Spatial gradients in plant leaf wax D/H across a coastal salt marsh in southern California

Coastal salt marsh ecosystems contain strong environmental gradients that are anticipated to influence the D/H ratios recorded in the leaf waxes of salt-tolerant plants. We characterized the molecular and hydrogen isotopic composition of alkanes in plant and sediment samples as well as the D/H ratios of environmental and plant waters across an elevation and inundation gradient in a southern Californian, coastal salt marsh. We sampled the dominant salt marsh plant species: Salicornia virginica, Arthrocnemum subterminale and Jamuea carnosa (all succulents), as well as Monanthochloe littoralis and Limonium californicum (nonsucculents). Plant xylem water hydrogen isotopic compositions indicate a shift in source waters from meteoric influences at upland sites (δD value −20‰) to seawater dominated values (0‰) at lowland areas. We found leaf water D enrichment relative to xylem water ranging from mean δD values of +54‰ (upland) to +28‰ (lowland), interpreted as a reduction of transpiration with increasing inundation time. This has the effect of increasing the net fractionation between source water and leaf wax product across the environmental gradient from mean values of −101‰ (upland) to −134‰ (lowland), with an attenuated signal recorded in the δD values of plant leaf wax n-alkanes (−122‰ to −136‰). These results constrain the hydrogen isotopic composition of salt marsh organic matter that may contribute to marine carbon budgets of the Santa Barbara Basin, and further indicate the potential for plant leaf waxes to resolve paleoenvironmental change, including sea level change, in sediment cores from salt marsh ecosystems.     

Biogeochemical processes in a clay formation in situ experiment: Part E - Equilibrium controls on chemistry of pore water from the Opalinus Clay, Mont Terri Underground Research Laboratory, Switzerland

The chemistry of pore water (particularly pH and ionic strength) is an important property of clay rocks being considered as host rocks for long-term storage of radioactive waste. Pore waters in clay-rich rocks generally cannot be sampled directly. Instead, their chemistry must be found using laboratory-measured properties of core samples and geochemical modelling. Many such measurements have been made on samples from the Opalinus Clay from the Mont Terri Underground Research Laboratory (URL). Several boreholes in that URL yielded water samples against which pore water models have been calibrated. Following a first synthesis report published in 2003, this paper presents the evolution of the modelling approaches developed within Mont Terri URL scientific programs through the last decade (1997-2009). Models are compared to the composition of waters sampled during dedicated borehole experiments. Reanalysis of the models, parameters and database enabled the principal shortcomings of the previous modelling efforts to be overcome. The inability to model the K concentrations correctly with the measured cation exchange properties was found to be due to the use of an inappropriate selectivity coefficient for Na-K exchange; the inability to reproduce the measured carbonate chemistry and pH of the pore waters using mineral-water reactions alone was corrected by considering clay mineral equilibria. Re-examination of the measured Ca/Mg activity ratios and consideration of the mineralogical composition of the Opalinus Clay suggested that Ca/Mg cation exchange rather than dolomite saturation may control the ratio of these ions in solution. This re-examination also suggests that the Ca/Mg ratio decreases with increasing pore-water salinity. Several possible reasons for this are proposed. Moreover, it is demonstrated that feldspar equilibria must not be included in Opalinus Clay modelling because feldspars are present only in very small quantities in the formation and because Na/K ratios measured in pore water samples are inconsistent with feldspar saturation. The principal need to improve future modelling is additional or better data on rock properties, in particular: (i) a more detailed identification of phases in the Opalinus Clay that include redox-sensitive elements together with evaluation of their thermodynamic properties; (ii) an improved understanding of the distribution of celestite throughout the Opalinus Clay for Sr/SO₄ concentrations control; (iii) improvements in analytic and thermodynamic data for Ca-Mg rock cation exchange and mineral chemical properties and (iv) the measurement of composition and stability constants of clay minerals actually present in the formation.     

Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand

Brothers volcano, of the Kermadec intraoceanic arc, is host to a hydrothermal system unique among seafloor hydrothermal systems known anywhere in the world. It has two distinct vent fields, known as the NW Caldera and Cone sites, whose geology, permeability, vent fluid compositions, mineralogy, and ore-forming conditions are in stark contrast to each other. The NW Caldera site strikes for ??600?m in a SW?CNE direction with chimneys occurring over a ??145-m depth interval, between ??1,690 and 1,545?m. At least 100 dead and active sulfide chimney spires occur in this field and are typically 2?C3?m in height, with some reaching 6?C7?m. Their ages (at time of sampling) fall broadly into three groups: <4, 23, and 35?years old. The chimneys typically occur near the base of individual fault-controlled benches on the caldera wall, striking in lines orthogonal to the slopes. Rarer are massive sulfide crusts 2?C3?m thick. Two main types of chimney predominate: Cu-rich (up to 28.5?wt.% Cu) and, more commonly, Zn-rich (up to 43.8?wt.% Zn). Geochemical results show that Mo, Bi, Co, Se, Sn, and Au (up to 91?ppm) are correlated with the Cu mineralization, whereas Cd, Hg, Sb, Ag, and As are associated with the dominant Zn-rich mineralization. The Cone site comprises the Upper Cone site atop the summit of the recent (main) dacite cone and the Lower Cone site that straddles the summit of an older, smaller, more degraded dacite cone on the NE flank of the main cone. Huge volumes of diffuse venting are seen at the Lower Cone site, in contrast to venting at both the Upper Cone and NW Caldera sites. Individual vents are marked by low-relief (??0.5?m) mounds comprising predominately native sulfur with bacterial mats. Vent fluids of the NW Caldera field are focused, hot (??300°C), acidic (pH????2.8), metal-rich, and gas-poor. Calculated end-member fluids from NW Caldera vents indicate that phase separation has occurred, with Cl values ranging from 93% to 137% of seawater values. By contrast, vent fluids at the Cone site are diffuse, noticeably cooler (??122°C), more acidic (pH?1.9), metal-poor, and gas-rich. Higher-than-seawater values of SO₄ and Mg in the Cone vent fluids show that these ions are being added to the hydrothermal fluid and are not being depleted via normal water/rock interactions. Iron oxide crusts 3?years in age cover the main cone summit and appear to have formed from Fe-rich brines. Evidence for magmatic contributions to the hydrothermal system at Brothers includes: high concentrations of dissolved CO₂ (e.g., 206?mM/kg at the Cone site); high CO₂/³He; negative ??D and ??¹⁸O_H2O for vent fluids; negative ??³⁴S for sulfides (to ?4.6??), sulfur (to ?10.2??), and ??¹⁵N₂ (to ?3.5??); vent fluid pH values to 1.9; and mineral assemblages common to high-sulfidation systems. Changing physicochemical conditions at the Brothers hydrothermal system, and especially the Cone site, occur over periods of months to hundreds of years, as shown by interlayered Cu?+?Au- and Zn-rich zones in chimneys, variable fluid and isotopic compositions, similar shifts in ³He/⁴He values for both Cone and NW Caldera sites, and overprinting of ??magmatic?? mineral assemblages by water/rock-dominated assemblages. Metals, especially Cu and possibly Au, may be entering the hydrothermal system via the dissolution of metal-rich glasses. They are then transported rapidly up into the system via magmatic volatiles utilizing vertical (??2.5?km long), narrow (??300-m diameter) ??pipes,?? consistent with evidence of vent fluids forming at relatively shallow depths. The NW Caldera and Cone sites are considered to represent stages along a continuum between water/rock- and magmatic/hydrothermal-dominated end-members.     

The role of granites in volcanic-hosted massive sulphide ore-forming systems: an assessment of magmatic�Chydrothermal contributions

