Direct observations of aluminosilicate weathering in the hyporheic zone of an Antarctic Dry Valley stream

This study focused on chemical weathering and bacterial ecology in the hyporheic zone of Green Creek, a McMurdo Dry Valley (Antarctica) stream. An in situ microcosm approach was used to observe dissolution features on the basal-plane surface of muscovite mica. Four mica chips were buried in December 1999 and dug up 39 d later. Atomic force microscopy (AFM) of the basal-plane surfaces revealed small, anhedral ∼10-Å-deep etch pits covering ∼4% of the surfaces, from which an approximate basal-plane dissolution rate of 8.3 × 10⁻¹⁸ mol muscovite cm⁻² s⁻¹ was calculated (on the basis of the geometric surface area) for the study period. This is an integrated initial dissolution rate on a fresh surface exposed for a relatively brief period over the austral summer and should not be compared directly to other long-term field rates. The observation of weathering features on mica agrees with previous stream- and watershed-scale studies in the Dry Valleys, which have demonstrated that weathering occurs where liquid water is present, despite the cold temperatures.AFM imaging of mica surfaces revealed biofilms including numerous small (<1 μm long), rounded, oblong bacteria. The AFM observations agreed well with X-ray photoelectron microscopy results showing increased organic C and N. Bacteriologic analysis of the hyporheic zone sediments also revealed <1-μm-long bacteria. α-Proteobacteria were observed, consistent with the oligotrophic conditions of the hyporheic zone. Nitrate-reducing bacteria were found, in agreement with a previous tracer test at Green Creek that suggested nitrate reduction occurs in the hyporheic zone. The results of this study thus provide direct evidence of dynamic geochemical and microbial processes in the hyporheic zone of a Dry Valley stream despite the extreme conditions; such processes were inferred previously from stream-scale hydrogeochemical studies.     

Oxygen fugacity and geochemical variations in the martian basalts: implications for martian basalt petrogenesis and the oxidation state of the upper mantle of Mars

The oxygen fugacity of the Dar al Gani 476 martian basalt is determined to be quartz-fayalite-magnetite (QFM) −2.3 ± 0.4 through analysis of olivine, low-Ca pyroxene, and Cr-spinel and is in good agreement with revised results from Fe-Ti oxides that yield QFM −2.5 ± 0.7. This estimate falls within the range of oxygen fugacity for the other martian basalts, QFM −3 to QFM −1. Oxygen fugacity in martian basalts correlates with ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, and La/Yb ratios, indicating that the mantle source of the basalts is reduced and that assimilation of crust-like material controls the oxygen fugacity. This allows constraints to be placed on the oxidation state of the martian mantle and on the nature of assimilated crustal material. The assimilated material may be the product of early and extensive hydrothermal alteration of the martian crust, or it may be amphibole- or phlogopite-bearing basaltic rock within the crust. In either case, water may play a significant role in the oxidation of basaltic magmas on Mars, although it may be secondary to assimilation of ferric iron-rich material.     

Comparative Re-Os systematics of chondrites: Implications regarding early solar system processes

A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average ¹⁸⁷Re/¹⁸⁸Os for carbonaceous chondrites is 0.392 ± 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ± 0.025 and 0.421 ± 0.013 for ordinary and enstatite chondrites (1σ standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ± 0.0031, 0.0876 ± 0.0052 and 0.0874 ± 0.0027, respectively. Correspondingly, the ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites average 0.1262 ± 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ± 0.0017 and 0.1281 ± 0.0004, respectively (1σ standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history.A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga.The ¹⁸⁷Os/¹⁸⁸Os ratio of Earth’s primitive upper mantle has been estimated to be 0.1296 ± 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites.     

Physical and chemical properties of the waters of saline lakes and their importance for deep-water renewal: Lake Issyk-Kul, Kyrgyzstan

The relationships between electrical conductivity, temperature, salinity, and density are studied for brackish Lake Issyk-Kul. These studies are based on a newly determined major ion composition, which for the open lake shows a mean absolute salinity of 6.06 g kg⁻¹. The conductivity-temperature relationship of the lake water was determined experimentally showing that the lake water is about 1.25 times less conductive than seawater diluted to the same absolute salinity as that of the lake water. Based on these results, an algorithm is presented to calculate salinity from in-situ conductivity measurements. Applied to the field data, this shows small but important vertical salinity variations in the lake with a salinity maximum at 200 m and a freshening of the surface water with increasing proximity to the shores. The algorithm we adopt to calculate density agrees well with earlier measurements and shows that at 20°C and 1 atm Lake Issyk-Kul water is about 530 g m⁻³ denser than seawater at the same salinity. The temperature of maximum density at 1 atm is about 0.15°C lower than that for seawater diluted to the same salinity. Despite its small variations, salinity plays an important role, together with temperature changes, in the static stability and in the production of deep-water in this lake. Changes in salinity may have had important consequences on the mixing regime and the fate of inflowing river water over geological time. Uncharged silicic acid is negligible for the stability of the water column except near an ∼15 m thick nepheloid layer observed at the bottom of the deep basin.     

