A method for precise measurement of argon 40/36 and krypton/argon ratios in trapped air in polar ice with applications to past firn thickness and abrupt climate change in Greenland and at Siple Dome, Antarctica

We describe a method for measuring the ⁴⁰Ar/³⁶Ar ratio and the ⁸⁴Kr/³⁶Ar ratio in air from bubbles trapped in ice cores. These ratios can provide constraints on the past thickness of the firn layer at the ice core site and on the magnitude of past rapid temperature variations when combined with measured ¹⁵N/¹⁴N. Both variables contribute to paleoclimatic studies and ultimately to the understanding of the controls on Earth’s climate. The overall precision of the ⁴⁰Ar/³⁶Ar method (1 standard error of the mean) is 0.012‰ for a sample analyzed in duplicate, corresponding to ±0.6 m in reconstructed firn thickness. We use conventional dynamic isotope ratio mass spectrometry with minor modifications and special gas handling techniques designed to avoid fractionation. About 100 g of ice is used for a duplicate pair of analyses. An example of the technique applied to the GISP2 ice core yields an estimate of 11 ± 3K of abrupt warming at the end of the last glacial period 15,000 years ago. The krypton/argon ratio can provide a diagnostic of argon leakage out of the bubbles, which may happen (naturally) during bubble close-off or (artifactually) if samples are warmed near the freezing point during core retrieval or storage. Argon leakage may fractionate the remaining ⁴⁰Ar/³⁶Ar ratio by +0.007‰ per ‰ change in ⁸⁴Kr/³⁶Ar, introducing a possible bias in reconstructed firn thickness of about +2 m if thermal diffusion is not accounted for or +6 m if thermal diffusion effects are quantified with measured ¹⁵N/¹⁴N. Reproducibility of ⁸⁴Kr/³⁶Ar measured in air is about ±0.2‰ (1 standard error of the mean) but is about ±1‰ for ice core samples. Ice core samples are systematically enriched in ⁸⁴Kr/³⁶Ar relative to atmosphere by ∼5‰, probably reflecting preferential size-dependent exclusion of the smaller argon atom during bubble entrapment. Recent results from the Siple Dome ice core reveal two climate events during the last deglaciation, including an 18-m reduction in firn thickness associated with an abrupt warming at sometime between 18 and 22 kyr BP and a partial or total removal of the firn during an ablation event at 15.3 kyr BP.     

Serpentinization of abyssal peridotites from the MARK area, Mid-Atlantic Ridge: sulfur geochemistry and reaction modeling

The opaque mineralogy and the contents and isotope compositions of sulfur in serpentinized peridotites from the MARK (Mid-Atlantic Ridge, Kane Fracture Zone) area were examined to understand the conditions of serpentinization and evaluate this process as a sink for seawater sulfur. The serpentinites contain a sulfur-rich secondary mineral assemblage and have high sulfur contents (up to 1 wt.%) and elevated δ³⁴S_sulfide (3.7 to 12.7‰). Geochemical reaction modeling indicates that seawater-peridotite interaction at 300 to 400°C alone cannot account for both the high sulfur contents and high δ³⁴S_sulfide. These require a multistage reaction with leaching of sulfide from subjacent gabbro during higher temperature (∼400°C) reactions with seawater and subsequent deposition of sulfide during serpentinization of peridotite at ∼300°C. Serpentinization produces highly reducing conditions and significant amounts of H₂ and results in the partial reduction of seawater carbonate to methane. The latter is documented by formation of carbonate veins enriched in ¹³C (up to 4.5‰) at temperatures above 250°C. Although different processes produce variable sulfur isotope effects in other oceanic serpentinites, sulfur is consistently added to abyssal peridotites during serpentinization. Data for serpentinites drilled and dredged from oceanic crust and from ophiolites indicate that oceanic peridotites are a sink for up to 0.4 to 6.0 × 10¹² g seawater S yr⁻¹. This is comparable to sulfur exchange that occurs in hydrothermal systems in mafic oceanic crust at midocean ridges and on ridge flanks and amounts to 2 to 30% of the riverine sulfate source and sedimentary sulfide sink in the oceans. The high concentrations and modified isotope compositions of sulfur in serpentinites could be important for mantle metasomatism during subduction of crust generated at slow spreading rates.     

P-SH conversions in a flat-layered medium with anisotropy of arbitrary orientation

P-SH conversion is commonly observed in teleseismic P waves, and is often attributed to dipping interfaces beneath the receiver. Our modelling suggests an alternative explanation in terms of flat-layered anisotropy. We use reflectivity techniques to compute three-component synthetic seismograms in a 1-D anisotropic layered medium. For each layer of the medium, we prescribe values of seismic velocities and hexagonally symmetric anisotropy about a common symmetry axis of arbitrary orientation. A compressional wave in an anisotropic velocity structure suffers conversion to both SV -and SH -polarized shear waves, unless the axis of symmetry is everywhere vertical or the wave travels parallel to all symmetry axes. The P-SV conversion forms the basis of the widely used 'receiver function' technique. The P-SH conversion occurs at interfaces where one or both layers are anisotropic. A tilted axis of symmetry and a dipping interface in isotropic media produce similar amplitudes of both direct ( P ) and converted ( Ps ) phases, leaving the backazimuth variation of the P-Ps delay as the main discriminant. Seismic anisotropy with a tilted symmetry axis leads to complex synthetic seismograms in velocity models composed of just a few flat homogeneous layers. It is possible therefore to model observations of P coda with prominent transverse components with relatively simple 1-D velocity structures. Successful retrieval of salient model characteristics appears possible using multiple realizations of a genetic-algorithm (GA) inversion of P coda from several backazimuths. Using GA inversion, we determine that six P coda recorded at station ARU in central Russia are consistent with models that possess strong (> 10 per cent) anisotropy in the top 5 km and between 30 and 43 km depth. The symmetry axes are tilted, and appear aligned with the seismic anisotropy orientation in the mantle under ARU suggested by SKS splitting.     

