Bayes estimation: A novel approach to derivation of internally consistent thermodynamic data for minerals,their uncertainties,and correlations. Part II: Application

Internally consistent thermodynamic data, including their uncertainties and correlations, are reported for 22 phases of the quaternary system CaO-Al₂O₃-SiO₂-H₂O. These data have been derived by simultaneous evaluation of the appropriate phase properties (PP) and reaction properties (RP) by the novel technique of Bayes estimation (BE). The thermodynamic model used and the theory of BE was expounded in Part I of this paper. Part II is the follow-up study illustrating an application of BE. The input for BE comprised, among others, the a priori values for standard enthalpy of formation of the i-th phase, Δ_f H _i ⁰ , and its standard entropy, S _i ⁰ , in addition to the reaction reversal constraints for 33 equilibria involving the relevant phases. A total of 269 RP restrictions have been processed, of which 107 turned out to be non-redundant. The refined values for Δ_f H _i ⁰ and S _i ⁰ obtained by BE, including their 2σ-uncertainties, appear in Table 4; the Appendix reproduces the corresponding correlation matrix. These data permit generation of computed phase diagrams with 2σ-uncertainty envelopes based on conventional error propagation; Fig. 3 depicts such a phase diagram for the system CaO-Al₂O₃-SiO₂. It shows that the refined dataset is capable of yielding phase diagrams with uncertainty envelopes narrow enough to be geologically useful. The results in Table 4 demonstrate that the uncertainties of the prior values for Δ_f H _i ^Emphasis>0 , given in Table 1, have decreased by up to an order of magnitude, while those for S _i ⁰ improved by a factor of up to two. For comparison, Table 4 also lists the refined Δ_f H _i ⁰ and S _i ⁰ data obtained by mathematical programming (MAP), minimizing a quadratic objective function used earlier by Berman (1988). Examples of calculated phase diagrams are given to demonstrate the advantages of BE for deriving internally consistent thermodynamic data. Although P-T curves generated from both MAP and BE databases will pass through the reversal restrictions, BE datasets appear to be better suited for extrapolations beyond the P-T range explored experimentally and for predicting equilibria not constrained by reversals.     

The stellar populations within theρ Oph cloud cores

We have obtained infrared colors and limiting magnitudes from 1.25–4.8µm for a sample of 26 of the cm continuum radio sources located in the core of the Oph molecular cloud. Their colors demonstrate that the majority of the sources appear to be heavily reddened objects surrounded by circumstellar accretion disks. In these cases the radio emission most likely diagnoses accretion driven energetic outflow phenomena: either ionized winds or possibly synchrotron emission from shocked gas associated with stellar jets.     

The history and impact of air pollution at Čertovo Lake,southwestern Czech Republic

This multi-disciplinary investigation documents the longterm effects of atmospheric pollution of metals and acids on a geologically sensitive catchment in the umava Mountains, southwestern Czech Republic, a region with a long history of human disturbance. A 30 cm long sediment core (I) from ertovo Lake was analyzed for natural and artifical radionuclides, metals, diatoms, chrysophytes, and pollen in sediments accumulated during the last 200 years. A second core (II), extending to 95 cm, included sediment judged to be free of atmospheric deposition of pollutants associated with the Industrial Revolution. Chronostratigraphic markers include several changes in the pollen assemblages corresponding to well-documented changes in land-use, and distinct distributions of ¹³⁷Cs, ¹³⁴Cs and ²⁴¹Am from weapons testing and the 1986 nuclear accident at Chernobyl, Russia. These markers corroborate the ²¹⁰Pb dating and, together, produce a reliable chronology extending back nearly to 1800 A.D.Stratigraphic profiles of Cu, Pb, and Zn in Core I are unlike any previously reported in the literature. Concentrations of Cu, Pb, and Zn remain generally above 100, 400, and 200 g g^-1, respectively, for the 200 years represented by Core I. These values are unusually high for sediments from a watershed with no known heavy-metal ore bodies. Accumulation rates for Cu, Pb, and Zn, which include both atmospheric and watershed contributions, are also high (ca 1, > 1 and > 1 g cm^-2 yr^-1, respectively) for the same period, although the anthropogenic contribution of Zn rose from nearly zero at 1800 A.D. The Cu and Pb accumulation rates rose dramatically about 1640 A.D.Accumulation rates of anthropogenically-derived Be, a relatively abundant element in the soft coals of the region, are also elevated by about 0.01 g cm^-2 yr^-1 in sediments of this period. Vanadium accumulation rates increased only since 1980 A.D., presumably along with increased consumption of oil.Diatom assemblages illustrate that the lake was acidic (pH between 4.5 and 5) through at least the past 200 years. The pH declined significantly (from ca 5 to 4) between 1960 and 1985 with a slight increase to 4.5 in the last few years. Recent diatom and chrysophyte assemblages suggest high trace metal concentrations, consistent with the present lake-water chemistry.     

