The role of organic coatings in the enrichment of marine particles with selenium. The fixation of selenite on an adsorbed amino acid

The enrichment of marine particles with selenium cannot be explained as that with metals present in cationic form by complexation with anionic functional groups of adsorbed organic matter. Physicochemical data obtained using a model system are reported. The surface of the particles is modelized by a mercury electrode whose surface charge density can be easily changed, covered by a layer of adsorbed polymers. Studies with different kinds of macromolecules and salts show a specific interaction between adsorbed polyalanine and selenite. The results can be explained by the concordance of the distances between two oxygen atoms in this oxyanion and between two amine groups of the adsorbed polypeptide. A similar mechanism could occur in marine aggregates whatever their nature, as long as they contain amine groups at their surface which result in this concordance. Some prospects derived from the results are discussed.     

Petroleum hydrocarbons in sediments of Southampton water estuary

The sediments of Southampton Water were analysed for petroleum hydrocarbons to determine the fate of petrochemical refinery waste in the estuary. Much of the petroleum hydrocarbons appears to be removed by adsorption onto estuarine sediments close to source. Surface sediment concentrations range from 3·1mg/g dry weight near a refinery to 0·5 mg/g dry weight at locations distant from the refinery.The absence of any change with depth in total hydrocarbon concentrations from some sediment cores and the presence of distinct ‘oil’ horizons in others suggests that mixing of sediments in the area is very random. Sedimentation rates in areas where a distinct oil horizon was observed ranged from 1 to 3cm a year.     

Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

Environmental Factors Contributing to the Development and Demise of a Toxic Dinoflagellate (<Emphasis Type="Italic">Karlodinium veneficum</Emphasis>) Bloom in a Shallow,Eutrophic, Lagoonal Estuary

A dense bloom of the ichthyotoxic dinoflagellate Karlodinium veneficum was discovered in the Neuse River Estuary, North Carolina, on 19 October 2006 and was associated with four subsequent fish kills. Microscopic, photopigment, DNA, and toxicological techniques confirmed bloom identity and toxicity. High-resolution spatio-temporal data from ship-board and fixed automated sampling stations provided a unique opportunity to investigate the environmental conditions that initiated, maintained, and terminated the K. veneficum bloom. Bloom initiation and growth were favored by high nutrient availability and reduced dispersal during the period of declining riverine discharge after Tropical Storm Ernesto. K. veneficum out-competed other co-occurring dinoflagellates, perhaps because of the production of karlotoxins that are known to act as grazing deterrents and to facilitate mixotrophic feeding. Once the bloom was established, small-scale hydrodynamic processes, coupled with vertical migration, concentrated cells along a frontal convergence to high densities (>200,000 cells per milliliter). By 26 October 2006, wind mixing and possible nutrient stress disrupted the bloom. Release of cell-bound toxins during the bloom collapse likely accounted for the associated fish kill events where fish were reported as exhibiting typical symptoms of karlotoxin poisoning. The dynamics of this bloom underscore the tight control of harmful algal blooms by meteorological forcing, hydrology, and sediment nutrient input in this shallow lagoonal estuary.     

A model of an exploding,radiating star in general relativity

In a previous paper Adams, Cary and Cohen (1994) presented a model of a supernova. In that paper the equations of General Relativity describing the evolution of a spherically symmetric, radiating star were solved analytically. The evolution of the star was determined by the application of boundary conditions at the center and at the edge. Due to lmitations in the presupernova model, only the very slow inward motion of an unstable, degenerate core could be considered. The solution was also limited by the need to exclude a runaway term, one that increased exponentially with time. Without the exclusion of the runaway, the luminosity would have increased without bound and the mass would have become negative.This paper presents a completely analytic solution to the equations of General Relativity describing the evolution of a Type II supernova. Professor S.E. Woosley kindly gave us data on the physical variables of a 12M ₀ presupernova star. In our model the core collapses within 1 s, leaving a 1.3M ₀ remnant. Shortly afterward 10.6M ₀ is ejected to infinity, and 0.17M ₀ is radiated away in the form of neutrinos. The distance of the edge from the center increases proportionally to the two-thirds power of the time. The luminosity decreases proportionally to the inverse four-thirds power.Although the runaway solution was modified by the exploding rather than a static envelope, it must still be excluded by adjusting initial conditions. Its character is changed from an exponential to a very large power (55) of time. The removal of a degree of freedom by this exclusion leads to physically non-sensical results such as negative luminosity. The inclusion of a term describing motion of the mantle due to neutrino interactions provides the additional degree of freedom necessary for physically reasonable results.     

