Sr-Isotope record of Quaternary marine terraces on the California coast and off Hawaii

Strontium-isotopic ratios of dated corals have been obtained from submerged reefs formed during Quaternary glacial periods off the Hawaiian islands. These data, combined with data from deep-sea sediments, tightly constrain the secular variation of marine ⁸⁷Sr/⁸⁶Sr for the past 800,000 yr. Although long-term trends are apparent, no significant (>0.02‰), rapid (<100,000 yr) excursions in ⁸⁷Sr/⁸⁶Sr were resolved nor did we observe any samples with ⁸⁷Sr/⁸⁶Sr greater than that of modern seawater. Strontium in mollusks from elevated marine terraces formed during interglacial periods on the southern California coast show resolvable and consistent variations in ⁸⁷Sr/⁸⁶Sr which, when compared to the trend of Quaternary marine ⁸⁷Sr/⁸⁶Sr, can be used to infer uplift rates and define approximate ages for the higher terraces. The Sr-isotope age estimates indicate that uplift rates vary among crustal blocks and were not necessarily constant with time. No contrast in Sr-isotopic ratios between similar-age Hawaiian and California fossils was observed, confirming that any change in marine ⁸⁷Sr/⁸⁶Sr from glacial to interglacial periods must be small. A realistic appraisal of the potential of Sr-isotope stratigraphy for chronometric applications in the Quaternary suggests that the technique will be limited to relatively coarse distinctions in age.     

A Brine Evolution Model and Mineralogy of Chemical Sediments in a Volcanic Crater,Lake Kitagata,Uganda

Lake Kitagata, Uganda, is a hypersaline crater lake with Na–SO₄–Cl–HCO₃–CO₃ chemistry, high pH and relatively small amounts of SiO₂. EQL/EVP, a brine evaporation equilibrium model (Risacher and Clement 2001), was used to model the major ion chemistry of the evolving brine and the order and masses of chemically precipitated sediments. Chemical sediments in a 1.6-m-long sediment core from Lake Kitagata occur as primary chemical mud (calcite, magadiite [NaSi₇O₁₃(OH)₃·3H₂O], burkeite [Na₆(CO₃)(SO₄)₂]) and as diagenetic intrasediment growths (mirabilite (Na₂SO₄·10H₂O)). Predicted mineral assemblages formed by evaporative concentration were compared with those observed in salt crusts along the shoreline and in the core from the lake center. Most simulations match closely with observed natural assemblages. The dominant inflow water, groundwater, plays a significant role in driving the chemical evolution of Lake Kitagata water and mineral precipitation sequences. Simulated evaporation of Lake Kitagata waters cannot, however, explain the large masses of magadiite found in cores and the formation of burkeite earlier in the evaporation sequence than predicted. The masses and timing of formation of magadiite and burkeite may be explained by past groundwater inflow with higher alkalinity and SiO₂ concentrations than exist today.     

Spatial variation in fluid flow and geochemical fluxes across the sediment-seawater interface at the Carlos Ribeiro mud volcano (Gulf of Cadiz)

Submarine mud volcanism is an important pathway for transfer of deep-sourced fluids enriched in hydrocarbons and other elements into the ocean. Numerous mud volcanoes (MVs) have been discovered along oceanic plate margins, and integrated elemental fluxes are potentially significant for oceanic chemical budgets. Here, we present the first detailed study of the spatial variation in fluid and chemical fluxes at the Carlos Ribeiro MV in the Gulf of Cadiz. To this end, we combine analyses of the chemical composition of pore fluids with a 1-D transport-reaction model to quantify fluid fluxes, and fluxes of boron, lithium and methane, across the sediment-seawater interface. The pore fluids are significantly depleted in chloride, but enriched in lithium, boron and hydrocarbons, relative to seawater. Pore water profiles of sulphate, hydrogen sulphide and total alkalinity indicate that anaerobic oxidation of methane occurs at 34-180 cm depth below seafloor. Clay mineral dehydration, and in particular the transformation of smectite to illite, produces pore fluids that are depleted in chloride and potassium. Profiles of boron, lithium and potassium are closely related, which suggests that lithium and boron are released from the sediments during this transformation. Pore fluids are expelled into the water column by advection; fluid flow velocities are 4 cm yr⁻¹ at the apex of the MV but they rapidly decrease to 0.4 cm yr⁻¹ at the periphery. The associated fluxes of boron, lithium and methane vary between 7-301, 0.5-6 and 0-806 mmol m⁻² yr⁻¹, respectively. We demonstrate that fluxes of Li and B due to mud volcanism may be important on a global scale, however, release of methane into the overlying water column is suppressed by microbial methanotrophy.     

