic storm period 3–4 August, 1972. The energy exchange between electron and ion gases, the cooling rate in collisions of O(³P) with thermal electrons with excitation of O(¹D), and the electron cooling rates by vibrational excitation of O₂ and N₂ are the largest cooling rates above 200 km in the SAR arc region on 4 August, 1972. The enhanced IZMIRAN model calculates also number densities of N₂(B³π_g⁺), N₂(C³π_u), and N₂(A³σ_u⁺) at several vibrational levels, O(¹S), and the volume emission rate and integral intensity at 557.7 nm in the region between 120 and 1000 km. We found from the model that the integral integral intensity at 557.7 nm is much less than the integral intensity at 630 nm.     

Density-dependent dispersion in heterogeneous porous media Part II: Comparison with nonlinear models

The results of a series of high-resolution numerical experiments are used to test and compare three nonlinear models for high-concentration-gradient dispersion. Gravity stable miscible displacement is considered. The first model, introduced by Hassanizadeh, is a modification of Fick’s law which involves a second-order term in the dispersive flux equation and an additional dispersion parameter β. The numerical experiments confirm the dependency of β on the flow rate. In addition, a dependency on travelled distance is observed. The model can successfully be applied to nearly homogeneous media (σ² = 0.1), but additional fitting is required for more heterogeneous media.The second and third models are based on homogenization of the local scale equations describing density-dependent transport. Egorov considers media that are heterogeneous on the Darcy scale, whereas Demidov starts at the pore-scale level. Both approaches result in a macroscopic balance equation in which the dispersion coefficient is a function of the dimensionless density gradient. In addition, an expression for the concentration variance is derived. For small σ², Egorov’s model predictions are in satisfactory agreement with the numerical experiments without the introduction of any new parameters. Demidov’s model involves an additional fitting parameter, but can be applied to more heterogeneous media as well.     

An oxygen isotope study of hydrothermal alteration in the Lake City caldera, San Juan Mountains, Colorado

A 23-m.y.-old, fossil meteoric-hydrothermal system in the Lake City caldera (11 × 14 km) has been mapped out by measuring δ ¹⁸O values of 300 rock and mineral samples. δ ¹⁸O varies systematically throughout the caldera, reaching values as low as −2. Great topographic relief, regional tilting, and variable degrees of erosion within the caldera all combine to give us a very complete section through the hydrothermal system, from the surface down to a depth of more than 2000 m. The initial δ ¹⁸O value of the caldera-fill Sunshine Peak Tuff was very uniform (+7.2 ± 0.1), making it easy to determine the exact amount of ¹⁸O depletion experienced by each sample during hydrothermal alteration. Also, we have excellent stratigraphic control on depths beneath the mid-Tertiary surface, quantitative information on mineralogical alteration products, and accurate data on the shape of the central resurgent intrusion, which was the principal ‘heat engine’ that drove the hydrothermal circulation. Major conclusions are: (1) Although pristine mid-Tertiary meteoric waters in this area had δ ¹⁸O −14, these fluids were ¹⁸O-shifted upward to about δ¹⁸O = −8 to −5 prior to entering the shallow convective system associated with the resurgent intrusive rocks. Although there was undoubtedly radial inflow toward the caldera from all directions, the highly fractured Eureka Graben, southwest of the caldera, was probably the principal source of recharge groundwater for the Lake City system. (2) Fluid flow within the caldera was dominated by three major categories of permeable zones: the porous megabreccia units (which dip outward from the resurgent dome), vertical fractures and faults related to resurgence, and the caldera ring fault itself. All of these zones exhibit marked ¹⁸O depletions, and they are also typically intensely mineralogically altered. (3) The resurgent intrusive stock and its contact metamorphic aureole of hornfels both experienced water/rock ratios lower than the permeable zones; however, they have similarly low δ ¹⁸O values because they were altered at higher temperatures. (4) Throughout the caldera, the δ ¹⁸O of Sunshine Peak Tuff decreases with increasing depth (about 6 per mil/km), indicative of a shallow thermal gradient, typical of a convective hydrothermal system. The near-surface portion of this gradient was controlled by the temperature drop associated with boiling in the uprising fluid. (5) Deeply circulating meteoric water rose along permeable ring fractures 3 to 5 km beneath the mid-Tertiary surface. These fluids were drawn into the shallow convective system through the lower, porous, megabreccia units. Near the resurgent intrusions, fluid flow was again directed upward where resurgence-related, near-vertical fractures intersect the megabreccia units.     

