Modelling carbon isotopes of carbonates in cave drip water

C isotopes in cave drip water are affected by both the C isotope composition of soil air and host rock carbonate. Furthermore, the C isotope composition of cave drip water strongly depends on the calcite dissolution system, i.e., open, closed and intermediate conditions. Here, we present a calcite dissolution model, which calculates the ¹⁴C activity and δ¹³C value of the dissolved inorganic carbon of the drip water. The model is based on the chemical equations describing calcite dissolution (). The most important improvement, relative to previous models, is the combination of the open and closed system conditions in order to simulate the C isotope composition during intermediate states of calcite dissolution and the application to carbon isotope measurements on cave drip waters from Grotta di Ernesto, Italy. The major changes in the C isotope composition of the drip water occur in response to variations in the open-closed system ratio. Additionally, the ¹⁴C activity and the δ¹³C value of the drip water depend on changes in the partial pressure of soil CO₂. Radiocarbon and δ¹³C values of the Grotta di Ernesto drip water are well reproduced by the model.     

Bounding difference: Intersectionality and the material production of gender, caste, class and environment in Nepal

Current theorising in human geography draws attention to the relational emergence of space and society, challenging ideas of difference that rely on fixed identities and emphasising the importance of the everyday in the production of social inequalities. Similarly, feminist political ecology has emphasised the role of ‘nature’ or ‘environment’ in the production of subjectivities such that ideas of gender and nature arise in relation to each other. In this paper I build from these insights to explore the ways in which the embodied performance of gender, caste and other aspects of social difference collapse the distinction between the material and the symbolic. Symbolic ideas of difference are produced and expressed through embodied interactions that are firmly material. Through this kind of conceptualisation, I hope to push forward debates in geography on nature and feminist political ecology on how to understand the intersectional emergence of subjectivities, difference and socio-natures. Importantly, it is the symbolic meanings of particular spaces, practices and bodies that are (re)produced through everyday activities including forest harvesting, agricultural work, food preparation and consumption, all of which have consequences for both ecological processes and social difference. Through the performance of everyday tasks, not only are ideas of gender, caste and social difference brought into view, but the embodied nature of difference that extends beyond the body and into the spaces of everyday life is evident. I use ethnographic evidence from rural Nepal to explore the ways in which boundaries between bodies, spaces, ecologies and symbolic meanings of difference are produced and maintained relationally through practices of work and ritual.     

Equivalent Permeability and Simulation of Two-Phase Flow in Heterogeneous Porous Media

The problem of calculating equivalent grid block permeability tensors for heterogeneous porous media is addressed. The homogenization method used involves solving Darcy's equation subject to linear boundary conditions with flux conservation in subregions of the reservoir and can be readily applied to unstructured grids. The resulting equivalent permeability tensor is stable as defined relative to G-convergence. It is proposed to use both conforming and mixed finite elements to solve the local problems and compute approximations from above and below of the equivalent permeability, respectively. Comparisons with results obtained using periodic, pressure and no-flux boundary conditions and the renormalization method are presented. A series of numerical examples demonstrates the effectiveness of the methodology for two-phase flow in heterogeneous reservoirs.     

Genesis of lithium pegmatites from the leinster granite margin,southeast ireland: Geochemical constraints

Extensive and economically-important lithium pegmatites have been described from the eastern flank of the large S-type peraluminous Leinster Granite batholith in southeast Ireland. This flank area is also the locus of a major dip-slip ductile shear zone which was active during emplacement of the Tullow Lowlands pluton of the batholith. All the known bedrock occurrences of lithium pegmatite are contained within this marginal deformation zone. Most previous studies have suggested derivation of the lithium pegmatites by fractionation from the Leinster Granite itself, though none are conclusive. More recently, an anatectic model has been proposed whereby the pegmatites were derived by melting of Li-rich sediments adjacent to the batholithic contact. Our investigation has been concerned with a detailed study of the Rb-Sr isotope systematics and trace element geochemistry of the pegmatites and their host granitoids in an attempt to resolve the problem of pegmatite genesis. The results suggest a strong geochemical and temporal coherence between the Leinster Granite and the lithium pegmatites. A model is proposed in which Li enrichment in residual magmas may be linked to the development of muscovite instead of biotite in the Leinster Granite itself. The Li excluded from entry to biotite then accumulates in highly mobile, low-viscosity pegmatitic fluids which migrate into the marginal shear zone of the Tullow Lowlands pluton where they crystallize at considerably lower temperatures.     

