Self-assembly of phosphate fluorosurfactants in carbon dioxide

Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and EUF types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scattering was used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions

Progress towards an accurate determination of the Boltzmann constant by Doppler spectroscopy

In this paper, we present significant progress performed on an experiment dedicated to the determination of the Boltzmann constant, k, by accurately measuring the Doppler absorption profile of a line in a gas of ammonia at thermal equilibrium. This optical method based on the first principles of statistical mechanics is an alternative to the acoustical method which has led to the unique determination of k published by the CODATA with a relative accuracy of 1.7 ppm. We report on the first measurement of the Boltzmann constant by laser spectroscopy with a statistical uncertainty below 10 ppm, more specifically 6.4 ppm. This progress results from improvements in the detection method and in the statistical treatment of the data. In addition, we have recorded the hyperfine structure of the probed saQ(6,3) rovibrational line of ammonia by saturation spectroscopy and thus determine very precisely the induced 4.36 (2) ppm broadening of the absorption linewidth. We also show that, in our well chosen experimental conditions, saturation effects have a negligible impact on the linewidth. Finally, we draw the route to future developments for an absolute determination of with an accuracy of a few ppm.Comment: 22 pages, 11 figure

The Impact of Global Warming and Anoxia on Marine Benthic Community Dynamics: an Example from the Toarcian (Early Jurassic)

The Pliensbachian-Toarcian (Early Jurassic) fossil record is an archive of natural data of benthic community response to global warming and marine long-term hypoxia and anoxia. In the early Toarcian mean temperatures increased by the same order of magnitude as that predicted for the near future; laminated, organic-rich, black shales were deposited in many shallow water epicontinental basins; and a biotic crisis occurred in the marine realm, with the extinction of approximately 5% of families and 26% of genera. High-resolution quantitative abundance data of benthic invertebrates were collected from the Cleveland Basin (North Yorkshire, UK), and analysed with multivariate statistical methods to detect how the fauna responded to environmental changes during the early Toarcian. Twelve biofacies were identified. Their changes through time closely resemble the pattern of faunal degradation and recovery observed in modern habitats affected by anoxia. All four successional stages of community structure recorded in modern studies are recognised in the fossil data (i.e. Stage III: climax; II: transitional; I: pioneer; 0: highly disturbed). Two main faunal turnover events occurred: (i) at the onset of anoxia, with the extinction of most benthic species and the survival of a few adapted to thrive in low-oxygen conditions (Stages I to 0) and (ii) in the recovery, when newly evolved species colonized the re-oxygenated soft sediments and the path of recovery did not retrace of pattern of ecological degradation (Stages I to II). The ordination of samples coupled with sedimentological and palaeotemperature proxy data indicate that the onset of anoxia and the extinction horizon coincide with both a rise in temperature and sea level. Our study of how faunal associations co-vary with long and short term sea level and temperature changes has implications for predicting the long-term effects of “dead zones” in modern oceans

Earliest Triassic microbialites in the South China Block and other areas; controls on their growth and distribution

Earliest Triassic microbialites (ETMs) and inorganic carbonate crystal fans formed after the end-Permian mass extinction (ca. 251.4 Ma) within the basal Triassic Hindeodus parvus conodont zone. ETMs are distinguished from rarer, and more regional, subsequent Triassic microbialites. Large differences in ETMs between northern and southern areas of the South China block suggest geographic provinces, and ETMs are most abundant throughout the equatorial Tethys Ocean with further geographic variation. ETMs occur in shallow-marine shelves in a superanoxic stratified ocean and form the only widespread Phanerozoic microbialites with structures similar to those of the Cambro-Ordovician, and briefly after the latest Ordovician, Late Silurian and Late Devonian extinctions. ETMs disappeared long before the mid-Triassic biotic recovery, but it is not clear why, if they are interpreted as disaster taxa. In general, ETM occurrence suggests that microbially mediated calcification occurred where upwelled carbonate-rich anoxic waters mixed with warm aerated surface waters, forming regional dysoxia, so that extreme carbonate supersaturation and dysoxic conditions were both required for their growth. Long-term oceanic and atmospheric changes may have contributed to a trigger for ETM formation. In equatorial western Pangea, the earliest microbialites are late Early Triassic, but it is possible that ETMs could exist in western Pangea, if well-preserved earliest Triassic facies are discovered in future work

The fundamental constants and their variation: observational status and theoretical motivations

This article describes the various experimental bounds on the variation of the fundamental constants of nature. After a discussion on the role of fundamental constants, of their definition and link with metrology, the various constraints on the variation of the fine structure constant, the gravitational, weak and strong interactions couplings and the electron to proton mass ratio are reviewed. This review aims (1) to provide the basics of each measurement, (2) to show as clearly as possible why it constrains a given constant and (3) to point out the underlying hypotheses. Such an investigation is of importance to compare the different results, particularly in view of understanding the recent claims of the detections of a variation of the fine structure constant and of the electron to proton mass ratio in quasar absorption spectra. The theoretical models leading to the prediction of such variation are also reviewed, including Kaluza-Klein theories, string theories and other alternative theories and cosmological implications of these results are discussed. The links with the tests of general relativity are emphasized.Comment: 56 pages, l7 figures, submitted to Rev. Mod. Phy

Organic carbon content and carbon isotope variations across the Permo-Triassic boundary in the Gartnerkofel-1 borehole, Carnic Alps, Austria

The Gartnerkofel borehole is one of the most thoroughly studied and described Permo-Triassic sections in the world. Detailed bulk organic carbon isotope studies show a negative base shift from − 24‰ to − 28‰ in the Latest Permian which latter value persists into the Earliest Triassic after which it decreases slightly to − 26‰. Two strongly negative peaks of > − 38‰ in the Latest Permian and a lesser peak of − 31‰ in the Early Triassic are too negative to be due to a greater proportion of more negative organic matter and must be due to very negative methane effects. The overall change to more negative values across the Bulla/Tesero boundary fits the relative rise in sea level for this transition based on the facies changes. A positive shift in organic carbon isotope values at the Late Permian Event Horizon may be due to an increase in land-derived organic detritus at this level—a feature shown by all Tethyan Permo-Triassic boundary sections though these other sections do not have the same values. Carbonate carbon isotope trends are similar in all sections dropping by 2–3 units across the Permo-Triassic boundary. Gartnerkofel carbonate oxygen values are surprisingly, considering the ubiquitous dolomitization, compatible with values elsewhere and indicate reasonable tropical temperatures of 60 °C in the Latest Permian sabkhas to 20–40 °C in the overlying marine transition beds. Increased land-derived input at the Late Permian Event Horizon may be due to offshore transport by tsunamis whose deposits have been recognized in India at this level