Chemical studies of copper-organic complexes isolated from estuarine waters using C18 reverse-phase liquid chromatography

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography employing C₁₈ Sep-Pak cartridges (Waters Associates). The cartridges were found to have a constant retention efficiency for processing ? 1-l volumes of seawater. Fractionation of the isolated material, by sequential elution of the Sep-Pak with water: methanol mixtures of increasing organic solvent concentration, yielded a fraction of the organic matter with a specific copper activity six times greater than the overall activity for the isolated DOM. Analysis of this fraction by high performance liquid chromatography suggested that the organic components are of intermediate polarity and have appreciable aromatic character.An investigation of the protonation characteristics of the isolated complexes indicated that most of the copper is associated with a broad range of acidic sites on the DOM. Analysis by electron paramagnetic resonance spectroscopy confirmed the organic association of the isolated copper and also suggested the presence of several types of binding sites which probably involve oxygen donor ligands.Studies of the exchange of ⁶⁴Cu with these binding sites on the isolated DOM indicated that 70% of the sites undergo rapid exchange with copper in seawater while 20% of these sites did not exchange in a 24-h time period.     

Exact formulas for approximating variogram function integrals

The application of regionalized variables requires the estimation of the variogram function and the evaluation of its integral. By representing the variogram by a polygonal function the integral may be easily approximated by closed form representations of polygonal integrals. This approach provides a basis for more extensive statistical evaluation not evident in existing approximation methods. This paper provides the closed form representations for two-dimensional variogram functions whose domain is represented by a finite collection of rectangles.     

AGRICULTURAL DROUGHT ON SOUTH-CENTRAL PACIFIC ISLANDS *

A pilot study of spatial patterns of agricultural drought hazard in the south-central Pacific is presented. The durations of crop stress periods are estimated using a water balance approach. A rainfall approach is used to identify dry periods corresponding to different durations. Strong correlation between the results of the two methods indicates that monthly rainfall data are sufficient for estimating the patterns of agricultural drought hazard in the region. The simpler rainfall method is particularly useful for high islands where data required for the water balance approach are not sufficient to characterize the complex climatic patterns. Drought hazard is greatest in the eastern and southwestern parts of the study area. Great spatial variation in drought hazard is observed in a small area on the high islands of Western Samoa, where the range of values found within a few tens of kilometers is about the same as the range found across thousands of kilometers for low islands.     

Scaling Properties of Biologically Active Scalar Concentration Fluctuations in the Atmospheric Surface Layer over a Managed Peatland

The higher-order scalar concentration fluctuation properties are examined in the context of Monin–Obukhov similarity theory for a variety of greenhouse gases that have distinct and separate source/sink locations along an otherwise ideal micrometeorological field site. Air temperature and concentrations of water vapour, carbon dioxide and methane were measured at high frequency (10 Hz) above a flat and extensive peat-land soil in the San Joaquin–Sacramento Delta (California, USA) area, subjected to year-round grazing by beef cattle. Because of the heterogeneous distribution of the sources and sinks of CO₂ and especially CH₄ emitted by cattle, the scaling behaviour of the higher-order statistical properties diverged from predictions based on a balance between their production and dissipation rate terms, which can obtained for temperature and H₂O during stationary conditions. We identify and label these departures as ‘exogenous’ because they depend on heterogeneities and non-stationarities induced by boundary conditions on the flow. Spectral analysis revealed that the exogenous effects show their signatures in regions with frequencies lower than those associated with scalar vertical transport by turbulence, though the two regions may partially overlap in some cases. Cospectra of vertical fluxes appear less influenced by these exogenous effects because of the modulating role of the vertical velocity at low frequencies. Finally, under certain conditions, the presence of such exogenous factors in higher-order scalar fluctuation statistics may be ‘fingerprinted’ by a large storage term in the mean scalar budget.     

The meteorological framework and the cultural memory of three severe winter-storms in early eighteenth-century Europe

Three violent eighteenth-century storms that ravaged the North Sea area (1703), western central Europe (1739) and Portugal (1739) are investigated from the point of view of their meteorological setting, their socio-economic impact, and whether and by what means they secured an enduring place in the cultural memory. The evidence draws on individual narrative sources such as chronicles and poems, and institutional sources such as ship’s logbooks and state-organised ‘windthrow’ inventories of tree loss. Each of the three storms had socio-economic impacts that could be described as ‘war-like’ in the damage caused to buildings and the destruction of forests. The “Great Storm” of December 1703 jeopardized English naval supremacy in the War of the Spanish Succession by sinking a number of Royal Navy ships and taking the life of more than 8000 seamen. In January 1739 two similarly destructive storms swept over mainland Europe. The cultural memory of the three events here considered was however strikingly different. The sequence of storms in January 1739 though being the most protracted of the last centuries, and well-chroniceled, did not persist in the collective memories of those in France, Switzerland and elsewhere who experienced them. Likewise, the “Great Storm” was quickly forgotten on the continent, whereas its memory remained deeply rooted in England through the writings of Defoe (1704). In Portugal the 1739 storm won a lasting place in the country’s cultural memory owing to two poems that it inspired. Furthermore, it was recorded in the Kingdom’s official newspaper, in the astronomical prognoses and in written records of the Old Regime’s cultural elite.     

