Some chemical characteristics of the brines in Bannock and Tyro Basins: salinity, sulphur compounds, Ca, F, pH, At, PO4, SiO2, NH3

Results of the chemical investigation on the Bannock and Tyro Basins are reported.Both basins were found to be hypersaline ( 10 times higher than salinity of normal seawater) and anoxic. In all investigated basins a region of transition, a few meters thick, was identified at depths > 3327 dbar. It is characterized by a sharp gradient of salinity, and all concentrations of analysed species increase strongly except for dissolved oxygen and nitrate, which immediately drop to zero. This region appears as a sharp boundary that prevents mixing. As a result, in the presence of organic matter, an anoxic condition developed with the complete depletion of dissolved oxygen. At the same time, hydrogen sulphide and ammonium accumulated within the brine. Between the Bannock and the Tyro brines differences occur in the measured concentrations of H₂S, SO²⁻₄, Ca²⁺ and NH₃. There are some differences also within the Bannock area sub-basins.The Libeccio sub-basin, in the Bannock area, contains a double-layered brine: the upper layer is 140 dbar thick and the lower layer is 300 dbar thick. A second interface between upper and lower brines develops at a depth of 3500 dbar. Nearly all of the measured concentrations vs. depth show the double layer, with the exception of ammonium, the concentration of which remains nearly constant throughout the anoxic column. Profiles of the other species analyzed show remarkable differences on passing from the upper to the lower brine. Hydrogen sulphide, sulphate and fluoride concentrations appear constant and then increase at the second interface. The calcium concentration is also constant in the upper brine, but decreases at the second interface. Total alkalinity and phosphate concentrations show a maximum peak just below the first interface. However, after passing through the second interface all the chemical parameters exhibit an almost constant behaviour down to the bottom.Hypersaline conditions are attributed to the dissolution of Messinian evaporite, and anoxia is suggested to originate from the oxidation of organic matter present in sediments and from the absence of bottom water circulation in such a deep and enclosed environment.The chemical conditions can be summarized as follows: in the Libeccio Basin the values for the species analysed have the ranges: 39–321 psu for ‘salinity’, 8.2−6.5 for pH, 2.7–4.0 mM for total alkalinity, 0.2-0 mM for dissolved oxygen, 0–1669 μM for hydrogen sulphide, 0–198 μM for thiol, 31–99 mM for sulphate, 11–21 mM for calcium, 7–100 μM for fluoride, 0.2–3080 μM for ammonium, 5.8-0 μM for nitrite, 0.2–12 μM for phosphate and 8–130 μM for silicate.     

Distinct modes of bidecadal and multidecadal variability in a climate reconstruction of the last centuries from a South Pacific coral

The Rarotonga coral Sr/Ca time series (Linsley et al. in Science 290:1145–1148, 2000) provides a near-monthly resolved proxy record of South Pacific climate variability over the last ~300 years. Here we show that two distinct interdecadal, quasi-periodic time components with periods of ~80 and ~25 years can be identified in this time series by Singular Spectrum Analysis. Their associated spatial patterns in the global sea surface temperature (SST) field show notable differences. Whereas the multidecadal component is associated with a global SST pattern that was recently associated with solar forcing on multidecadal timescales, the bidecadal component is associated with a well known pattern of Pacific decadal to interdecadal SST variability.     