Downslope flow models of a Bingham liquid: Implications for lava flows

It is widely recognized that lavas behave as Bingham liquids, which are characterized by a yield stress σ and a plastic viscosity η. We consider two models describing downslope flows of a Bingham liquid with different aspect ratios A (= flow height/flow width): model 1 with A 1 and model 2 with A ≈ 1. Sufficiently uphill with respect to the front, such flows can be considered as laminar and locally isothermal. For both models, we obtain analytically the steady-state solution of the Navier-Stokes equations and the constitutive equation for a Bingham liquid. We study the flow height and velocity as functions of flow rate, rheological parameters and ground slope. It is found that such flows remain in the Newtonian regime at low yield stresses (σ 10³dyne/cm²), but the transition to the Bingham regime also depends on flow rate and occurs at higher values of σ for higher flow rates: for instance, a high aspect ratio flow (model 2) is still very close to the Newtonian regime at σ = 10⁴ dyne/cm², if the flow rate is greater than 10⁵ g/s. In the Bingham regime, flow heights are generally greater and flow velocities are smaller than in the Newtonian regime; moreover, flow heights are independent of flow rate, so that a change in flow rate results exclusively in a velocity change. After assuming a specific temperature dependence of σ and η between the solidus and the liquidus temperatures of an ideal Bingham liquid (1000°C and 1200 °C respectively), flow heights and velocities are examined as functions of temperature along the flow. Several effects observed in lava flows are predicted by these models and allow a more quantitative insight into the behaviour of lava flows.     

O, S, Sr, and Pb isotope variations in volcanic rocks from the Northern Mariana Islands: implications for crustal recycling in intra-oceanic arcs

Quaternary lavas from the Northern Mariana Islands have respective O- and S-isotope ranges ofδ¹⁸O = +5.7 to +6.6 (‰ SMOW) andδ³⁴S = +2.0to+20.7 (‰ CDT). Chemically evolved andesites and dacites with meanδ¹⁸O = +6.3 ± 0.2 are slightly enriched in¹⁸O with respect to unfractionated basalts of<53%SiO₂ with meanδ¹⁸O = +6.0 ± 0.1. This¹⁸O enrichment can be explained in terms of differentiation of parental mafic magmas havingδ¹⁸O values between +5.7 to +6.2‰ through closed-system crystal fractionation because the lavas from all nine islands of the arc define a coherentδ¹⁸OSiO₂ trend. The S-isotope composition of oxidized magmas is not modified extensively through the degassing of SO₂; therefore, the meanδ³⁴S value of ca. +11‰ for the Mariana lavas is considered to be representative of their source region.The enrichment of¹⁸O and³⁴S in Mariana Arc parental magmas relative to ocean floor basalts withδ¹⁸O ca. + 5.7‰ andδ³⁴S = ca.0.3‰ is attributed to the recycling of¹⁸O- and³⁴S-rich crustal components (sediment withδ¹⁸O = ca. + 25‰ and seawater sulfate withδ³⁴S = ca. +20‰ into the upper mantle source region for these arc magmas. This interpretation is consistent with enrichments of radiogenic Sr and Pb in the same lavas relative to ocean-floor basalts erupted either side of the arc, which are presumed to share a common upper mantle source. This enrichment is considered to reflect the mixing of two components, one having a typical upper mantle composition and the other having a more radiogenic character similar to that of western Pacific pelagic sediments.     

Orographic controls on rain water isotope distribution in the Mount Lofty Ranges of South Australia