The impact of vertebrate herbivores on wetland vegetation in Atchafalaya Bay, Louisiana

Delta islands in the Atchafalaya and Wax Lake deltas in Atchafalaya Bay, Louisiana, are in an extremely dynamic successional phase. These islands initially supported large marshes dominated by the pioneering plant species Sagittaria latifolia and Sagittaria platyphylla. A general decrease in vegetated areas has occurred in the delta island marshes in the Atchafalaya Delta since about 1980, while in the Wax Lake Delta portion of the complex the vegetation still flourished. The Atchafalaya Delta provides an interesting setting for the study of herbivory because of the complex interaction of biotic and physical factors operating in this delta. We hypothesized that grazing by herbivores has a marked effect on vegetation in these developing marshes. To test this hypothesis, exclosures were erected on islands in both deltas in September 1985 and January 1986. Each set of exclosure treatments included an openly-grazed control area, an ungrazed area, an area allowing nutria grazing, and one allowing waterfowl grazing in each site. Results of the experiment, based on field sampling of vegetation, indicated decreases in plant biomass and changes in plant species composition in grazed treatments. Waterfowl and nutria reduced biomass aboul equally, but there was a more marked effect in the openly grazed areas. These findings may be extrapolated to sediment diversion areas along the Mississippi River.     

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100–350° for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100°. Exchange rates were 3–5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure.Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O¹⁸ exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O¹⁸ exchange.At 350° kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O¹⁸ exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor.     

Solubility of alumina in orthopyroxene plus spinel as a geobarometer in complex systems. Applications to spinel-bearing alpine-type peridotites

The addition of Fe and Cr to the simple system MgO-SiO₂-Al₂O₃ markedly affects the activities of phases involved in the equilibrium

Controls on the chemistry of springs at Teels Marsh,Mineral County,Nevada

Evaporative process plays a dominant role in determining the water chemistry of the springs at Teels Marsh, a closed basin in western Nevada. Analysis of the spring waters indicates that calcium, magnesium, sulfate, and silica are removed from solution during dry periods, even though groundwater is undersaturated with respect to gypsum, amorphous silica, and sepiolite. The removal mechanism is precipitation of authigenic phases such as gypsum above the water table, in the vadose zone.In episodes of rain and snowfall in which none of the waters enters the phreatic zone, ions in the rain and snow accumulate near the ground surface. This accumulation of material, together with the sparse rain and snowfall, inhibits chemical weathering of silicate minerals. Only at high elevations in the basin is there sufficient fluxing of water through the alluvium for silicate weathering to make a significant contribution to the sodium content of the springs. When a sufficiently heavy rainfall occurs, salts are partially dissolved and the ions transported to the permanent groundwater. The kinetics of dissolution of secondary phases in the vadose zone exert an important control on the composition of the springs.     

