Thermochemistry of glasses along joins of pyroxene stoichiometry in the system Ca2Si2O6-Mg2Si2O6-Al4O6

Enthalpies of solution in 2PbO · B₂O₃ at 974 K have been measured for glasses along the joins Ca₂Si₂O₆ (Wo)-Mg₂Si₂O₆ (En) and Mg₂Si₂O₆-MgAl₂SiO₆ (MgTs). Heats of mixing are symmetric and negative for Wo-En with W_H = ?31.0 ± 3.6 kJ mol^?. Negative heats of mixing were also found for the En-MgTs glasses (W_H = ?33.4 ± 3.7 kJ mol^?).Enthalpies of vitrification of pyroxenes and pyroxenoids generally increase with decreasing alumina content and with decreasing basicity of the divalent cation.Heats of mixing along several glassy joins show systematic trends. When only non-tetrahedral cations mix (outside the aluminosilicate framework), small exothermic heats of mixing are seen. When both nontetrahedral and framework cations mix (on separate sublattices, presumably), the enthalpies of mixing are substantially more negative. Maximum enthalpy stabilization near compositions with Al/Si ≈ 1 is suggested.     

Thermochemistry of carbonate-pyroxene equilibria

The enthalpies of drop solution of calcite, magnesite, dolomite, wollastonite and diopside have been measured in a lead borate solvent at 977 K in a Calvettype microcalorimeter. The carbonate calorimetry was done under flowing gas atmosphere. Both natural and synthetic samples were used. From these calorimetric data, the enthalpies of several reactions of carbonate with quartz were calculated. The enthalpies of these reactions (kJ/mol) at 298 K are: calcite+quartzwollastonite+CO₂, 92.3±1.0; magnesite+quartzenstatite+CO₂, 82.9±2.8; dolomite+quartzdiopside+CO₂, 163.0±1.9. These values generally are in agreement with those calculated from Robie et al., Helgeson et al., Berman and Holland and Powell. The enthalpy of dolomite-quartz reaction overlaps marginally with those from Berman and Holland and Powell. The enthalpy of formation of dolomite from magnesite and calcite (-11.1±2.5 kJ/mol) was also derived from the measured enthalpies, and this value is consistent with that from acid solution calorimetric measurements as shown by Navrotsky and Capobianco, but different from values in the earlier literature. These results support the premise that drop-solution of carbonates into molten lead borate results in a well-defined final state consisting of dissolved oxide and evolved CO₂. This was also confirmed by weight change experiments. Thus, oxide melt calorimetry is applicable to carbonates.     

H<Subscript>2</Subscript>O solubility in basalt at upper mantle conditions

This study presents a new experimental approach for determining H₂O solubility in basaltic melt at upper mantle conditions. Traditional solubility experiments are limited to pressures of ~600 MPa or less because it is difficult to reliably quench silicate melts containing greater than ~10 wt% dissolved H₂O. To overcome this limitation, our approach relies on the use of secondary ion mass spectrometry to measure the concentration of H dissolved in olivine and on using the measured H in olivine as a proxy for the concentration of H₂O in the co-existing basaltic melt. The solubility of H₂O in the melt is determined by performing a series of experiments at a single pressure and temperature with increasing amounts of liquid H₂O added to each charge. The point at which the concentration of H in the olivine first becomes independent of the amount of initial H₂O content of the charge (added + adsorbed H₂O) indicates its solubility in the melt. Experiments were conducted by packing basalt powder into a capsule fabricated from San Carlos olivine, which was then pressure-sealed inside a Ni outer capsule. Our experimental results indicate that at 1000 MPa and 1200 °C, the solubility of H₂O in basaltic melt is 20.6 ± 0.9 wt% (2 × standard deviation). This concentration is considerably higher than predicted by most solubility models but defines a linear relationship between H₂O fugacity and the square of molar H₂O solubility when combined with solubility data from lower pressure experiments. Further, our solubility determination agrees with melting point depression determined experimentally by Grove et al. (2006) for the H₂O-saturated peridotite solidus at 1000 MPa. Melting point depression calculations were used to estimate H₂O solubility in basalt along the experimentally determined H₂O-saturated peridotite solidus. The results suggest that a linear relationship between H₂O fugacity and the square of molar solubility exists up to ~1300 MPa, where there is an inflection point and solubility begins to increase less strongly with increasing H₂O fugacity.     