Compositions of group IVB iron meteorites and their parent melt

The concentrations of P, V, Cr, Fe, Co, Ni, Cu, Ga, Ge, As, Mo, Ru, Rh, Pd, W, Re, Os, Ir, Pt, and Au in the group IVB iron meteorites Cape of Good Hope, Hoba, Skookum, Santa Clara, Tawallah Valley, Tlacotepec, and Warburton Range have been measured by laser ablation inductively coupled plasma mass spectrometry. The data were fitted to a model of fractional crystallization of the IVB parent body core, from which the composition of the parent melt and metal/melt distribution coefficients for each element in the system were determined, for a chosen value of D(Ni). Relative to Ni and chondritic abundances, the parent melt was enriched in refractory siderophiles, with greatest enrichment of 5× chondritic in the most refractory elements, and was strongly volatile-depleted, down to 0.00014× chondritic in Ge. Comparison to an equilibrium condensation sequence from a gas of solar composition indicates that no single temperature satisfactorily explains the volatility trend in the IVB parent melt; a small (<1%) complement of ultrarefractory components added to metal that is volatile-depleted but otherwise has nearly chondritic abundances (for Fe, Co and Ni) best explains the volatility trend. In addition to this volatility processing, which probably occurred in a nebular setting, there was substantial oxidation of the metal in the IVB parent body, leading to loss of Fe and other moderately siderophile elements such as Cr, Ga, and W, and producing the high Ni contents that are observed in the IVB irons. By assuming that the entire IVB parent body underwent a similar chemical history as its core, the composition of the silicate that is complementary to the IVB parent melt was also estimated, and appears to be similar to that of the angrite parent.     

Concentration, isotopic composition, and sources of lead in Southern Ocean air during 1999/2000, measured at the Cape Grim Baseline Air Pollution Station, Tasmania

Southern Ocean aerosols were collected at the Cape Grim Baseline Air Pollution Station from onshore air under baseline conditions between February 1999 and April 2000. Thermal ionization techniques (TIMS) and isotope dilution mass spectrometry (IDMS) were used to measure the isotopic composition and concentration of lead in the air giving concentrations as low as 0.6 ± 0.1 pg · m⁻³. Air collected under baseline conditions for 12 months (May 1999-April 2000) yielded an overall lead concentration of 11.0 ± 0.2 pg · m⁻³ and isotopic composition of ²⁰⁶Pb/²⁰⁷Pb = 1.154, ²⁰⁸Pb/²⁰⁷Pb = 2.387 and ²⁰⁶Pb/²⁰⁴Pb = 17.93. The range in isotopic ratios was consistent with the mixing of lead from major population centers in the Southern Hemisphere in the mid to high latitudes, except for the presence of highly radiogenic lead in some samples. Contributions from radiogenic lead of up to ∼0.8% were observed. Three periods with the highest percentage contribution of radiogenic lead (>0.5%) were investigated in more detail, and 4-d back-trajectories and radon concentrations were used to help identify the sources. The sources are probably associated with the mining and processing of uranium rich ores in southern Africa and possibly South Australia.     

Detecting trends in seagrass abundance using aerial photograph interpretation: Problems arising with the evolution of mapping methods

In the late 1970s and early 1980s an inventory of seagrass distribution in southeast Australia was made from multiscale aerial photographs using a simple analog mapping method, referred to here as theCamera lucida technique. Four priority estuaries were remapped in 2003, also using multi-scale aerial photographs, but using a geographic information system (GIS)-based analog mapping technique. We quantified the degree of error that arose when estimates of seagrass distribution were compared for the two techniques be ressessing. with GIS, the same aerial photographs used earlier for four estuaries: Port Hacking, Bermagui River, Merimbula Lake, and St Georges Basin.Camera lucida produced a larger estimate of total seagrass area than GIS in all four locations: 8% of total seagrass area or 12.9 ha in Port Hacking, 15% or 5 ha in Bermagui River, 20% or 38.0 ha in Merimbula Lake, and 243% or 502.2 ha in St Georges Basin. The consistent and moderate discrepancy in Port Hacking, Bermagui River, and Merimbula Lake was attributed mainly to differences betweenCamera lucida and GIS, such as the tendency ofCamera lucida to overestimate seagrass area by amalgamating disjunct seagrass patches into continuous meadows. The large discrepancy at St Georges Basin was attributed to interoperator error; i.e., the operators who mapped photographs taken in 1979 had widely differing interpretations of the aerial photographs. A 20-yr trend was calculated for each estuary using either theCamera lucida or revised GIS value as the start point. Perceived management status of the seagrass depended greatly on the initial data used. In St Georges Basin, a catastrophic decline (65%, 553.9 ha) occurred based on theCamera lucida-GIS comparison but only a small decline (14.7%, 51.8 ha) when all photos were GIS assessed, In view of the technical developments in habitat mapping, evaluation of change in seagrass abundance using remote sensing needs an assessment of intra-operator error, inter-operator error, and systemic error before maps produced by superseded technology are considered useful baselines.     