A comparative study of the modelling of cement hydration and cement-rock laboratory experiments

The use of cement and concrete as fracture grouting or as tunnel seals in a geological disposal facility for radioactive wastes creates potential issues concerning chemical reactivity. From a long-term safety perspective, it is desirable to be able model these interactions and changes quantitatively. The ‘Long-term Cement Studies’ (LCS) project was formulated with an emphasis on in situ field experiments with more realistic boundary conditions and longer time scales compared with former experiments. As part of the project programme, a modelling inter-comparison has been conducted, involving the modelling of two experiments describing cement hydration on one hand and cement-rock reaction on the other, with teams representing the NDA (UK), Posiva (Finland), and JAEA (Japan).This modelling exercise showed that the dominant reaction pathways in the two experiments are fairly well understood and are consistent between the different modelling teams, although significant differences existed amongst the precise parameterisation (e.g. reactive surface areas, dependences of rate upon pH, types of secondary minerals), and in some instances, processes (e.g. partition of alkali elements between solids and liquid during cement hydration; kinetic models of cement hydration). It was not conclusive if certain processes such as surface complexation (preferred by some modellers, but not by others) played a role in the cement-rock experiment or not. These processes appear to be more relevant at early times in the experiment and the evolution at longer timescales was not affected. The observed permeability profile with time could not be matched. The fact that no secondary minerals could be observed and that the precipitated mass calculated during the simulations is minor might suggest that the permeability reduction does not have a chemical origin, although a small amount of precipitates at pore throats could have a large impact on permeability.The modelling exercises showed that there is an interest in keeping the numerical models as simple as possible and trying to obtain a reasonable fit with a minimum of processes, minerals and parameters. However, up-scaling processes and model parameterisation to the timescales appropriate to repository safety assessment are of considerable concern. Future modelling exercises of this type should focus on a suitable natural or industrial analogue that might aid assessing mineral-fluid reactions at these longer timescales.     

Density functional theory predictions of equilibrium isotope fractionation of iron due to redox changes and organic complexation

We present molecular orbital/density functional theory (MO/DFT) calculations that predict a greater isotopic fractionation in redox reactions than in reactions involving ligand exchange. The predicted fractionation factors, reported as 1000·ln(^56-54α), associated with equilibrium between Fe-organic and Fe-H₂O species were <1.6‰ in vacuo and <1.2‰ in solution when the oxidation state of the system was held constant. These fractionation factors were significantly smaller than those predicted for equilibrium between different oxidation states of Fe, for which 1000·ln(^56-54α) was >2.7‰ in vacuo and >2.2‰ in solution when the bound ligands were unchanged. The predicted ⁵⁶Fe/⁵⁴Fe ratio was greater in complexes containing Fe³⁺ and in complexes with shorter Fe-O bond lengths; both of these trends follow previous theoretical results. Our predictions also agree with previous experimental measurements that suggest that the largest biological fractionations will be associated with processes that change the oxidation state of Fe, and that identification of biologically controlled Fe isotope fractionation may be difficult when abiotic redox fractionations are present in the system. The models studied here also have important implications for future theoretical isotope calculations, because we have discovered the necessity of using vibrational frequencies instead of reduced masses when predicting reduced partition functions in aqueous-phase species.     

Holocene History of the Bering Sea Bowhead Whale (Balaena mysticetus) in Its Beaufort Sea Summer Grounds off Southwestern Victoria Island, Western Canadian Arctic

The fossil remains of 43 bowhead whales were mapped on the raised beaches of western Wollaston Peninsula, Victoria Island, Canadian Arctic, near the historic summer range limit of the Bering Sea stock in the Beaufort Sea. The elevations and radiocarbon ages of the remains demonstrate that the bowhead ranged commonly into the region following the submergence of Bering Strait at ca. 10,000 ¹⁴C yr B.P. until ca. 8500 ¹⁴C yr B.P. During the same interval, bowheads ranged widely from the Beaufort Sea to Baffin Bay. Subsequently, no whales reached Wollaston Peninsula until ca. 1500 ¹⁴C yr B.P. Late Holocene populations evidently were small, or occupations were brief, in comparison to those of the early Holocene. Although the late Holocene recurrence may relate to the expansion of pioneering Thule whalers eastward from Alaska, there are few Thule sites and limited evidence of Thule whaling in the area surveyed to support this suggestion.