Oxidation of the Kaapvaal lithospheric mantle driven by metasomatism

The oxidation state, reflected in the oxygen fugacity (fO₂), of the subcratonic lithospheric mantle is laterally and vertically heterogeneous. In the garnet stability field, the Kaapvaal lithospheric mantle becomes progressively more reducing with increasing depth from Δlog fO₂ FMQ-2 at 110 km to FMQ-4 at 210 km. Oxidation accompanying metasomatism has obscured this crystal-chemical controlled depth-fO₂ trend in the mantle beneath Kimberley, South Africa. Chondrite normalized REE patterns for garnets, preserve evidence of a range in metasomatic enrichment from mild metasomatism in harzburgites to extensive metasomatism by LREE-enriched fluids and melts with fairly unfractionated LREE/HREE ratios in phlogopite-bearing lherzolites. The metasomatized xenoliths record redox conditions extending up to Δlog fO₂ = FMQ, sufficiently oxidized that magnesite would be the stable host of carbon in the most metasomatized samples. The most oxidized lherzolites, those in or near the carbonate stability field, have the greatest modal abundance of phlogopite and clinopyroxene. Clinopyroxene is modally less abundant or absent in the most reduced peridotite samples. The infiltration of metasomatic fluids/melts into diamondiferous lithospheric mantle beneath the Kaapvaal craton converted reduced, anhydrous harzburgite into variably oxidized phlogopite-bearing lherzolite. Locally, portions of the lithospheric mantle were metasomatized and oxidized to an extent that conversion of diamond into carbonate should have occurred. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Calculating surface water PCO2 from foraminiferal organic δC

The δ¹³C of organic matter bound within the crystal lattice of foraminiferal calcite tests may provide a potential tracer of the isotopic composition of the surface water primary photosynthate. Using δ¹³C of the organic matter extracted from the crystal lattice and the calcite test, it is theoretically possible to estimate the paleo-surface water pCO₂. We have tailored this technique initially for the subpolar planktonic foraminifera species Globigerina bulloides. Initial surface water pCO₂ estimates from deep-sea core BOFS 5K (50°41.3′N, 21°51.9′W, water depth 3547 m) indicate that the northeast Atlantic Ocean may have been a greater sink for CO₂ during the last glacial than during the Holocene. Greatly reduced benthic foraminifera abundances, especially phytodetritus feeders, in BOFS 5K during the last glacial indicates low surface productivity. This rules out a productivity-driven CO₂ sink. The enhanced glacial CO₂ sink must, therefore, have results from a southwards shift of the centre of deep water formation.     

Transport of water in frozen soil: I: Experimental determination of soil-water diffusivity under isothermal conditions

A new experimental method for measuring the soil-water diffusivity of frozen soil under isothermal conditions is introduced. The theoretical justification of the method is presented and the feasibility of the method is demonstrated by experiments conducted using marine deposited clay. The measured values of the soil-water diffusivity are found comparable to reported experimental data.     

Differing controls on river‐ and lake‐water hydrogen and oxygen isotopic values in the western United States

Surface water oxygen and hydrogen isotopic values are commonly used as proxies of precipitation isotopic values to track modern hydrologic processes while proxies of water isotopic values preserved in lake and river sediments are used for paleoclimate and paleoaltimetry studies. Previous work has been able to explain variability in USA river‐water and meteoric‐precipitation oxygen isotope variability with geographic variables. These studies show that in the western United States, river‐water isotopic values are depleted relative to precipitation values. In comparison, the controls on lake‐water isotopic values are not well constrained. It has been documented that western United States lake‐water input values, unlike river water, reflect the monthly weighted mean isotopic value of precipitation. To understand the differing controls on lake‐ and river‐water isotopic values in the western United States, we examine the seasonal distribution of precipitation, evaporation and snowmelt across a range of seasonality regimes. We generate new predictive equations based on easily measured factors for western United States lake‐water, which are able to explain 69–63% of the variability in lake‐water hydrogen and oxygen isotopic values. In addition to the geographic factors that can explain river and precipitation values, lake‐water isotopic values need factors related to local hydrologic and climatic characteristics to explain variability. Study results suggest that the spring snowmelt runs off the landscape via rivers and streams, depleting river and stream‐water isotopic values. By contrast, lakes receive seasonal contributions of precipitation in proportion to the seasonal fraction of total annual precipitation within their watershed. Climate change may alter the ratio of snow to rain fall, affecting water resource partitioning between rivers and lakes and by implication of groundwater. Paleolimnological studies must account for the multiple drivers of water isotopic values; likewise, studies based on the isotopic composition of fossil material need to distinguish between species that are associated with rivers versus lakes. Copyright © 2010 John Wiley & Sons, Ltd.     