Hydrocarbons generated by hydropyrolysis of suspended marine particulate organic matter: Relationship to the oceanography of the Black Sea and the Rhodes Gyre

The suspended particulate organic matter, SPOM, in the autumnal Black Sea has been characterised using catalytic hydropyrolysis (HyPy) of the total (bound plus free) lipid material. The technique, which generates maximum yields of volatile products from sediments, kerogens and phytoplankton, was followed using gas chromatography and gas chromatography/mass spectrometry. The generated alkanes were dominated by n-C₁₈, hypothesised to arise predominantly from unsaturated C₁₈ fatty acids. Steranes were generated from reductive conversion of free and bound sterols. The generation of branched alkanes and especially of hopanes provided formal evidence for the participation of bacteria in the mineralisation of the SPOM. Whereas similar distributions of n-alkanes were generated from SPOM sampled from different depths of the comparatively well-stirred Rhodes Gyre (eastern Mediterranean), mineralisation of the SPOM at each depth of the central Black Sea produced characteristic changes in the composition and concentration of the HyPy products. Depth profiles of the n-alkanes generated from SPOM in the region of the Rim Current were affected by the local hydrography. Polynuclear aromatic hydrocarbons (PAHs) of anthropogenic origin were present in the surface waters of the central Black Sea. Some methyl benzenes, thiophenes and pyrroles were also generated.     

Krieger’s conceptualization and measurement of discrimination and internalized oppression in studies of adverse health outcomes

Embodiment is a central concept in Krieger’s ecosocial theory, and is said to be of relevance to the understanding of the relationship between social conditions and a variety of adverse health outcomes. The most detailed empirical investigation of this in Krieger’s work is to be found in her studies of the relationship between racial discrimination and high blood pressure. Of especial relevance here is the idea of internalized oppression which is said to explain the observed association between self-reports of no racial discrimination and increased levels of blood pressure among working-class African Americans. Here we critically examine the empirical evidence pertaining to internalized oppression. Specifically, we focus on the measurement of the construct and the quality of the empirical evidence that has been presented in support of the hypothesis that there is an association between internalized oppression and adverse health outcomes. We argue that the validity of the concept has yet to be established and that the available data linking it to poor health outcomes are open to alternative explanations, notably measurement error and misclassification.

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Rheologies and ages of lava flows on Elysium Mons,Mars

We present results of our study of the rheologies and ages of lava flows in the Elysium Mons region of Mars. Previous studies have shown that the geometric dimensions of lava flows reflect rheological properties such as yield strength, effusion rate and viscosity. In this study the rheological properties of lava flows in the Elysium Mons region were determined and compared to the rheologies of the Ascraeus Mons lava flows. We also derived new crater size-frequency distribution measurements (CSFDs) for the Elysium lava flows to identify possible changes in the rheological properties with time. In addition, possible changes in the rheological properties with the distance from the caldera of Elysium Mons were analyzed.In total, 35 lava flows on and around Elysium Mons were mapped, and divided into three groups, lava flows on the flanks of Elysium Mons, in the plains between the three volcanoes Elysium Mons, Hecates and Albor Tholus and lava flows south of Albor Tholus. The rheological properties of 32 of these flows could be determined. Based on our morphometric measurements of each individual lava flow, estimates for the yield strengths, effusion rates, viscosities, and eruption duration of the studied lava flows were made. The yield strengths of the investigated lava flows range from ～3.8 × 10² Pa to ～1.5 × 10⁴ Pa, with an average of ～3.0 × 10³ Pa. These yield strengths are in good agreement with estimates for terrestrial basaltic lava flows. The effusion rates are on average ～747 m³ s^?1, ranging from ～99 to 4450 m³ s^?1. The viscosities are on average ～4.1 × 10⁶ Pa s, with a range of 1.2 × 10⁵ Pa s to 3.1 × 10⁷ Pa s. The eruption durations of the flows were calculated to be between 6 and 183 days, with an average of ～51 days. The determined rheological properties are generally very similar to those of other volcanic regions on Mars, such as on Ascraeus Mons in the Tharsis region. Calculated yield strengths and viscosities point to a basaltic/andesitic composition of the lava flows, similar to basaltic or andesitic a’a lava flows on Earth.Absolute model ages of all 35 lava flows on Elysium Mons were derived from crater size-frequency distribution measurements (CSFD). The derived model ages show a wide variation from about 632 Ma to 3460 Ma. Crater size-frequency distribution measurements of the Elysium Mons caldera show an age of ～1640 Ma, which is consistent with the resurfacing age of Werner (2009). Significant changes of the rheologies with time could not be observed. Similarly, we did not observe systematic changes in ages with increasing distances of lava flows from the Elysium Mons caldera.