Theoretical infrared spectra of some model polycyclic aromatic hydrocarbons: effect of ionization

In order to test the hypothesis of ionized polycyclic aromatic hydrocarbons (PAHs) as possible carriers of the UIR bands, we realized a computational exploration on selected PAHs of small dimension in order to identify which changes ionization would induce on their IR spectra. In this study we performed ab initio calculations of the spectra of neutral and positively ionized naphthalene, anthracene, and pyrene. The results are significantly important. The frequencies in the cations are slightly shifted with respect to the neutral species, but no general conclusion can be reached from the three molecules considered. By contrast, the relative intensities of most vibrations are strongly affected by ionization, leading to a much better agreement between the calculated CH/CC vibration intensity ratios and those deduced from observations.     

Cycle anatomy and variability in the storm-dominated type cincinnatian (Upper Ordovician): coming to grips with cycle delineation and genesis

Although parasequence and sequence are scale-independent terms, they are frequently applied only to specific scales of cycles. For example, meter-scale cycles are commonly assumed to be parasequences or PACs. In the Upper Ordovician Kope and Fairview Formations of northern Kentucky, we examined a succession of 50 meter-scale cycles that have been variously interpreted as deepening-upward, shallowing-upward, or showing no relationship with water depth. Our analysis shows that these cycles, characterized by shifts in storm-bed proximality, are highly variable in their thickness and internal construction. Most cycles are best considered high-frequency sequences, because deepening-upward intervals are common, and many cycles contain evidence of abrupt basinward shifts in facies as expected at sequence boundaries. A minority fit the parasequence model of shallowing-upward cycles bounded by flooding surfaces. Larger, 20 m scale cycles are defined by systematic thickening and thinning trends of meter-scale cycles. However, meter-scale cycles do not display any systematic trends in cycle anatomy as a function of position within the 20 m cycles or position within the Kope and Fairview Formations. The high cycle variability and the lack of systematic stratigraphic organization with respect to longer-term cyclicity reflect either the irregularity of relative sea-level changes, the poor recording of sea-level changes in this deep-water setting, or the generation of these cycles by climate-induced cyclicity in storm intensity. These three mechanisms would generate similar patterns at the outcrop scale, so it is not possible at the present to distinguish between them.     

Geochemistry of the Grenville Dyke Swarm: role of plume-source mantle in magma genesis

Major and trace element data of samples from the approximately 590 Ma Grenville dyke swarm, in the southeastern parts of the Canadian Shield, were used to evaluate the extent of crustal contamination of the dyke magma and to model its probable mantle source. The dyke rocks are mostly saturated, quartz tholeiites. A few samples represent transitional basalts. Their overall chemistries are similar to those of continental flood basalts. Their compositions resemble those of liquids initially produced in the garnet peridotite mantle zone and then subjected to polybaric fractionation. However, fractionation models fail to mass-balance Ti, Fe, K, and P. Geochemical and isotopic criteria indicate that crustal contamination was minimal. The incompatible elements Zr, Y, K, Rb, Nb, V, Ta, Hf, and Th show hyperbolic elemental ratio-ratio distributions indicative of mixing between two end-members. One end-member has elemental ratios similar to those of a depleted N-MORB source and the second of a P-MORB i.e. ertile or plume MORB source. The more enriched dyke compositions can be successfully reproduced by mixing models in the ratio of 6:1 between the most depleted MORB-like dyke magma and a liquid composition similar to metasomatic glass veinlets coexisting with mica peridotite mantle xenoliths, and subsequent crystal fractionation. The Grenville dykes are probably a synrift swarm that was emplaced along a rift arm related to an Iapetan rrr triple junction that is thought to have formed over a mantle plume. The chemistry of the dyke swarm is consistent with its derivation from a plume head, in that the minor enriched source can be identified with plume-source mantle and the major depleted source with entrained mantle. The magma probably originated in the upper cooler parts of the plume head.     

Association of orogenic activity with the Ordovician radiation of marine life

The Ordovician radiation of marine life was among the most substantial pulses of diversification in Earth history and coincided in time with a major increase in the global level of orogenic activity. To investigate a possible causal link between these two patterns, the geographic distributions of 6576 individual appearances of Ordovician vician genera around the world were evaluated with respect to their proximity to probable centers of orogeny (foreland basins). Results indicate that these genera, which belonged to an array of higher taxa that diversified in the Middle and Late Ordovician (trilobites, brachiopods, bivalves, gastropods, monoplacophorans), were far more diverse in, and adjacent to, foreland basins than they were in areas farther removed from orogenic activity (carbonate platforms). This suggests an association of orogeny with diversification at that time.     