Spawning densities,egg densities,size structure,and movement patterns of spawning horseshoe crabs,<Emphasis Type="Italic">Limulus polyphemus</Emphasis>, within four coastal embayments on Cape Cod,Massachusetts

Spawning densities, spawning indices, egg densities, size distributions, and movement patterns of horseshoe crabs (Limulus polyphemus) were quantified for four coastal embayments (Monomoy National Wildlife Refuge, Pleasant Bay, Nauset Estuary, and Cape Cod Bay) on Cape Cod, Massachusetts from 2000 to 2002. Spawning activity was highest from mid May through mid June, but densities varied throughout the Cape Cod region. Average spawning densities (male and female crabs combined), measured using 25-m² quadrats, were lower than 1 crab 25 m^?2, although certain locations had consistently higher densities averaging 2 to 3 crabs 25 m^?2 with individual survey densities recorded as high as 17 crabs 25 m^?2. Spawning densities during night surveys were either similar or slightly higher than day surveys, except at a few sites within Pleasant Bay. Spawning indices were considerably lower ranging from 0 to 1.3 females 25 m^?2 throughout the Cape Cod region. Spawning sex ratios varied from 1∶1.6 to 1∶3.1 (females:males) throughout the region, except within Pleasant Bay where highly male skewed ratios were observed (e.g., 1∶5.8, 3-yr average). Egg densities were low overall (<1 egg cm^?2) throughout Cape Cod and egg densities tended to be higher in deeper sediments (5–20 cm deep) compared to shallow sediments (0–5 cm deep) at most locations. Over 7,800 horseshoe crabs were tagged on Cape Cod from 2000 to 2002. Average size and size frequency distributions of tagged crabs varied among regions. Larger individuals were observed at Monomoy National Wildlife Refuge while the smallest individuals were from Cape Cod Bay. We documented an overall recapture rate of 6.7% and our tag-recapture data indicated that 62% of crabs were recaptured at the original tagging location and 70% of recaptures traveled less than 2 km from the original tagging location, providing evidence for localized populations on Cape Cod. We have observed that horseshoe crabs differ among embayments within a regional area, suggesting the potential need for management plans specific to embayments or subregions depending on the characteristics of a population.     

Cu(II) adsorption at the calcite-water interface in the presence of natural organic matter: Kinetic studies and molecular-scale characterization

We have characterized the adsorption of Suwannee River humic acid (SRHA) and Cu(II) on calcite from preequilibrated solutions at pH 8.25. Sorption isotherms of SRHA on calcite follow Langmuir-type behavior at SRHA concentrations less than 15 mg C L⁻¹, whereas non-Langmuirian uptake becomes evident at concentrations greater than 15 mg C L⁻¹. The adsorption of SRHA on calcite is rapid and mostly irreversible, with corresponding changes in electrostatic properties. At pH 8.25, Cu(II) uptake by calcite in the presence of dissolved SRHA decreases with increasing dissolved SRHA concentration, suggesting that formation of Cu-SRHA aqueous complexes is the primary factor controlling Cu(II) sorption at the calcite surface under the conditions of our experiments. We also observed that surface-bound SRHA has little influence on Cu(II) uptake by calcite, suggesting that Cu(II) coordinates to calcite surface sites rather than to surface-bound SRHA.Cu K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) spectroscopic results show that the local coordination of Cu adsorbed at the calcite surface is very similar in the presence and absence of SRHA. Ca backscatterers at ∼3.90 Å indicate that Cu(II) forms tetragonally distorted inner-sphere adsorption complexes in both binary and ternary systems. Subtle differences in the XANES and EXAFS between binary sorption samples and ternary sorption samples, however, prevent us from ruling out the formation of ternary Cu-SRHA surface complexes. Our findings demonstrate that SRHA plays an important role in controlling the fate and transport of Cu(II) in calcite-bearing systems.     

Platinum-group element systematics in Mid-Oceanic Ridge basaltic glasses from the Pacific, Atlantic, and Indian Oceans

The concentrations of Ir, Ru, Pt and Pd have been determined in 29 Mid-Oceanic Ridge basaltic (MORB) glasses from the Pacific (N = 7), the Atlantic (N = 10) and the Indian (N = 11) oceanic ridges and the Red Sea (N = 1) spreading centers. The effect of sulfide segregation during magmatic differentiation has been discussed with sample suites deriving from parental melts produced by high (16%) and low (6%) degrees of partial melting, respectively. Both sample suites define positive and distinct covariation trends in platinum-group elements (PGE) vs. Ni binary plots. The high-degree melting suite displays, for a given Ni content, systematically higher PGE contents relative to the low-degree melting suite. The mass fraction of sulfide segregated during crystallization (X_sulf), the achievement of equilibrium between sulfide melt and silicate melts (R_eff), and the respective proportions between fractional and batch crystallization processes (S_b) are key parameters for modeling the PGE partitioning behavior during S-saturated MORB differentiation. Regardless of the model chosen, similar sulfide melt/silicate melt partition coefficients for Ir, Ru, Pt and Pd are needed to model the sulfide segregation process, in agreement with experimental data. When corrected for the effect of magmatic differentiation, the PGE data display coherent variations with partial melting degrees. Iridium, Ru and Pt are found to be compatible in nonsulfide minerals whereas the Pd behaves as a purely chalcophile element. The calculated partition coefficients between mantle sulfides and silicate melts (assuming a PGE concentration in the oceanic mantle at ∼0.007 × CI-chondritic abundances) increase from Pd (∼10³) to Ir (∼10⁵). This contrasting behavior of PGE during S-saturated magmatic differentiation and mantle melting processes can be accounted for by assuming that Monosufide Solid Solution (Mss) controls the PGE budget in MORB melting residues whereas MORB differentiation processes involve Cu-Ni-rich sulfide melt segregation.