Amplitude of ENSO cycles in the Santa Barbara Basin,off California,during the past 15 000 years

Varve thickness time series from ODP Site 893 in the Santa Barbara Basin (off California) were analysed to determine variation in the strength of El Niño/Southern Oscillation (ENSO) cycles during the past 15 000 yr. Mean varve thickness and variance changed over time, with thicker varves before ～8000 yr BP indicative of wetter than modern climates. A 100‐yr running standardisation was applied to correct for non‐stationarity. The contribution of ENSO‐scale variability was then estimated as the amplitude of 3–8 year bandpassed data. Results show multidecadal‐ to centennial‐scale modulation of the amplitude. On average, however, the amplitude of ENSO scale variability remained constant throughout the past 15 000 yr. We therefore conclude that, although the expression of ENSO cycles may have changed during the Holocene, there is no indication for a significant change in amplitude of interannual variability. Copyright © 2005 John Wiley & Sons, Ltd.     

Revisiting the Gow Lake impact structure,Saskatchewan, Canada

The ~5 km diameter Gow Lake impact structure formed in the Canadian Shield of northern Saskatchewan approximately 197 Myr ago. This structure has not been studied in detail since its discovery during a regional gravity survey in the early 1970s. We report here on field observations from a 2011 expedition that, when combined with subsequent laboratory studies, have revealed a wealth of new information about this poorly studied Canadian impact structure. Initially considered to be a prototypical central peak (i.e., a complex) impact structure, our observations demonstrate that Gow Lake is actually a transitional impact structure, making it one of only two identified on Earth. Despite its age, a well-preserved sequence of crater-fill impactites is preserved on Calder Island in the middle of Gow Lake. From the base upward, this stratigraphy is parautochthonous target rock, lithic impact breccia, clast-rich impact melt rock, red clast-poor impact melt rock, and green clast-poor impact melt rocks. Discontinuous lenses of impact melt-bearing breccia also occur near the top of the red impact melt rocks and in the uppermost green impact melt rocks. The vitric particles in these breccias display irregular and contorted outlines. This, together with their setting within crater-fill melt rocks, is indicative of an origin as flows within the transient cavity and not an airborne mode of origin. Following impact, a hydrothermal system was initiated, which resulted in alteration of the crater-fill impactites. Major alteration phases are nontronite clay, K-feldspar, and quartz.     

Sub-recent nitrogen-isotope trends in sediments from Skagerrak (North Sea) and Kattegat: Changes in N-budgets and N-sources?

We determined ¹⁵N/¹⁴N ratios of total nitrogen in surface sediments and dated sediment cores to reconstruct the history of N-loading of the North Sea. The isotopic N composition in modern surface sediments is equivalent to and reflects the isotopic mixture of oceanic nitrate on the one hand (δ¹⁵N = 5‰) and the imprint of river-borne nitrogen input into the SE North Sea (δ¹⁵N up to 12‰ in estuaries of the SE North Sea) on the other hand. We compare the results with δ¹⁵N records from pre-industrial sediment intervals in cores from the Skagerrak and Kattegat areas, which both constitute significant depositional centres for N in the North Sea and the Baltic Sea/North Sea transition. As expected, isotopically enriched anthropogenic nitrogen was found in the two records from the Kattegat area, which is close to eutrophication sources on land. Enrichment of δ¹⁵N in cores from the Skagerrak – the largest sediment sink for nitrogen in the entire North Sea – was not significant and values were similar to those found in sediment layers representing pre-industrial conditions. We interpret this isotopic uniformity as an indication that most riverine reactive nitrogen with its characteristic isotopic signature is removed by denitrification in shallow shallow-water sediments before reaching the main sedimentary basin of the North Sea.     

