Voltammetric estimation of iron(III) thermodynamic stability constants for catecholate siderophores isolated from marine bacteria and cyanobacteria

Thermodynamic stability constants have been estimated for the complexation of iron(III) with catecholate-type siderophores isolated from the marine bacterium Alteromonas luteoviolacea and from the marine cyanobacterium Synechococcus sp. PCC 7002. Stability constants were determined utilizing the “chelate scale” of Taylor et al. (1994). The scale is based upon a linear relationship between the reduction potentials and the pH-independent thermodynamic stability constants for known iron(III) complexes. Log K values for the alterobactin B ferric iron complex are 43.6 ± 1.5 at pH 8.2 and 37.6 ± 1.2 at pH 6, consistent with a shift from bis-catecholate to monosalicylate/monocatecholate iron coordination with decreasing pH. Synechococcus isolates PCC 7002 Nos. 1 and 3 formed iron(III) complexes with stability constants of approximately 38.1 ± 1.2 and 42.3 ± 1.5, respectively. The binding strengths of the iron(III) complexes examined in this study are quite high, suggesting that catecholate siderophores may play a role in the solubilization and biological uptake of iron in the marine environment.     

Submersible observations of an iceberg pit and scour on the Grand Banks of Newfoundland

An elongated sea bed depression (pit), 80 by 125 m and 10 m deep located on the Grand Banks of Newfoundland was identified on high resolution surficial geophysical survey lines and investigated using a manned submersible. The pit occurs at the termination of a long (greater than 3 km) iceberg scour, 1.5 m deep, and 80 m wide in 91 m of water. It is similar to other depressions in the region that indent the sea bed up to seven times deeper than the surrounding deepest iceberg furrows. The pit is interpreted to be the sea bed response to impact and loading by a rolling and grounding iceberg. The iceberg scour and pit appear to be of recent origin.     

The effects of light and nutrients on rates of ammonium transformation in a eutrophic river

Rates for nitrification, phytoplankton uptake of ammonium, and regeneration of ammonium were measured in the Delaware River as functions of irradiance and nutrient concentrations, using ¹⁵N labeling methods. Phytoplankton uptake increased and nitrification rates declined with increased light intensity. The irradiance level required for maximum uptake by phytoplankton was similar to that for maximal inhibition of nitrification (about 300μEm⁻² s⁻¹). Daily, water-column averaged rates, calculated by integration of the observed rate-intensity relationships, indicate that light plays a key role in regulating the balance between oxidation of NH₄⁺ by bacteria and assimilation by phytoplankton in the Delaware. The results show that uptake of ammonium by phytoplankton in the dark may exceed uptake in the light in optically thick systems.     

Contributions to atmospheric methane by natural seepages on the U.K. continental shelf [Mar. Geol. 137 (1997) 165–189]

Natural gas seepages occur on the United Kingdom's continental shelf and although published reports suggest that they are very rare, the petroleum industry has identified, but not publicly reported, many more. There is also very little data on the flux of gas from seabed seepages, and even less on the contribution of seepages to atmospheric concentrations of gases such as methane.

Potential gas source rocks include Quaternary and Tertiary peats as well as petroliferous source rocks such as the Carboniferous Coal Measures and the Upper Jurassic Kimmeridge Clays. There are also other organic-rich sediments which are potential source rocks. Together these cover a considerable part of the U.K. continental shelf.

Analogue seismic reflection (pinger) profiles acquired during the British Geological Survey's regional mapping programme have been reviewed to identify water column targets including fish and plumes of gas bubbles. The ability to distinguish targets is critical to an assessment of the distribution of gas seepages. Both theoretical predictions of target identity and the habits of shoaling fish have been investigated in order to identify a method of distinction.

Data from seabed seepages and measurements of seepage rates have been used to establish likely ranges of gas flux rates and the sizes of gas bubbles. The likelihood that a rising bubble will survive and escape into the atmosphere is determined primarily by bubble size and water depth; methane, the principal constituent of seepage gas, is relatively unreactive and sparingly soluble.

