Chemistry and mineralogy of ODP Leg 124 sediment samples

From X-ray mineralogical studies and chemical analyses of the whole rocks and the fine fractions (<2 µm) of ten to fifteen samples at each site of ODP Leg 124, two major sources were identified in the sedimentary components of the Celebes and Sulu basins: (1) a terrestrial and continental contribution; (2) a volcanic influx that gives way to well-defined volcanic units or to a dilute contamination, consisting of coarse-grained minerals (Plagioclase, pyroxene, olivine, spinel) or a smectitic-rich fraction produced by the alteration of volcanic glasses and ashes. The continental signature increases the amount of quartz in the rocks and the phyllitic association is complex: micas, kaolinite, disordered interstratified clay-minerals. The chemical compositions of the bulk rocks and the fractions <2 µm are more potassic and aluminum-rich. The volcanic imprint depends on the grain-size and chemical properties of the components. Ca/Na contents highly variable compared to the K content of the bulk composition are due to the presence of coarse-grained volcanic Plagioclase. The fractions <2 µm are more magnesian than in the continental regime. The diagenesis is revealed by the crystallization of zeolites, the fixation of magnesium into the smectites that depletes the pore fluids in this element. Smectitization of the disordered interstratified clay minerals enriches the alkalinity of the pore fluids. Some deep formations of the Sulu Basin are affected by a thermal event, but no thermal event was recognized in the Celebes Basin.

Sr/Ca ratios and oxygen isotopes from sclerosponges

We investigate aragonitic skeletons of the Caribbean sclerosponge Ceratoporella nicholsoni from Jamaica, 20 m below sea level (mbsl), and Pedro Bank, 125 mbsl. We use d18O and Sr/Ca ratios as temperature proxies to reconstruct the Caribbean mixed layer and thermocline temperature history since 1400 A.D. with a decadal time resolution. Our age models are based on U/Th dating and locating of the radiocarbon bomb spike. The modern temperature difference between the two sites is used to tentatively calibrate the C. nicholsoni Sr/Ca thermometer. The resulting calibration points to a temperature sensitivity of Sr/Ca in C. nicholsoni aragonite of about -0.1 mmol/mol/K. Our Sr/Ca records reveal a pronounced warming from the early 19th to the late 20th century, both at 20 and 125 mbsl. Two temperature minima in the shallow water record during the late 17th and early 19th century correspond to the Maunder and Dalton sunspot minima, respectively. Another major cooling occurred in the late 16th century and is not correlatable with a sunspot minimum. The temperature contrast between the two sites decreased from the 14th century to a minimum in the late 17th century and subsequently increased to modern values in the early 19th century. This is interpreted as a long-term deepening and subsequent shoaling of the Caribbean thermocline. The major trends of the Sr/Ca records are reproduced in both specimens but hardly reflected in the d18O records.

pH and calcium change in the microenvironment of a benthic foraminifer (Ammonia sp.) and its size during experiments

Calcareous foraminifera are well known for their CaCO3 shells. Yet, CaCO3 precipitation acidifies the calcifying fluid. Calcification without pH regulation would therefore rapidly create a negative feedback for CaCO3 precipitation. In unicellular organisms, like foraminifera, an effective mechanism to counteract this acidification could be the externalization of H+ from the site of calcification. In this study we show that a benthic symbiont-free foraminifer Ammonia sp. actively decreases pH within its extracellular microenvironment only while precipitating calcite. During chamber formation events the strongest pH decreases occurred in the vicinity of a newly forming chamber (range of gradient about 100 µm) with a recorded minimum of 6.31 (< 10 µm from the shell) and a maximum duration of 7 h. The acidification was actively regulated by the foraminifera and correlated with shell diameters, indicating that the amount of protons removed during calcification is directly related to the volume of calcite precipitated. The here presented findings imply that H+ expulsion as a result of calcification may be a wider strategy for maintaining pH homeostasis in unicellular calcifying organisms.