Solar gravitational redshift

Wavelengths of solar spectrum lines should be shifted toward the red by the Sun's gravitational field as predicted by metric theories of gravity according to the principle of equivalence. Photographic wavelengths of 738 solar Fe i lines and their corresponding laboratory wavelengths have been studied. The measured solar wavelength minus the laboratory wavelength (_observed) averaged for the strong lines agrees well with the theoretically predicted shift (_theoretical). Studies show that the departures depend on line strength. No dependence of the departures on wavelength was found within the existing data.By studying strong lines over a wide spectral range, velocity shifts caused by the complex motions in the solar atmosphere seem to affect the results in a minimal fashion.     

Radius of convergence of Lie series for some elliptic elements

For equatorial orbits about an oblate body, we show that the Lie series for the elliptic elementse,f,l and diverge when the oblateness exceeds a critical multiple of the transformed eccentricity constant. The use of similar truncated series expansions for such elliptic elements by Brouwer accounts for the first-order errors at low eccentricity in his derived coordinates for an artificial satellite.     

Application of the QUILF thermobarometer to the peralkaline trachytes and pantellerites of the Eburru volcanic complex, East African Rift, Kenya

The Quaternary Eburru volcanic complex in the south-central Kenya Rift consists of pantelleritic trachytes and pantellerites. The phenocryst assemblage in the trachytes is sanidine + fayalite + ferrohedenbergite + aenigmatite ± quartz ± ilmenite ± magnetite ± pyrrhotite ± pyrite. In the pantellerites, the assemblage is sanidine + quartz + ferrohedenbergite + fayalite + aenigmatite + ferrorichterite + pyrrhotite ± apatite, although fayalite, ferrohedenbergite and ilmenite are absent from more evolved rocks (e.g. with SiO₂ > 71%). QUILF temperature calculations for the trachytes range from 709 to 793 °C and for the pantellerites 668–708 °C, the latter temperatures being among the lowest recorded for peralkaline silicic magmas. The QUILF thermobarometer demonstrates that the Eburru magmas crystallized at relatively low oxidation states (ΔFMQ + 0.5 to − 1.6) for both trachytes and pantellerites. The trachytes and pantellerites evolved along separate liquid lines of descent, the trachytes possibly deriving from a more mafic parent by fractional crystallization and the pantellerites from extreme fractionation of comenditic magmas.     

Late Holocene linkages between decade–century scale climate variability and productivity at Lake Tanganyika, Africa

Microlaminated sediment cores from the Kalya slope region of Lake Tanganyika provide a near-annually resolved paleoclimate record between ∼∼2,840 and 1,420 cal. yr B.P. demonstrating strong linkages between climate variability and lacustrine productivity. Laminae couplets comprise dark, terrigenous-dominated half couplets, interpreted as low density underflows deposited from riverine sources during the rainy season, alternating with light, planktonic diatomaceous ooze, with little terrigenous component, interpreted as windy/dry season deposits. Laminated portions of the studied cores consist of conspicuous dark and light colored bundles of laminae couplets. Light and dark bundles alternate at decadal time scales. Within dark bundles, both light and dark half couplets are significantly thinner than within light bundles, implying slower sediment accumulation rates during both seasons over those intervals.Time series analyses of laminae thickness patterns demonstrate significant periodicities at interannual–centennial time scales. Longer time scale periodicities (multidecadal to centennial scale) of light and dark half couplet thicknesses are coherent and in some cases are similar to solar cycle periods on these time scales. Although laminae thickness cycles do not strongly covary with the actual Δ¹⁴C record for this same time period, two large Δ¹⁴C anomalies are associated with substantial decreases in both light and dark laminae thickness. In contrast to the multidecadal– centennial time scale, significant annual to decadal periodicities, which are broadly consistent with ENSO/PDO forcing and their impact on East African climate, are not coherent between light and dark half couplets. The coherency of light–dark couplets at decadal–centennial time scales, but not at shorter time scales, is consistent with a model of a long-term relationship between precipitation (recorded in wet season dark laminae thickness) and productivity (light laminae thickness), which is not manifest at shorter time scales. We hypothesize that this coupling results from long-term recharging of internal nutrient loading during wet periods (higher erosion of soil P) and reduced loading during drought intervals. The relationship is not expressed on short time scales during which the dominant control on productivity is wind-driven, dry season upwelling, which is uncorrelated with wet-season precipitation. Our record greatly extends the temporal record of this quasi-periodic behavior throughout the late Holocene and provides the first evidence linking decade- to century-scale episodes of enhanced productivity to enhanced precipitation levels and nutrient recharge in a productive tropical lake.