A Comparison of Two-Phase Dynamic Upscaling Methods Based on Fluid Potentials

Although a number of methods for calculating dynamic pseudo-functions have been developed over the years, there is still a lack of understanding as to why a certain method will succeed in some cases but fail in others. In this paper, we describe the results of an assessment of several upscaling methods, namely the Kyte and Berry (KB) method, the Stone method, the Hewett and Archer (HA) method and the Transmissibility-Weighted (TW) method. We have analyzed the equations for deriving the methods and investigated the results of numerical simulations of gas displacing oil, in a variety of models to enable us to gain new insights into these, and related, upscaling methods. In particular, some novel observations on methods based on fluid potential are presented and the issue of using predicted fluid mobilities as a criterion of accuracy of an upscaling method is clarified.     

Structural relaxation in the MnCO3–CaCO3 solid solution: a Mn K-edge EXAFS study

Mn K-edge EXAFS spectroscopy of solid-solution samples encompassing the complete MnCO₃–CaCO₃ series shows that first-shell Mn–O distances deviate little from the 2.19-Å distance observed in pure MnCO₃. Very slight lengthening is observed only in the limiting case of dilute Mn(II) calcite solid solutions, where the Mn–O distance is 2.21 Å. The observed nearly complete structural relaxation and the composition independence of the Mn–O distance are consistent with the Pauling model behavior of solid solutions, and agree with previous studies showing a high degree of relaxation around hetero-sized substituents in the calcite structure. Strain occurs through bond bending, which is facilitated by the exclusively corner-sharing topology of calcite. Observed distances from Mn to more distant neighbors show significant variation across the solid-solution series that resembles Vegard's law-type behavior but reflects averaging. The high degree of relaxation suggests modest enthalpies of mixing in the solution, consistent with calorimetric studies.     

Multiple stressors in an estuarine system: Effects of nutrients, trace elements, and trophic complexity on benthic photosynthesis and respiration

The effects of nutrients, trace elements, and trophic complexity on benthic photosynthesis and respriation were studied in the Paxtuxent River estuary near St. Leonard, Maryland. Experiments were conducted over three years (1995–1997) in mesocosms containing riverine sediment and water. The experimental design was 2×2×3 factorial with two levels of nutrients (ambient and + nutrients), two of trace elements (ambient and + trace elements) and three of trophic complexity (plankton, plankton + fish, and plankton + fish + benthos). Trace elements included arsenic (As), copper (Cu), and cadmium (Cd). The experiment was conducted three times in 1995 and 1997 and four times in 1996. In 1995 and 1996, sediments were muddy, while in the final year sediments were sandy. In mesocoms with sandy sediments, nutrient additions increased benthic photosynthesis overall, while trace element additions increased benthic photosynthesis in two of three experimental runs. Benthic photosynthesis in these mesocosms appeared to be related to nitrogen loading. Benthic respiration increased in nutrient and trace element amended mesocosms with sandy sediments, apparently in response to higher benthic photosynthesis. Increasing trophic complexity, particularly the presence of benthic organisms, also increased benthic respiration in mesocosms with sandy sediments. There were no effects of nutrient or trace element additions on benthic photosynthesis and respiration when the sediments were muddy. The lack of consistent responses to nutrient additions was surprising given that benthic respiration rates (and presumably nutrient regeneration) were similar in all three years, regardless of sediment type. Muddy, sediments did not mask, the effects of nutrient addition by supplying more nutrients to benthic microalgae than sandy sediments. In 1996, the presence of filter feeding bivalves increased the relative heterotrophy of sediments, measured as production: respiration. Consistent with increased heterotrophy, effluxes of ammonium and soluble reactive phosphorus from sediments were greater in mesocosms containing benthic organisms. Anthropogenically-induced changes in estuaries, such as loading of nutrients and trace elements or reduced trophic complexity, can have important effects on benthic processes and potentially pelagic processes through feedback mechanisms.