On the interpretation of Fraunhofer line Doppler shifts at supergranule boundaries

We have used the SPO tower telescope and echelle spectrograph to study differences in the profiles of three Fei lines, between magnetic network and cells. Ca K slit-jaw pictures were used to identify the network and cell areas, and mean network and cell profiles were computed from digitized spectra for the g = 0 lines 4065, 5434, and the g = 1.5 line 5233. The profile bisectors show that the wings of all three lines are red-shifted in the network by between 75–200 m s^–1 relative to the cell profiles. But the redshift decreases in the line core and becomes less than the standard error of 20 m s^–1 near the line core minimum. This disappearance of the redshift at the cores of all 3 lines formed over the height range 250–500 km above _0.5 = 1, argues against a steady downflow at supergranule boundaries. We show that such red-shifted wings and a relatively unshifted core can result if granular convection is suppressed near the network flux tubes, without implying any downflow in the vicinity of these flux tubes. Our results also indicate that searches for large-scale convective velocity patterns should measure shifts of the line core, rather than the line wings which appear to be very sensitive to inhomogeneities in granule structure.Visiting Astronomers, Sacramento Peak Observatory.     

Part II. Evaluation of Ar-Ar quartz ages: Implications for fluid inclusion retentivity and determination of initial Ar/Ar values in Proterozoic samples

The argon isotope systematics of vein-quartz samples with two different K-reservoirs have been evaluated in detail. Potassium is hosted by ultra-high-salinity fluid inclusions in quartz samples from the Eloise and Osborne iron-oxide-copper-gold (IOCG) deposits of the Mt Isa Inlier, Australia. In contrast, K is hosted by accidentally trapped mica within lower-salinity fluid inclusions of a sample selected from the Railway Fault, 13 km south of the Mt Isa copper mine, Australia. Imprecise apparent ages have been obtained for all of the samples studied and conclusively demonstrate that quartz fluid inclusions are retentive to Ar and have not leaked over billions of years. IOCG samples that host K in fluid inclusions only, have K/Cl values of <1 and the ages obtained represent the maximum ages for mineralization. In contrast, the Railway Fault samples that include accidentally trapped mica have K/Cl values of ?1. Excess ⁴⁰Ar_E plus Cl hosted by fluid inclusions, and radiogenic ⁴⁰Ar_R plus K, are strongly correlated in these samples and define a plane in 3D ⁴⁰Ar-³⁶Ar-K-Cl space. In this case, the plane yields an ‘excess ⁴⁰Ar_E’ corrected age of ∼1030 Ma that is 100’s of Ma younger than nearby Cu-mineralization at Mt Isa. The age is interpreted to reflect ⁴⁰Ar-loss from the accidentally trapped mica into the surrounding fluid inclusions, and is not related to the samples’ age of formation. The initial ⁴⁰Ar/³⁶Ar value of fluid inclusions is widely used to provide information on fluid origin. For the IOCG samples that host K in fluid inclusions only, the initial ⁴⁰Ar/³⁶Ar values are close to the measured values at every temperature of stepped heating experiments. For samples that include accidentally trapped mica, the correction for post-entrapment radiogenic ⁴⁰Ar_R production is significant. Furthermore, because ³⁹Ar_K present in accidentally trapped mica crystals is released at different temperatures to radiogenic ⁴⁰Ar_R lost to the surrounding fluid inclusions, intra-sample ⁴⁰Ar/³⁶Ar variation cannot be reliably documented. The results demonstrate that noble gas analysis is readily applicable to Proterozoic, or older, samples but that if K-mineral impurities are present within quartz the abundance of K must be determined before calculation of mean ⁴⁰Ar/³⁶Ar values that are representative of the samples’ initial composition.     

Responses of resident marsh fishes to stages ofPhragmites australis invasion in three mid Atlantic estuaries

Modification of brackish marshes by nonindigenousPhragmites australis has occurred across a broad geographical area in eastern North America. Among its effects on marsh processes,Phragmites may be increasingly unfavorable to marsh surface fishes as its invasion progresses within an estuary. We assessed the effect of thePhragmites invasion on resident marsh surface fishes by examining the population response ofFundulus heteroclitus (mummichog, 5–48 mm TL) andF. luciae (spotfin killifish, 5–41 mm TL) to four distinct invasion stages in three estuaries of the U.S. mid Atlantic region (New Jersey, Delaware, and Maryland). We documented precipitous declines in mean catch per unit effort ofF. heteroclitus in pit traps from natural marsh (51.6), through initial (33.8), early (12.3), and late invasion stages (2.4) across all sites. A similar pattern was documented forF. luciae, with mean catch per unit effort in pit traps declining from natural marsh (48.9), through initial (39.1), early (9.3), and late invasion stages (2.7). Population structure of both species also changed somewhat across invasion stages such that we collected a narrower size range of individuals of both species from late invasion stages. Patterns suggest that as thePhragmites invasion progresses, there is a decline in habitat function for larval and juvenileF. heteroclitus and an increased risk of extirpation ofF. luciae from brackish marshes along the east coast of the U.S.