Regional studies of dolomites and their included fluids: recognizing multiple chemically distinct fluids during the complex diagenetic history of Lower Carboniferous (Mississippian) rocks of the Irish Zn-Pb ore field

This study provides a regional framework within which studies of ore-related dolomite and dolomite cements may be placed. Fluid inclusion data indicate the presence of three distinct fluids following early dolomitization: 1) a ubiquitous low-temperature, higher salinity fluid found in saddle dolomite; 2) a low-temperature, lower salinity fluid limited to sub-Waulsortian and Waulsortian carbonates; and 3) a higher temperature, lower salinity fluid found in Waulsortian and supra-Waulsortian rocks. Similar fluids have been reported in ore-associated minerals and postmineralization dolomite (Type 1) and in ore-stage carbonates and sphalerite (Types 2 and 3). The halogen geochemistry of included fluids indicates genesis from evaporated seawater. Type 1 fluids are enriched in chloride relative to bromide, reflecting a component of salinity derived via dissolution of halite or from dehydration of seawater. These data suggest that dolomitization and mineralization of Mississippian rocks in the Midlands requires both regionally extensive and localized fluid flow.     

Adsorption of organic matter at mineral/water interfaces: I. ATR-FTIR spectroscopic and quantum chemical study of oxalate adsorbed at boehmite/water and corundum/water interfaces

The types and structures of adsorption complexes formed by oxalate at boehmite (γ-AlOOH)/water and corundum (α-Al₂O₃)/water interfaces were determined using in situ attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy and quantum chemical simulation methods. At pH 5.1, at least four different oxalate species were found at or near the boehmite/water interface for oxalate surface coverages (Γ_ox) ranging from 0.25 to 16.44 μmol/m². At relatively low coverages (Γ_ox < 2.47), strongly adsorbed inner-sphere oxalate species (IR peaks at 1286, 1418, 1700, and 1720 cm⁻¹) replace weakly adsorbed carbonate species, and a small proportion of oxalate anions are adsorbed in an outer-sphere mode (IR peaks at 1314 and 1591 cm⁻¹). IR peaks indicative of inner-sphere adsorbed oxalate are also observed for oxalate at the corundum/water interface at Γ_ox = 1.4 μmol/m². With increasing oxalate concentration (Γ_ox > 2.47 μmol/m²), the boehmite surface binding sites for inner-sphere adsorbed oxalate become saturated, and excess oxalate ions are present dominantly as aqueous species (IR peaks at 1309 and 1571 cm⁻¹). In addition to these adsorption processes, oxalate-promoted dissolution of boehmite following inner-sphere oxalate adsorption becomes increasingly pronounced with increasing Γ_ox and results in an aqueous Al(III)-oxalate species, as indicated by shifted IR peaks (1286 → 1297 cm⁻¹ and 1418 → 1408 cm⁻¹). At pH 2.5, no outer-sphere adsorbed oxalate or aqueous oxalate species were observed. The similarity of adsorbed oxalate spectral features at pH 2.5 and 5.1 implies that the adsorption mechanism of aqueous HOx⁻ species involves loss of protons from this species during the ligand-exchange reaction. As a consequence, adsorbed inner-sphere oxalate and aqueous Al(III)-oxalate complexes formed at pH 2.5 have coordination geometries very similar to those formed at pH 5.1.The coordination geometry of inner-sphere adsorbed oxalate species was also predicted using quantum chemical geometry optimization and IR vibrational frequency calculations. Geometry-optimized Al₈O₁₂ and Al₁₄O₂₂ clusters with the reactive surface Al site coordinated by three oxygens were used as model substrates for corundum and boehmite surfaces. Among the models considered, calculated IR frequencies based on a bidentate side-on structure with a 5-membered ring agree best with the observed frequencies for boehmite/oxalate/water samples at Γ_ox = 0.25 to 16.44 μmol/m² and pH 2.5 and 5.1, and for a corundum/oxalate/water sample at Γ_ox = 1.4 μmol/m² and pH 5.1. Based on these results, we suggest that oxalate bonding on boehmite and corundum surfaces results in 5-coordinated rather than 4- or 6-coordinated Al surface sites.     

