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.     

Effect of adsorbed metal ions on the transport of Zn- and Ni-EDTA complexes in a sand and gravel aquifer

Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales.     

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.     

Climate change impacts on U.S. Coastal and Marine Ecosystems

Increases in concentrations of greenhouse gases projected for the 21st century are expected to lead to increased mean global air and ocean temperatures. The National Assessment of Potential Consequences of Climate Variability and Change (NAST 2001) was based on a series of regional and sector assessments. This paper is a summary of the coastal and marine resources sector review of potential impacts on shorelines, estuaries, coastal wetlands, coral reefs, and ocean margin ecosystems. The assessment considered the impacts of several key drivers of climate change: sea level change; alterations in precipitation patterns and subsequent delivery of freshwater, nutrients, and sediment; increased ocean temperature; alterations in circulation patterns; changes in frequency and intensity of coastal storms; and increased levels of atmospheric CO₂. Increasing rates of sea-level rise and intensity and frequency of coastal storms and hurricanes over the next decades will increase threats to shorelines, wetlands, and coastal development. Estuarine productivity will change in response to alteration in the timing and amount of freshwater, nutrients, and sediment delivery. Higher water temperatures and changes in freshwater delivery will alter estuarine stratification, residence time, and eutrophication. Increased ocean temperatures are expected to increase coral bleaching and higher CO₂ levels may reduce coral calcification, making it more difficult for corals to recover from other disturbances, and inhibiting poleward shifts. Ocean warming is expected to cause poleward shifts in the ranges of many other organisms, including commercial species, and these shifts may have secondary effects on their predators and prey. Although these potential impacts of climate change and variability will vary from system to system, it is important to recognize that they will be superimposed upon, and in many cases intensify, other ecosystem stresses (pollution, harvesting, habitat destruction, invasive species, land and resource use, extreme natural events), which may lead to more significant consequences.     

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.     

Persistence of tidally-oriented vertical migration by zooplankton in a temperate estuary

Tidal vertical migration by zooplankton is a common phenomenon in estuaries, usually associated with landward movement of meroplankton or position maintenance of holoplankton. Little is known about the persistence of this behavior, its spatial variability, or its response to changing environmental conditions. We extended a previous study of tidal movements of zooplankton in the low-salinity zone (LSZ) of the San Francisco estuary in 1994 to include data from two additional years with very different hydrology. Freshwater flow during sampling in 1995 was about 7-fold greater than in 1994; the LSZ was about 28 km further seaward, and gravitational circulation in the LSZ was strong. In 1996 freshwater flow and LSZ position were intermediate but, because the LSZ was in shallower water in 1996 than in 1995, gravitational circulation was uncommon. Behavior of copepods in both years was similar to that reported in 1994 with some tidal migration observed during most cruises. An exception was the introduced carnivorous copepodTortanus dextrilobatus, which did not migrate and maintained a position deep in the water column (1995 only). In 1996, mysids mainly stayed near the bottom with evidence for vertical migration from only 1 of 6 data sets, whereas amphipods migrated slightly on a diel schedule; these behaviors contrasted with the tidal migration observed in 1994. The bay shrimpCrangon franciscorum did not appear to migrate, but was more abundant in the water column during both ebb and flood, suggesting passive vertical dispersal. Zooplankton did not appear to maintain position by interactions with lateral circulation cells. The results for copepods suggest rigidity in behavior with little or no relaxation of the vertical movement in 1995 when strong gravitational circulation would have made upstream movement relatively easy. Mysids and amphipods altered their behavior depending on local conditions related to freshwater flow.     

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.     

Celestite formation, bacterial sulphate reduction and carbonate cementation of Eocene reefs and basinal sediments (Igualada, NE Spain)

Petrographic and geochemical studies of an Upper Eocene reef and associated basinal sediments from the mixed carbonate–siliciclastic fill of the south‐eastern Pyrenean foreland basin near Igualada (NE Spain) provide new insights into the evolution of subsurface hydrology during the restriction of a marine basin. The reef deposits are located on delta‐lobe sandstones and prodelta marls, which are overlain by hypersaline carbonates and Upper Eocene evaporites. Authigenic celestite (SrSO₄) is an important component in the observed diagenetic sequences. Celestite is a significant palaeohydrological indicator because its low solubility constrains transportation of Sr²⁺ and SO₄^2? in the same diagenetic fluid. Stable isotopic analyses of carbonates in the reef indicate that meteoric recharge was responsible for aragonite stabilization and calcite cementation. Sulphur and oxygen isotope geochemistry of the celestite demonstrates that it formed from residual sulphate after bacterial sulphate reduction, but also requires that there was a prior episode of sulphate recycling. Meteoric water reaching the reef and basinal areas was most probably charged with SO₄^2? from the dissolution of younger Upper Eocene marine evaporites. This sulphate, combined with organic matter present in the sediments, fuelled bacterial sulphate reduction in the meteoric palaeoaquifer. Strontium for celestite precipitation was partly derived in situ from dissolution of aragonite corals in the reef and basinal counterparts. However, ⁸⁷Sr/⁸⁶Sr data also suggest that Sr²⁺ was partly derived from dissolution of overlying evaporites. Mixing of these two fluids promoted celestite formation. The carbonate stable isotopic data suggest that the local meteoric water was enriched in ¹⁸O compared with that responsible for stabilization of other reefs along the basin margin. Furthermore, meteoric recharge at Igualada post‐dated evaporite deposition in the basin, whereas other parts of the same reef complex were stabilized before evaporite formation. This discrepancy resulted from the spatial distribution of continental siliciclastic units that acted as groundwater conduits.