Hydrogen and oxygen isotopes of water are common environmental tracers used to investigate hydrological processes, such as evaporation, vegetation water use, surface water–groundwater interaction, and groundwater recharge. The water isotope signature in surface water and groundwater evolves from the initial rain signature. In mountain terrain, rain water stable isotope composition spatially varies due to complex orographic precipitation processes. Many studies have examined the isotope–elevation relationships, while few have quantitatively investigate the terrain aspect and slope effect on rain isotope distribution. In this paper, we examine the orographic effects more completely, including elevation, terrain slope and aspect, on stable isotope distribution in the Mount Lofty Ranges (MLR) of South Australia, using a multivariate regression model. The regression of precipitation isotope composition suggests that orographic effects are the dominant controls on isotope spatial variability. About 75% of spatial variability in δ¹⁸O and deuterium excess is represented by the regression using solely orography-related variables (elevation, terrain aspect and slope), with about 25% of δ¹⁸O spatial variability attributed to the terrain aspect and slope effect. The lapse rate is about −0.25‰ for every 100 m at both windward and leeward slopes. However, at the same elevation, δ¹⁸O at the leeward slope (eastern MLR) is 0.5‰ larger than that at the windward slope. The difference can be explained by different mechanisms – continuous rain-out processes on the windward side and sub-cloud evaporation on the leeward side. Both δ¹⁸O and deuterium excess maps (1 km resolution) are constructed based on the regression results for the MLR. Both maps are consistent with groundwater of local precipitation origin, and useful to examine groundwater recharge.     

Energy mode distribution: An analysis of the ratio of anti-Stokes to Stokes amplitudes generated by a pair of counterpropagating Langmuir waves

Results from plasma wave experiments in spacecrafts give support to nonlinear interactions involving Langmuir, electromagnetic, and ion-acoustic waves in association with type III solar radio bursts. Starting from a general form of Zakharov equation (Zakharov, V.E., 1985. Collapse and self-focusing of Langmuir waves. Hand-book of Plasma Physics Cap.2, 81–121) the equations for electric fields and density fluctuations (density gratings) induced by a pair of counterpropagating Langmuir waves are obtained. We consider the coupling of four triplets. Each two triplets have in common the Langmuir pump wave (forward or backward wave) and a pair of independent density gratings. We numerically solve the dispersion relation for the system, extending the work of (Alves, M.V., Chian, A.C.L., Moraes, M.A.E., Abalde, J.R., Rizzato, F.B., 2002. A theory of the fundamental plasma emission of type- III solar radio bursts. Astronomy and Astrophysics 390, 351–357). The ratio of anti-Stokes (AS) (ω₀+ω) to Stokes (S) (ω₀-ω^*) electromagnetic mode amplitudes is obtained as a function of the pump wave frequency, wave number, and energy. We notice that the simultaneous excitation of AS and S distinguishable modes, i.e., with Re{ω}=ω_r≠0, only occurs when the ratio between the pump wave amplitudes, r is ≠1 and the pump wave vector k₀ is , W₀ being the forward pump wave energy. We also observe that the S mode always receives more energy.     

Leaf breakdown in two tropical streams: Differences between single and mixed species packs

We assessed leaf breakdown of five native riparian species from Brazilian Cerrado (Myrcia guyanensis, Ocotea sp., Miconia chartacea, Protium brasiliense, and Protium heptaphyllum), incubated in single and mixed species packs in two headwater streams with different physico-chemical properties in the Espinhaço Mountain range (Southeastern Brazil). Leaves were placed in plastic litter bags (15 cm×20 cm, 10 mm mesh size) and the experiments were carried out during the dry seasons of 2003 and 2004. Leaf nitrogen and phosphorus contents were similar in all species, but polyphenolic contents were different (P<0.001). M. guyanensis showed higher polyphenolics content (8.48% g⁻¹ dry mass) and leaf toughness. Individually, higher breakdown rates were found in M. guyanensis at Indaiá stream (k=0.0063±0.0005 d⁻¹) and in Ocotea sp. at Garcia stream (k=0.0088±0.0006 d⁻¹). However, P. brasiliense and P. heptaphyllum showed lower breakdown rates at Indaiá and Garcia streams (Indaiá: k=0.0020±0.0002 and 0.0019±0.0001 d⁻¹; Garcia: k=0.0042±0.0001 and 0.0040±0.0002 d⁻¹). Single and mixed breakdown processes of each species were not statistically different on both streams. However, all species showed higher breakdown rates at Garcia stream (P<0.01). These results suggest that leaf breakdown is not altered when litter benthic patches are composed by a mixture of species in the same proportions that they occur on riparian leaf falls.     