Mitigating the Effects of Climate Change on the Water Resources of the Columbia River Basin

The potential effects of climate change on the hydrology and water resources of the Columbia River Basin (CRB) were evaluated using simulations from the U.S. Department of Energy and National Center for Atmospheric Research Parallel Climate Model (DOE/NCAR PCM). This study focuses on three climate projections for the 21st century based on a `business as usual' (BAU) global emissions scenario, evaluated with respect to a control climate scenario based on static 1995 emissions. Time-varying monthly PCM temperature and precipitation changes were statistically downscaled and temporally disaggregated to produce daily forcings that drove a macro-scale hydrologic simulation model of the Columbia River basin at 1/4-degree spatial resolution. For comparison with the direct statistical downscaling approach, a dynamical downscaling approach using a regional climate model (RCM) was also used to derive hydrologic model forcings for 20-year subsets from the PCM control climate (1995–2015) scenario and from the three BAU climate(2040–2060) projections. The statistically downscaled PCM scenario results were assessed for three analysis periods (denoted Periods 1–3: 2010–2039,2040–2069, 2070–2098) in which changes in annual average temperature were +0.5,+1.3 and +2.1 °C, respectively, while critical winter season precipitation changes were –3, +5 and +1 percent. For RCM, the predicted temperature change for the 2040–2060 period was +1.2 °C and the average winter precipitation change was –3 percent, relative to the RCM controlclimate. Due to the modest changes in winter precipitation, temperature changes dominated the simulated hydrologic effects by reducing winter snow accumulation, thus shifting summer streamflow to the winter. The hydrologic changes caused increased competition for reservoir storage between firm hydropower and instream flow targets developed pursuant to the Endangered Species Act listing of Columbia River salmonids. We examined several alternative reservoir operating policies designed to mitigate reservoir system performance losses. In general, the combination of earlier reservoir refill with greater storage allocations for instream flow targets mitigated some of the negative impacts to flow, but only with significant losses in firm hydropower production (ranging from –9 percent in Period1 to –35 percent for RCM). Simulated hydropower revenue changes were lessthan 5 percent for all scenarios, however, primarily due to small changes inannual runoff.     

Dislocating modernity: Identity, space and representations of street trade in Durban, South Africa

South Africa’s cities have experienced dramatic changes over the past decade. Cities are now home to a multiracial population, and have been transformed by new forms of economic and social interaction. For some, these changes have become a significant source of fear and anxiety. In this paper, we examine reactions to urban spatial change in the city of Durban, as expressed in local newspapers and interviews with suburban residents. We describe how the discourses of urban change in Durban have centred on the increased presence of street traders within the city’s public spaces, and the various ways in which the activity of street trade has disrupted long-established modernist norms governing the occupation and use of the urban space. Specifically, we offer a detailed reading of three prominent narratives within the discussion of street traders in Durban--chaos, congestion and pollution. We argue that street traders have come to embody a wide range of more deeply seated cultural anxieties, which have been brought to the fore in the context of South Africa’s transition. These anxieties arise from the ways in which modern understandings of order, agency and subjectivity have been called into question by material changes in the city, and have implications for the nature of citizenship and civic engagement in post-apartheid South Africa.     

Mercury in Eastern Kentucky coals: Geologic aspects and possible reduction strategies

Mercury emissions from US coal-fired power plants will be regulated by the US Environmental Protection Agency (USEPA) before the end of the decade. Because of this, the control of Hg in coal is important. Control is fundamentally based on the knowledge of the amounts of Hg in mined, beneficiated, and as-fired coal. Eastern Kentucky coals, on a reserve district level, have Hg contents similar to the USA average for coal at mines. Individual coals show greater variation at the bench scale, with Hg enrichment common in the top bench, often associated with enhanced levels of pyritic sulfur. Some of the variation between parts of eastern Kentucky is also based on the position relative to major faults. The Pine Mountain thrust fault appears to be responsible for elemental enrichment, including Hg, in coals on the footwall side of the thrust.Eastern Kentucky coals shipped to power plants in 1999, the year the USEPA requested coal quality information on coal deliveries, indicate that coals shipped from the region have 0.09 ppm Hg, compared to 0.10 ppm for all delivered coals in the USA. On an equal energy basis, and given equal concentrations of Hg, the high volatile bituminous coals from eastern Kentucky would emit less Hg than lower rank coals from other USA regions.     

Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (a_w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a_w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO₄·12H₂O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.     

Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.