Marine organic geochemistry of the Eastern Mediterranean: 1. Aliphatic and polyaromatic hydrocarbons in Cretan Sea surficial sediments

As part of a lipid biogeochemical study, aliphatic and polyaromatic hydrocarbons were determined in surficial sediments from the Cretan Sea (South Aegean Sea) in the Eastern Mediterranean. Total concentrations of both aliphatic (AHC) and polyaromatic (PAH) hydrocarbons were low (562–5697 and 14.6–158.5 ng/g, respectively) with respect to other coastal sediments worldwide and compare with concentrations found in open sea areas. The composition of AHC was dominated by unresolved complex mixture (UCM) indicating the presence of petroleum-related hydrocarbon inputs as confirmed by the detection of specific α,β-hopanes. PAH consisted mainly of pyrolytic four- to five-ring compounds. UCM and PAH amounts revealed that Cretan Sea receives low supply of anthropogenic material compared to NW Mediterranean. The spatial distributions of AHC and PAH indicated that urban run-off and transport from the continental self are the major input pathway of anthropogenic and biogenic hydrocarbons from terrestrial sources in the near shore area, whereas atmospheric transport might be the significant source of hydrocarbons in the deep area.     

The effects of meteorite impacts on the availability of bioessential elements for endolithic organisms

Abstract– Meteorite impacts, one of the most ubiquitous processes in the solar system, have the ability to destroy as well as create habitats for life. The impact process can increase the translucency and porosity of the target substrate, as well as mobilize biologically relevant elements within the substrate. For endolithic organisms, this process has important implications, especially in extreme environments where they are forced to seek refuge in the interior of rocks. Here, we show that unshocked target rocks and rocks that have experienced pressures up to about 80 GPa from the Haughton impact structure, Devon Island, Canada, possess a small, but discernible change in bulk chemistry within the major oxide analysis. However, changes in the distribution of elements did occur with increasing shock level for both the sedimentary and crystalline target. Both the crystalline and sedimentary target rocks contain significant amounts of glasses at higher shock levels (up to about 95% by volume), which would improve the availability of these elements to potential microbial endoliths as glasses are more easily dissolved by organic acids. The implication that impact events do not impoverish their capacity to serve as a “substrate” through volatilization is important with respect to analogous impact structures on Mars. After the deleterious effects of the direct meteorite impact, any microorganisms on Mars would have benefited from the input of heat, the mobilization of a possible frozen groundwater system, as well as increased translucency, porosity, and trace nutrient availability of the target substrate.     

New 40Ar/39Ar constraints for the “Grande Nappe”: The largest rhyolitic eruption from the Mont-Dore Massif (French Massif Central)

Since the 1960s, an early explosive activity in the Mont-Dore Massif is associated with a major pyroclastic rhyolitic eruption (5–7 km³) known as the “Grande Nappe” (GN). This event, linked to the formation of a 6-km-diameter cryptic caldera named “Haute Dordogne”, was before our investigation dated by ⁴⁰Ar/³⁹Ar at 3.07 ± 0.04 Ma. Our new single-crystal laser fusion ⁴⁰Ar/³⁹Ar dates obtained on two outcrops of the GN (Rochefort-Montagne and Ludières) questioned several hypotheses made concerning this “landmark” event of the Mont-Dore Massif history. We demonstrate that: (1) the GN rhyolitic eruption has occurred much later than previously estimated (i.e. 2.77 ± 0.02–0.07 Ma full external uncertainties); (2) the correlation made between the Vendeix rhyolitic complexes (intra-caldera position) dated back to 2.74 ± 0.04 Ma and the GN is proposed; (3) xenocryst contamination could be very high (i.e. 70% for the Rochefort-Montagne GN outcrop) and explains the noticeable older age obtained previously; (4) a link between the GN eruption and the formation of a caldera is questionable; the hypothesis of a northward-oriented blast channeled eastward toward the paleo-Allier River is thus proposed.