Dynamics of the transport of the phosphorus and silicon at the water-bottom boundary in the Baltic Sea

The study of the fine structure of the phosphorus and silicon distribution in near-bottom layers and in the interstitial water of the sediments has been carried out in the different Baltic Sea regions (Gulf of Finland, Bornholm, Gotland). The data of this study are used to calculate the flows and effective transport coefficients for mineral phosphorus and silicon exchange processes between sediment and near-bottom layer. The values of nutrient flows varied depending on sediment type from 9.8 to 632 μg-at. m⁻² year⁻¹ for phosphorus and from 232.4 to 1881.1 μg-at. m⁻² year⁻¹ for silicon. The dependence of the effective transport coefficients versus the distance from the bottom (h) is expressed by empirically-derived equation: K_eff = Ah^−b. The values of constants “A” and “b” depend on the hydrochemical conditions, sediment type and hydrophysical conditions in the near-bottom layers. Calculated constants for regions are discussed.     

Temperature dependence of the oxygen isotopic fractionation between diatom silica and water

We present a new paleotemperature scale, based on the oxygen isotopic ratio of the non-exchangeable fraction of the oxygen from diatom silica. The equation t = 17.2 − 2.4 (δ¹⁸O_silica − δ¹⁸O_water − 40) − 0.2 (δ¹⁸O_silica − δ¹⁸O_water − 40)² was derived using recent sediment samples from different oceanic areas, the temperature and isotopic composition of the local surface water. Comparison of our results with other relationships established for quartz-water or amorphous silica-water at higher temperature suggests no difference in isotopic fractionation between quartz-water and biogenic silica-water couples.     

Very high-frequency and seasonal cave atmosphere PCO2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

Cave air P_CO2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO₂ production, resulting in high summer P_CO2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO₂ degassing rates from drip water, by considering both the seasonal and high-frequency cave air P_CO2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h^− 1) and minima in late June/early July (0.033 μm h^− 1). For well-mixed ‘diffuse flow’ cave drips such as those that feed CC-Bil, high summer cave air P_CO2 depresses summer calcite deposition, while low winter P_CO2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ¹⁸O, integrated annual stalagmite calcite δ¹⁸O is unaffected; however, seasonality in cave air P_CO2 may influence non-conservative geochemical climate proxies (e.g., δ¹³C, Sr/Ca). Stalagmites fed by ‘seasonal’ drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air P_CO2 may increase relative to cave air P_CO2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ¹⁸O records towards isotopically heavier summer drip water δ¹⁸O values, resulting in elevated calcite δ¹⁸O values compared to the ‘equilibrium’ values predicted by calcite–water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air P_CO2 variability and the resulting intra-annual variability in calcite deposition rates.     

Sediment-transport competence of rain-impacted interrill overland flow

Laboratory experiments to determine the maximum size of sediment transported in shallow, rain-impacted flow were conducted in a recirculating flume 4·80 m long and 0·50 m wide. Rainfall intensities were varied between 51 and 138 mm h⁻¹, flow was introduced from a header tank into the flume at rates ranging from 0 to 0·64 l s⁻¹, and experiments were conducted on gradients between 3·5 and 10°. The following equation was developed: ML = (REFE)^1·6363 in which M is particle mass, L is distance moved in unit time (cm min⁻¹), RE is rainfall energy (J m⁻² s⁻¹) and FE is flow energy (J m⁻² s⁻¹). This equation can be used to predict sediment-transport competence of interrill overland flow. The equation is limited in its utility insofar as it has been developed using quartz grains and takes no account of variations in absorption of rain energy by natural ground surfaces. © 1998 John Wiley & Sons, Ltd.     

Evaluation of approximations in modelling the cooling of magmatic bodies

The cooling of a magmatic intrusion is simulated by a simple model of a non-homogeneous earth, with thermal properties depending on temperature, in which heat transfer is assumed to take place by conduction only. The mathematical problem consists in solving a non-linear partial differential equation with continuity conditions on temperature and heat flux imposed at the contacts between different rocks. This has been done numerically by a finite difference method. The model is then adopted as “reality” against which a number of commonly used approximations are tested. It is found that the effect of latent heat liberation can be reasonably taken into account by attributing an effective initial temperature to the magma (errors within 20°C for t > 10⁵ years, when the temperature of the magma is still as high as 600°C); the effective specific heat approximation does not work as well. The dependence of thermal conductivity and specific heat on temperature may be eliminated by maintaining the errors within 30°C for t < 5 × 10⁵ years. The assumption that magma and country rocks have the same thermal properties allows an estimate of the temperature field in the host rocks with errors of 50°C at most. The assumption that all rocks have the same constant conductivity yields results that are far from “reality” (errors of 100–200°C even at shallow depth).