Assessment of geological, geochemical and isotopic data indicates that a significant subgroup of volcanic-hosted massive sulphide (VHMS) deposits has a major or dominant magmatic?Chydrothermal source of ore fluids and metals. This group, which is typically characterised by high Cu and Au grades, includes deposits such as those in the Neoarchean Doyon-Bousquet-LaRonde and Cambrian Mount Lyell districts. These deposits are distinguished by aluminous advanced argillic alteration assemblages or metamorphosed equivalents intimately associated with ore zones. In many of these deposits, ??³⁴S_sulphide is low, with a major population below ?3??; ??³⁴S_sulphate differs from coexisting seawater and ??³⁴S_{sulphate?Csulphide}????20?C30??. These characteristics are interpreted as the consequence of disproportionation of magmatic SO₂ as magmatic?Chydrothermal fluids ascended and cooled and as a definitive evidence for a significant magmatic?Chydrothermal contribution. Other characteristics that we consider diagnostic of significant magmatic?Chydrothermal input into VHMS ore fluids include uniformly high (>3 times modern seawater values) salinities or very ¹⁸O-enriched (??¹⁸O?>?5??) ore fluids. We do not consider other criteria [e.g. variable salinity, moderately high ??¹⁸O_fluid (2?C5??), ??³⁴S_sulphide near 0??, metal assemblages or a spatial association with porphyry Cu or other clearly magmatic-hydrothermal deposits] that have been used previously to advocate significant magmatic?Chydrothermal contributions to be diagnostic as they can be produced by non-magmatic processes known to occur in VHMS mineral systems. However, in general, a small magmatic?Chydrothermal contribution cannot be excluded in most VHMS systems considered. Conclusive data that imply minimal magmatic?Chydrothermal contributions are only available in the Paleoarchean Panorama district where coeval seawater-dominated and magmatic?Chydrothermal systems appear to have been physically separated. This district, which is characterised by chloritic and sericitic alteration assemblages and lacks aluminous advanced argillic alteration assemblages, is typical of many VHMS deposits around the world, suggesting that for ??garden variety?? VHMS deposits, a significant magmatic?Chydrothermal contribution is not required. Other than deposits associated with advanced argillic alteration assemblages, the only deposit for which we ascribe a major magmatic?Chydrothermal contribution is the Devonian Neves Corvo deposit. This deposit differs from other deposits in the Iberian Pyrite Belt and around the world in being extremely Sn-rich, with the Sn closely associated with Cu and in having formed from high ¹⁸O-rich fluids (??¹⁸O_fluid ??8.5??). We consider these characteristics, particularly the last, as diagnostic of a significant magmatic hydrothermal contribution. Our analysis indicates that two subgroups of VHMS deposits have a major magmatic?Chydrothermal contribution: Cu/Au-rich deposits with aluminous alteration assemblages and reduced, very Sn-rich deposits in which Sn was introduced in a high-temperature ore assemblage. Comparison with ??normal?? VHMS deposits suggests that these subgroups of VHMS deposits may form in specialised tectonic environments. The Cu/Au-rich deposits appear to form adjacent to magmatic arcs, an environment conducive to the generation of hydrous, oxidised melts by melting metasomatised mantle in the wedge above the subducting slab. This contrasts with the back-arc setting of ??normal?? VHMS deposits in which relatively dry granites (In this contribution, we use the term granite sensu latto) formed by decompression melting drive seawater-dominated hydrothermal circulation. The tectonic setting of highly Sn-rich VHMS deposits such as Neves Corvo is less clear; however, thick continental crust below the ore-hosting basin may be critical, as it is in other Sn deposits.     

An Equation of State for Hypersaline Water in Great Salt Lake,Utah, USA

Great Salt Lake (GSL) is one of the largest and most saline lakes in the world. In order to accurately model limnological processes in GSL, hydrodynamic calculations require the precise estimation of water density (ρ) under a variety of environmental conditions. An equation of state was developed with water samples collected from GSL to estimate density as a function of salinity and water temperature. The ρ of water samples from the south arm of GSL was measured as a function of temperature ranging from 278 to 323 degrees Kelvin (^oK) and conductivity salinities ranging from 23 to 182 g L⁻¹ using an Anton Paar density meter. These results have been used to develop the following equation of state for GSL (σ = ± 0.32 kg m⁻³):

Boron incorporation into mullite

Summary Boron-doped mullites were synthesized using aluminium nitrate-nonahydrate, tetraethoxysilane and boric acid in a sol–gel process with subsequent annealing at 950 and 1300 °C for five hours. Two different bulk compositions with constant Al₂O₃ contents (60 and 70 mol%, respectively) and varying SiO₂ plus B₂O₃ contents were investigated. X-ray powder diffraction analyses yielded a linear decrease of the lattice parameters with increasing bulk B₂O₃ content, which was interpreted as to be due to boron incorporation. Related to the increasing boron content, corresponding infrared spectra revealed a slight and continuous shift for most of the absorption bands. These data show that mullite is able to incorporate large amounts of boron into its structure (up to about 20 mol% B₂O₃ depending on the bulk composition of the starting materials). Infrared analyses suggest that boron is incorporated into the mullite structure in form of planar three-fold coordinated BO₃ groups. Author’s address: A. Beran, Institut für Mineralogie und Kristallographie, Universit?t Wien-Geozentrum, Althanstra?e 14, 1090 Wien, Austria     