Seasonal and interannual patterns of distribution and diet of bluefish within a Middle Atlantic bight estuary in relation to abiotic and biotic factors

Seasonal and interannual patterns in the spatial distribution of bluefish (Pomatomus saltatrix) within a Middle Atlantic Bight estuary were examined using multipanel gillnets fished biweekly at 14 fixeds stations in the Sandy Hook Bay-N avesink River estuary during May–November of 1998 and 1999. To characterize habitats along the estuarine gradient, we measured several abiotic and biotic variables concurrently with gillnet sampling. Juvenile (age-0 and age-1+) bluefish were captured regularly during both years along with large numbers of Atlantic menhaden (Brevoortia tyrannus), which were confirmed by diet analyses to be bluefish’s primary forage species. The date of initial appearance of age-0 bluefish and menhaden in the estuary varied between years and may have been related to interannual differences in seawater temperatures on the continental shelf during spring. Delayed estuarine arrival of prey fishes may have contributed to variability in bluefish diets between years. Within the estuary, bluefish spatial distribution were consistent across seasons and years: bluefish were most common in areas associated with high concentrations of suspended materials and the presence of menhaden. Community analyses also indicated habitat overlap between bluefish and menhaden. Spatial distribution patterns revealed the consistent occurrence of piscivorous bluefish in shallow estuarine habitats that retained suspended materials and aggregated prey fishes. Foraging success of bluefish and other estuarine piscivores may be closely linked with the availability of these productive habitat, highlighting the need for future study of biological interactions and the governing physical processes.     

Non-monotonic chemical and O,Sr, Nd,and Pb isotope zonations and heterogeneity in the mafic- to silicic-composition magma chamber of the Grizzly Peak Tuff,Colorado

Strong compositional zonation of the 34 Ma Grizzly Peak Tuff in west-central Colorado is attended by non-monotonic trends in O, Sr, Nd, and Pb isotope ratios. Fiamme from the tuff cluster in chemical compositions and petrographic characteristics, indicating the magma chamber was not continuously zoned but consisted of at least seven compositional layers. The most mafic magma erupted (57 wt% SiO₂, fiamme group 7) had ¹⁸O= +8.5, initial ⁸⁷Sr/⁸⁶Sr=0.7099, _Nd, and ²⁰⁶Pb/²⁰⁴Pb=17.80, suggesting that the magma was produced by 50% fractional crystallization of basaltic magma that assimilated 20 to 40 wt% Proterozoic crust. Isotopic compositions of more evolved parts of the chamber (up to 77 wt% SiO₂, fiamme group 1) depart from the mafic base-level composition of fiamme group 7, and reflect late-stage assimilation that occurred largely after compositional layering was established. ¹⁸O values decrease by as much as 1.5 from fiamme groups 7 through 4, indicating assimilation of hydrothermally altered roof rocks. ¹⁸O values abruptly inerease by up to 1.5 between fiamme groups 4 and 3. This discontinuity is interpreted to reflect evolution in an asymmetric chamber that had a split-level roof, allowing assimilation of wall rocks that varied vertically in degree of hydrothermal alteration. This chamber geometry is also supported by collapse structures in the caldera. Late-stage assimilation of heterogeneous wall rocks is also indicated by variations in Sr, Nd, and Pb isotope ratios. Large Sr isotope disequilibrium exists between some phenocrysts and whole-rock fiamme, and initial ⁸⁷Sr/⁸⁶Sr ratios in phenocrysts are as high as 0.7170. values regularly increase from-13.0 in fiamme group 7 to-11.3 in fiamme group 3, and then decrease to-12.2 in fiamme group 1. ²⁰⁶Pb/²⁰⁴Pb ratios generally increase from 17.80 to 17.94 for fiamme groups 7 through 1. The rhyolitic parts of the Grizzly Peak Tuff have isotopic compositions that could be attributed to a purely crustal melt. It is unlikely, however, that the mafic parts of the tuff were generated by crustal melting, and the compositional and isotopic variations across the entire zonation of the tuff are best explained by fractional crystallization of mantle-derived magmas, accompanied by extensive assimilation of Proterozoic crust.     