Skeletal density of Porites

Paleotemperature estimates based on coral Sr/Ca have not been widely accepted because the reconstructed glacial-Holocene shift in tropical sea-surface temperature (~4-6°C) is larger than that indicated by foraminiferal Mg/Ca (~2-4°C). We show that corals over-estimate changes in sea-surface temperature (SST) because their records are attenuated during skeletogenesis within the living tissue layer. To quantify this process, we microprofiled skeletal mass accumulation within the tissue layer of Porites from Australasian coral reefs and laboratory culturing experiments. The results show that the sensitivity of the Sr/Ca and d18O thermometers in Porites will be suppressed, variable, and dependent on the relationship between skeletal growth rate and mass accumulation within the tissue layer. Our findings help explain why d18O-SST sensitivities for Porites range from -0.08 per mil/°C to -0.22 per mil/°C and are always less than the value of -0.23 per mil/°C established for biogenic aragonite. Based on this observation, we recalibrated the coral Sr/Ca thermometer to determine a revised sensitivity of -0.084 mmol/mol/°C. After rescaling, most of the published Sr/Ca-SST estimates for the Indo-Pacific region for the last ~14,000 years (-7°C to +2°C relative to modern) fall within the 95% confidence envelope of the foraminiferal Mg/Ca-SST records. We conclude that two types of calibration scales are required for coral paleothermometry; an attenuated Porites-specific thermometer sensitivity for studies of seasonal to interannual change in SST and, importantly, the rescaled -0.084 mmol/mol/°C Sr/Ca sensitivity for studies of 20th-century trends and millennial-scale changes in mean SST. The calibration-scaling concept will apply to the development of transfer functions for all geochemical tracers in corals.

Ba, Mn, and Mg record derived from Hoeglundina elegans of sediment core SLA-9

The evolution of productivity, redox conditions, temperature, and ventilation during the deposition of an Aegean sapropel (S1) is independently constrained using bulk sediment composition and high-resolution single specimen benthic foraminiferal trace metal and stable isotope data. The occurrence of benthic foraminifer, Hoeglundina elegans (H. elegans), through a shallow water (260 m) sapropel, permits for the first time a comparison between dissolved and particulate concentrations of Ba and Mn and the construction of a Mg/Ca-based temperature record through sapropel S1. The simultaneous increase in sedimentary Ba and incorporated Ba in foraminiferal test carbonate, (Ba/Ca)H. elegans, points to a close coupling between Ba cycling and export productivity. During sapropel deposition, sedimentary Mn content ((Mn/Al)sed) is reduced, corresponding to enhanced Mn2+ mobilization from sedimentary Mn oxides under suboxic conditions. The consequently elevated dissolved Mn2+ concentrations are reflected in enhanced (Mn/Ca)H. elegans levels. The magnitude and duration of the sapropel interruption and other short-term cooling events are constrained using Mg/Ca thermometry. Based on integrating productivity and ventilation records with the temperature record, we propose a two-mode hysteresis model for sapropel formation.

Low-pressure melting relations of a basalt from ODP Hole 127-797C

One-atmosphere melting experiments, controlled to approximately the fayalite-magnetite-quartz oxygen buffer, performed on a basalt from Hole 797C crystallized olivine and plagioclase nearly simultaneously from about 1235°C and augite from about 1175°C. The liquid compositions indicate systematic trends of increasing FeO and TiO2 and decreasing Al2O3 with decreasing MgO. Experimental olivine compositions vary from Fo90 to Fo78, plagioclase from An79 to An67, and augite from En49 to En46. The KD value for the Fe2+ and Mg distribution between olivine and liquid is 0.31. The KD value for the distribution of Fetotal and Mg between augite and liquid averages 0.24. These KD values suggest experimental equilibrium. The KD values for Na and Ca distribution between plagioclase and liquid range between 0.55 and 0.99 and are dependent on crystallization temperature. Projected on pseudoternary basaltic phase diagrams, the liquid line of descent moves toward increasing quartz normative compositions, revealing a typical tholeiitic crystallization trend with marked Fe and Ti enrichments. Such enrichments are a reflection of the dominance of plagioclase in the crystallizing assemblage. The experimental results can explain the marked Fe- and Ti-enrichment trends observed for the sills of the lower part of Hole 797C, but have no direct bearing on the origin of the relatively evolved high-Al basalts of Hole 794C.

