A revised model for the density and thermal expansivity of K2O-Na2O-CaO-MgO-Al2O3-SiO2 liquids from 700 to 1900 K: extension to crustal magmatic temperatures

A revised model for the volume and thermal expansivity of K₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂ liquids, which can be applied at crustal magmatic temperatures, has been derived from new low temperature (701–1092 K) density measurements on sixteen supercooled liquids, for which high temperature (1421–1896 K) liquid density data are available. These data were combined with similar measurements previously performed by the present author on eight sodium aluminosilicate samples, for which high temperature density measurements are also available. Compositions (in mol%) range from 37 to 75% SiO₂, 0 to 27% Al₂O₃, 0 to 38% MgO, 0 to 43% CaO, 0 to 33% Na₂O and 0 to 29% K₂O. The strategy employed for the low temperature density measurements is based on the assumption that the volume of a glass is equal to that of the liquid at the limiting fictive temperature, T _f ^′. The volume of the glass and liquid at T _f ^′ was obtained from the glass density at 298 K and the glass thermal expansion coefficient from 298 K to T _f ^′. The low temperature volume data were combined with the existing high temperature measurements to derive a constant thermal expansivity of each liquid over a wide temperature interval (767–1127 degrees) with a fitted 1 error of 0.5 to 5.7%. Calibration of a linear model equation leads to fitted values of Vˉ _i ±1 (cc/mol) at 1373 K for SiO₂ (26.86 ± 0.03), Al₂O₃ (37.42±0.09), MgO (10.71±0.08), CaO (15.41±0.06), Na₂O (26.57±0.06), K₂O (42.45 ± 0.09), and fitted values of dVˉ _i /dT (10⁻³ cc/mol-K) for MgO (3.27±0.17), CaO (3.74±0.12), Na₂O (7.68±0.10) and K₂O (12.08±0.20). The results indicate that neither SiO₂ nor Al₂O₃ contribute to the thermal expansivity of the liquids, and that dV/dT ^liq is independent of temperature between 701 and 1896 K over a wide range of composition. Between 59 and 78% of the thermal expansivity of the experimental liquids is derived from configurational (vs vibrational) contributions. Measured volumes and thermal expansivities can be recovered with this model with a standard deviation of 0.25% and 5.7%, respectively. Received: 2 August 1996 / Accepted: 12 June 1997     

Biological production off Southern California is linked to climatic change

To obtain clues about how coastal primary production might be affected by interannual and interdecadal changes in climate, we studied marine laminated sediments from the center of the Santa Barbara Basin. We report here a large decrease in the flux of diatoms between the periods 1954–1972 and 1973–1986, by a factor of five, and sustained reductions from 1973 to 1978 by a factor of ten below the pre-1972 period. Planktonic foraminifera flux shows a consistent trend of decrease with lowest values from 1981 to 1984. On the whole, the 1954–1972 period is considerably cooler than the 1973–1986 period, over the entire North Pacific. The decrease in biological production in this coastal system is accompanied by an overall intensification of the Aleutian Low in the North Pacific over the past 14 years, providing for a weakening of the California Current, and an overall reduction of mixing and upwelling. The possibility that the low coastal production could provide positive feedback to global warming through reduction of CO₂-uptake, and its relation to the greenhouse effect is considered. On a shorter time-scale, the effects of El Niño phenomena are clearly seen in the sediments of this basin, as decreases in total diatom flux and increases in the relative abundance of certain warm-water diatoms.     

Possible diagenetic mobilization of barium in sapropelic sediment from the eastern Mediterranean

In the last few years it has frequently been suggested that Ba is a useful indicator of paleoproductivity. The formation of some sapropels in the Eastern Mediterranean is considered to be related to, or to coincide with, periods of enhanced productivity. A high-resolution sampling study has been undertaken in order to investigate whether the Ba distribution in sapropels reflects a primary input signal or whether it has been altered by diagenetic processes.