Feasibility of pre-earthquake strengthening of buildings based on cost-benefit and life-cycle cost analysis, with the aid of fragility curves

There are two fundamental questions this article aims to deal with. First, whether a pre-earthquake strengthening of a large and heterogeneous building stock (the emphasis here is on building types common in S. Europe), is economically feasible or not, and second what is the optimal retrofit level for mitigating the seismic risk. To this purpose contemporary decision making tools, namely cost-benefit and life-cycle cost analyses, are tailored to the needs of the present study, and implemented with the aid of an ad-hoc developed new software application (COBE06). A method for estimating the reduction in structural vulnerability due to retrofit is proposed, as well as a methodology to determine the optimum retrofit level using the fragility curve approach. Finally, the proposed methodology is used in a pilot application that concerns the city of Thessaloniki, and results are drawn for the feasibility of strengthening the reinforced concrete building stock in this city.     

Water and Boating Activity as Dispersal Vectors for <Emphasis Type="Italic">Schinus terebinthifolius</Emphasis> (Brazilian pepper) Seeds in Freshwater and Estuarine Habitats

Schinus terebinthifolius (Brazilian pepper), a native of South America, is currently naturalized in 20 countries worldwide and can alter native systems by displacing flora and forming monotypic stands. The primary described mechanism of seed dispersal is through consumption of fruits by birds and mammals. We evaluated an alternative dispersal method by evaluating the potential for S. terebinthifolius growing in freshwater and estuarine environments to disperse via water currents. Specifically, we: (1) determined the duration fruits remained buoyant in three salinities, (2) estimated the viability of seeds after 7 days in water, (3) estimated the dispersal rate of floating solitary fruits, and (4) examined the role of boat wakes in moving seeds above mean high water at the shoreline. The length of time fruits floated in 0 ppt water (4.9 days) was significantly less than 15 ppt saltwater (6.2 days), and 30 ppt saltwater (6.9 days). After 7 days, over 13% of seeds remained viable in 0 ppt, 15 ppt, and 30 ppt water. By combining mean dispersal rates and the mean number of days fruits floated, we calculated individual fruits could be transported 16.9 km in 0 ppt and over 22 km in 15 and 30 ppt water. To increase germination, seeds must be stranded above the intertidal zone. Wind wakes alone never achieved this result; however, boat wakes plus wind wakes significantly increased the movement of fruits above the intertidal region into drier soils. The use of both vertebrate dispersal vectors and water dispersal may potentially increase the rate of invasion, establishment, and survival of S. terebinthifolius in freshwater and estuarine environments.     

The arsenic source term for an in-pit uranium mine tailings facility and its long-term impact on the regional groundwater

Detailed field sampling and analyses and laboratory-based diffusion-cell experiments were used in conjunction with 3-D reactive transport modeling (MODFLOW and MT3D99) to quantify the fate and long-term (10 ka) transport of As in the Rabbit Lake In-pit Tailings Management Facility (RLITMF), northern Saskatchewan, Canada. The RLITMF (300 m × 425 m × 90 m thick) was engineered to ensure solute transport within the RLITMF is dominated by diffusion. Concentrations of As in the tailings pore fluids ranged from 0.24 to 140 mg/L (n = 43). Arsenic speciation analyses indicate 90% of this arsenic exists as As⁵⁺. This observation is supported by pH–Eh measurements of pore fluids (n = 135). Geochemical analyses yielded a strong inverse correlation between the Fe/As molar ratio in the tailings solids and the corresponding concentration of dissolved As, which is attributed to the adsorption of As to secondary 2-line ferrihydrite present in the tailings. Diffusion-cell testing yielded values for the effective diffusion coefficient, sorption coefficient, and effective porosity of As in the tailings of 4.5 × 10⁻¹⁰ m²/s, 2–4 cm³/g and 0.36, respectively. Reactive transport simulations using the field and laboratory data show adsorption of As to the tailings and diffusive transport of dissolved As in the tailings should reduce the source term concentration of As to between 40% and 70% of the initial concentrations over the 10 ka simulation period. Based on these simulations, the As concentrations in the regional groundwater, 50 m down gradient of the tailings facility, should be maintained at background concentrations of 0.001 mg/L over the 10 ka period. These findings suggest the engineered in-pit disposal of U mine tailings can provide long-term protection for the local groundwater regime from As contamination.