High-resolution climate simulation of the last glacial maximum

The climate of the last glacial maximum (LGM) is simulated with a high-resolution atmospheric general circulation model, the NCAR CCM3 at spectral truncation of T170, corresponding to a grid cell size of roughly 75 km. The purpose of the study is to assess whether there are significant benefits from the higher resolution simulation compared to the lower resolution simulation associated with the role of topography. The LGM simulations were forced with modified CLIMAP sea ice distribution and sea surface temperatures (SST) reduced by 1°C, ice sheet topography, reduced CO₂, and 21,000 BP orbital parameters. The high-resolution model captures modern climate reasonably well, in particular the distribution of heavy precipitation in the tropical Pacific. For the ice age case, surface temperature simulated by the high-resolution model agrees better with those of proxy estimates than does the low-resolution model. Despite the fact that tropical SSTs were only 2.1°C less than the control run, there are many lowland tropical land areas 4–6°C colder than present. Comparison of T170 model results with the best constrained proxy temperature estimates (noble gas concentrations in groundwater) now yield no significant differences between model and observations. There are also significant upland temperature changes in the best resolved tropical mountain belt (the Andes). We provisionally attribute this result in part as resulting from decreased lateral mixing between ocean and land in a model with more model grid cells. A longstanding model-data discrepancy therefore appears to be resolved without invoking any unusual model physics. The response of the Asian summer monsoon can also be more clearly linked to local geography in the high-resolution model than in the low-resolution model; this distinction should enable more confident validation of climate proxy data with the high-resolution model. Elsewhere, an inferred salinity increase in the subtropical North Atlantic may have significant implications for ocean circulation changes during the LGM. A large part of the Amazon and Congo Basins are simulated to be substantially drier in the ice age—consistent with many (but not all) paleo data. These results suggest that there are considerable benefits derived from high-resolution model regarding regional climate responses, and that observationalists can now compare their results with models that resolve geography at a resolution comparable to that which the proxy data represent.     

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

Inertial instability of large Rossby number horizontal shear flows in a thin homogeneous layer

A horizontal shear flow having a Rossby number, Ro, greater than unity on a rotating plane can become unstable when its shear value is less than −f, the Coriolis frequency. In this paper, this instability is investigated for an O(10 km) submesoscale, sinusoidal shear flow in a thin homogeneous fluid layer as in an oceanic mixed layer or a shallow sea. The most unstable mode is shown by a linear analysis to occur in a narrow localized region centered around the maximum anticyclonic current shear. However, nonlinear numerical calculations show that the instability can grow to encompass both unstable and stable regions of the current. A consequence of this finite-amplitude evolution is the formation of surface convergence/shear fronts. The possibility that inertial instability mechanism is a source of some surface convergence/shear features seen in remote sensing images of the sea surface is discussed. A comparison is made with the shear-flow instability that can occur concurrently in a sinusoidal shear current, and inertial instability is shown to be the dominant instability mechanism in the immediate range above Ro=2.     

Geology and impact features of Vargeão Dome,southern Brazil

Abstract– Vargeão Dome (southern Brazil) is a circular feature formed in lava flows of the Lower Cretaceous Serra Geral Formation and in sandstones of the Paraná Basin. Even though its impact origin was already proposed in the 1980s, little information about its geological and impact features is available in the literature. The structure has a rim‐rim diameter of approximately 12 km and comprises several ring‐like concentric features with multiple concentric lineaments. The presence of a central uplift is suggested by the occurrence of deformed sandstone strata of the Botucatu and Pirambóia formations. We present the morphological/structural characteristics of Vargeão Dome, characterize the different rock types that occur in its interior, mainly brecciated volcanic rocks (BVR) of the Serra Geral Formation, and discuss the deformation and shock features in the volcanic rocks and in sandstones. These features comprise shatter cones in sandstone and basalt, as well as planar microstructures in quartz. A geochemical comparison of the target rock equivalents from outside the structure with the shocked rocks from its interior shows that both the BVRs and the brecciated sandstone have a composition largely similar to that of the corresponding unshocked lithologies. No traces of meteoritic material have been found so far. The results confirm the impact origin of Vargeão Dome, making it one of the largest among the rare impact craters in basaltic targets known on Earth.