On the basis of our results we suggest that three diagenetic stages determine the distribution of Ba. During deposition of the sapropel (stage 1) Ba is mobilized as anoxic conditions prograde. After deposition of the sapropel (stage 2), a progressive oxidation front develops. This front induces the formation of Mn and Fe enrichments and barite precipitation at the oxic/anoxic boundary. Barite precipitation is believed to be caused mainly by a rise in the porewater sulphate concentration after sulphides have been oxidized by the front.

Upon burial (stage 3), suboxic conditions develop as the oxygen becomes exhausted again. In contrast to Fe- and Mn-oxyhydroxides which dissolve and reprecipitate at higher levels, barite is preserved because dissolved sulphate is not depleted.

The interpretation of the Ba distribution in organic-rich sediment is not straightforward. Diagenetic reallocation of a primary Ba signal will possibly disturb the relationship between Ba and organic production. Consequently, one must be very cautious when invoking Ba as a paleoproductivity indicator.     

Geochemistry of eastern Mediterranean sediments: Primary sediment composition and diagenetic alterations

Two cores recovered in the eastern Mediterranean were analysed for major, minor and trace elements. The primary chemical composition of the sediment is different at each location, probably because the lithological sources and the relative biogenic contributions differ.

Carbonates are important for the concentration of Ca, Mg and Sr, whereas aluminosilicates determine the concentration of Si, Al, K, Li, Y and Be, and to a lesser extent that of Fe, Cr, Ti, Mg, Zn and Zr. In sapropels, organic carbon and sulphur seem to be closely related. Bromine, Mo, P, Fe, V, Cu, Zn, Co, Ni and Cr are closely associated with organic and sulphidic compounds. The concentration versus depth profile for organic carbon in two sapropels points to a rapid establishment of conditions that gave rise to sapropel formation, followed by a gradual transition back to “normal” conditions.

The primary composition is overprinted by diagenetic processes. Sulphate-reducing conditions occurred during and just after sapropel deposition. A progressive oxidation front mechanism, which became active after sapropel deposition, is responsible for additional major geochemical changes. This diagenetic phenomenon has strong implications for the chemistry of Fe, Mn, Ni, Co, Zn, Cu, Cr, V, U, As and Sb.     

An early warning system for wave-driven coastal flooding at Imperial Beach,CA

Natural Hazards - Waves overtop berms and seawalls along the shoreline of Imperial Beach (IB), CA when energetic winter swell and high tide coincide. These intermittent, few-hour long events flood...     

Water and related chemistry in the solar system. A guaranteed time key programme for Herschel

“Water and related chemistry in the Solar System” is a Herschel Space Observatory Guaranteed-Time Key Programme. This project, approved by the European Space Agency, aims at determining the distribution, the evolution and the origin of water in Mars, the outer planets, Titan, Enceladus and the comets. It addresses the broad topic of water and its isotopologues in planetary and cometary atmospheres. The nature of cometary activity and the thermodynamics of cometary comae will be investigated by studying water excitation in a sample of comets. The D/H ratio, the key parameter for constraining the origin and evolution of Solar System species, will be measured for the first time in a Jupiter-family comet. A comparison with existing and new measurements of D/H in Oort-cloud comets will constrain the composition of pre-solar cometary grains and possibly the dynamics of the protosolar nebula. New measurements of D/H in giant planets, similarly constraining the composition of proto-planetary ices, will be obtained. The D/H and other isotopic ratios, diagnostic of Mars’ atmosphere evolution, will be accurately measured in H₂O and CO. The role of water vapor in Mars’ atmospheric chemistry will be studied by monitoring vertical profiles of H₂O and HDO and by searching for several other species (and CO and H₂O isotopes). A detailed study of the source of water in the upper atmosphere of the Giant Planets and Titan will be performed. By monitoring the water abundance, vertical profile, and input fluxes in the various objects, and when possible with the help of mapping observations, we will discriminate between the possible sources of water in the outer planets (interplanetary dust particles, cometary impacts, and local sources). In addition to these inter-connected objectives, serendipitous searches will enhance our knowledge of the composition of planetary and cometary atmospheres.