Treatment of pulsating white dwarfs including general relativistic effects

In this paper, pulsating white dwarfs are treated via general relativity. Numerical integration of Einstein's equations was used to find equilibrium white dwarfs models and the fundamental periods of small oscillations about these equilibrium models. In these calculations account was taken of coulomb, Thomas-Fermi, and exchange interactions as well as ion zero point energies. It is shown that general relativity makes not just a quantitative difference in the results but a qualitative differences; pure C¹² models which are stable in Newtonian mechanics can be unstable against collapse (at a central density of 3×10¹⁰ g/cm³) when general relativity is taken into account. The collapsing model may become a neutron star or may continue towards the Schwarzschild radius.More realistic white dwarf models with carbon burning products at the center, also were studied. For these models, the density at which the star becomes unstable against collapse due to electron capture (3×10⁹ g/cm³) was found to be lower than the density at which general relativistic instability occurs.     

Seasat-A satellite scatterometer instrument evaluation

The Seasat-A satellite scatterometer (SASS) was designed to measure ocean surface wind speed and direction in twenty-four (24) independent cells over a 1000-km swath. It operated in the interrupted CW mode at a frequency of 14.6 GHz with four (4) fan beam antennas and used Doppler filtering in the receiver for resolving the cells on the surface. The instrument began operating in space on July 6, 1978, and gathered normalized radar cross section (sigma^{0}) data for approximately 2290 h. The purpose of this paper is to describe the in-orbit evaluation of the SASS hardware and its compatibility with the spacecraft. It has been determined that the scatterometer operated flawlessly throughout the mission, met all design requirements, and established a good data base for geophysical processing.     

Nitrate sources and sinks in Elkhorn Slough,California: Results from long-term continuous in situ nitrate analyzers

Nitrate and water quality parameters (temperature, salinity, dissolved oxygen, turbidity, and depth) were measured continuously with in situ NO₃ analyzers and water quality sondes at two sites in Elkhorn Slough in Central California. The Main Channel site near the mouth of Elkhorn Slough was sampled from February to September 2001. Azevedo Pond, a shallow tidal pond bordering agricultural fields further inland, was sampled from December 1999 to July 2001. Nitrate concentrations were recorded hourly while salinity, temperature, depth, oxygen, and turbidity were recorded every 30 min. Nitrate concentrations at the Main Channel site ranged from 5 to 65 μM. The propagation of an internal wave carrying water from ≈100 m depth up the Monterey Submarine Canyon and into the lower section of Elkhorn Slough on every rising tide was a major source of nitrate, accounting for 80–90% of the nitrogen load during the dry summer period. Nitrate concentrations in Azevedo Pond ranged from 0–20 μM during the dry summer months. Nitrate in Azevedo Pond increased to over 450 μM during a heavy winter precipitation event, and interannual variability driven by differences in precipitation was observed. At both sites, tidal cycling was the dominant forcing, often changing nitrate concentrations by 5-fold or more within a few hours. Water volume flux estimates were combined with observed nitrate concentrations to obtain nitrate fluxes. Nitrate flux calculations indicated a loss of 4 mmol NO₃ m^?2 d^?1 for the entire Elkhorn Slough and 1 mmol NO₃ m^?2 d^?1 at Azevedo Pond. These results suggested that the waters of Elkhorn Slough were not a major source of nitrate to Monterey Bay but actually a nitrate sink during the dry season. The limited winter data at the Main Channel site suggest that nitrate was exported from Elkhorn Slough during the wet season. Export of ammonium or dissolved organic nitrogen, which we did not monitor, may balance some or all of the NO₃ flux.     

The distribution of iodine and chlorine in soils over lead-zinc mineralisation,East of Glogfawr,mid-Wales

The potential pathfinder elements iodine, as total (I_tot) and watersoluble (I_aq), chlorine (Cl_tot and Cl_aq) together with F, As, Pb, Zn and Cu have been determined in B horizon soils over proved lead-zinc mineralisation east of the disused Glogfawr mine, Dyfed, Wales. Pb and Cu are anomalous in soils over this occurrence while Zn fails to reflect underlying mineralisation. Total and water soluble I and Cl show anomalously high values over the proved mineralisation and also indicate extensions along the trend of the mineralised fracture system to the south-southwest and the north-northeast; these anomalies are more extensive than those formed by Pb or Cu.In the soils analysed there is a strong correlation between I_tot and I_aq and Cl_tot and Cl_aq and it is possible that a simple water-extractable method could be of use in geochemical prospecting.