The studies have enabled a new estimate of the distribution of gas seepages on the U.K. continental shelf, and of the contribution to atmospheric methane levels. The results suggest that natural gas seepages are significantly more important as a source of methane than had hitherto been established. It is estimated that between 120,000 and 3.5 mtonnes of methane per year come from a continental shelf area of about 600,000 km². This represents between 2% and 40% of the total United Kingdom methane emission. It is suggested that similar contributions arise from other continental shelf areas worldwide, and that geological sources of atmospheric methane are more significant than is generally acknowledged.     

An overview and general results of the Lopez island OBS experiment

The purpose of the experiment was to determine the effects of coupling and bottom currents on ocean bottom seismometers. Twelve operational OBSs, three specially designed three-component systems, and a hydrophone were compared with each other. Unlike seismometers placed on hard rock at land stations, ocean bottom seismometers can be affected by soft sediments (which act as lossy mechanical springs) and by buoyancy. Coupling through soft sediments can modify the response to ground motion much as a low pass filter does, and high buoyancy tends to counteract this effect. These effects are observed in the Lopez data, which consist of signals from mechanical transient tests, cap shots, airgun pulses, and general background noise. The modification of response is pronounced for some instruments and barely noticeable in others. Instruments that stand high in the water relative to their base width tend to be susceptible to rocking motion that shows up as a mechanical cross coupling between horizontal and vertical motion. Correlation of Lopez results with coupling theory suggests that it is possible to design ocean bottom seismometers that will couple well to any sediment. Current levels at the Lopez site (<5 cm s^-1) were too small to produce noticeable effect on any of the instruments; however, the same design criteria that will minimize coupling problems will also lessen problems caused by ocean currents.Hawaii Institute of Geophysics Contribution No. 1171.     

Regional trends in crude birth,death, and natural increase rates in Russia and the USSR: 1897-1989

"This paper establishes and discusses briefly regional patterns and trends in crude birth, death, and natural increase rates in Russia and the USSR from the turn of the century to 1989. The study is based on a comparable regional framework and placed in the context of the demographic transition theory. It discusses sources, collection, and quality of data, as well as necessary estimating procedures. An attempt also is made to examine briefly regional age-standardized rates."     

Primodial retention of carbon by the terrestrial planets

Chemical equilibrium calculations on the stability of pure and dissolved graphite and cohenite (Fe₃C), several other carbides, and several carbonates have been carried out for a system with solar elemental abundances over a very wide range of temperature and pressure. The calculated abundances of condensed carbon compounds are similar to the observed inventories on Earth and Venus, but fully 10 times smaller than the minimum carbon abundance found in ordinary chondrites. The total carbon content of most iron meteorites is compatible with their origin as a cooling FeNiCSP solution which was saturated with dissolved carbon at the solidus, such as would be produced by melting an ordinary chondrite, not by direct condensation from or equilibrium with the primitive solar nebula. It is argued that the carbon content of Mars need not be appreciably greater than that of the Earth. Material with even lower formation temperatures than Mars, such as the primitive material in the asteroid belt, may retain substantially more carbon as disequilibrium polymeric organic matter, possibly by the Fischer-Tropsch mechanism favored by Anders. Carbonates are not found as equilibrium products in a solar-composition system, and are probably secondary alteration products. CaCO₃ might, however, persist in a solar-composition gas at temperatures below 460°K and pressures below 10^?6.6 bar. The most stable condensed carbon compounds are found to be graphite, Fe₃C, and possibly TiC, all in solid solution in the metal phase.     

Thermodynamics of selected trace elements in the Jovian atmosphere

The thermochemistry of several hundred compounds of twelve selected trace elements (Ge, Se, Ga, As, Te, Pb, Sn, Cd, Sb, Tl, In, and Bi) has been investigated for solar composition material along a Jupiter adiabat. The results indicate that AsF₃, InBr, TlI, and SbS, in addition to CO, PH₃, GeH₄, AsH₃, H₂Se, HCl, HF, and H₃BO₃ proposed by Barshay and Lewis (1978), may be potential chemical tracers of atmospheric dynamics. The reported observations of GeH₄ is interpreted on the basis of new calculations as implying rapid vertical transport from levels where T ? 800°K. Upper limits are also set on the abundances of many gaseous compounds of the elements investigated.