Uranium in larval shells as a barometer of molluscan ocean acidification exposure

As the ocean undergoes acidification, marine organisms will become increasingly exposed to reduced pH, yet variability in many coastal settings complicates our ability to accurately estimate pH exposure for those organisms that are difficult to track. Here we present shell-based geochemical proxies that reflect pH exposure from laboratory and field settings in larvae of the mussels Mytilus californianus and M. galloprovincialis. Laboratory-based proxies were generated from shells precipitated at pH 7.51 to 8.04. U/Ca, Sr/Ca, and multielemental signatures represented as principal components varied with pH for both species. Of these, U/Ca was the best predictor of pH and did not vary with larval size, with semidiurnal pH fluctuations, or with oxygen concentration. Field applications of U/Ca were tested with mussel larvae reared in situ at both known and unknown pH conditions. Larval shells precipitated in a region of greater upwelling had higher U/Ca, and these U/Ca values corresponded well with the laboratory-derived U/Ca-pH proxy. Retention of the larval shell after settlement in molluscs allows use of this geochemical proxy to assess ocean acidification effects on marine populations.

Mn/Ca and Fe/Ca systematics in benthic foraminifera from the Peruvian OMZ

In this study we present an initial dataset of Mn/Ca and Fe/Ca ratios in tests of benthic foraminifera from the Peruvian oxygen minimum zone (OMZ) determined with SIMS. These results are a contribution to a better understanding of the proxy potential of these elemental ratios for ambient redox conditions. Foraminiferal tests are often contaminated by diagenetic coatings, like Mn rich carbonate- or Fe and Mn rich (oxyhydr)oxide coatings. Thus, it is substantial to assure that the cleaning protocols are efficient or that spots chosen for microanalyses are free of contaminants. Prior to the determination of the element/Ca ratios, the distributions of several elements (Ca, Mn, Fe, Mg, Ba, Al, Si, P and S) in tests of the shallow infaunal species Uvigerina peregrina and Bolivina spissa were mapped with an electron microprobe (EMP). To visualize the effects of cleaning protocols uncleaned and cleaned specimens were compared. The cleaning protocol included an oxidative cleaning step. An Fe rich phase was found on the inner test surface of uncleaned U. peregrina specimens. This phase was also enriched in Al, Si, P and S. A similar Fe rich phase was found at the inner test surface of B. spissa. Specimens of both species treated with oxidative cleaning show the absence of this phase. Neither in B. spissa nor in U. peregrina were any hints found for diagenetic (oxyhydr)oxide or carbonate coatings. Mn/Ca and Fe/Ca ratios of single specimens of B. spissa from different locations have been determined by secondary ion mass spectrometry (SIMS). Bulk analyses using solution ICP-MS of several samples were compared to the SIMS data. The difference between SIMS analyses and ICP-MS bulk analyses from the same sampling sites was 14.0-134.8 µmol mol-1 for the Fe/Ca and 1.68(±0.41) µmol mol-1 for the Mn/Ca ratios. This is in the same order of magnitude as the variability inside single specimens determined with SIMS at these sampling sites (1sigma[Mn/Ca] = 0.35-2.07 µmol mol-1; 1sigma[Fe/Ca] = 93.9-188.4 µmol mol-1). The Mn/Ca ratios in the calcite were generally relatively low (2.21-9.93 µmol mol-1) but in the same magnitude and proportional to the surrounding pore waters (1.37-6.67 µmol mol-1). However, the Fe/Ca ratios in B. spissa show a negative correlation to the concentrations in the surrounding pore waters. Lowest foraminiferal Fe/Ca ratios (87.0-101.0 µmol mol-1) were found at 465 m water depth, a location with a strong sharp Fe peak in the pore water next to the sediment surface and respectively, high Fe concentrations in the surrounding pore waters. Previous studies found no living specimens of B. spissa at this location. All these facts hint that the analysed specimens already were dead before the Fe flux started and the sampling site just recently turned anoxic due to fluctuations of the lower boundary of the OMZ near the sampling site (465 m water depth). Summarized Mn/Ca and Fe/Ca ratios are potential proxies for redox conditions, if cleaning protocols are carefully applied. The data presented here may be rated as base for the still pending detailed calibration.

The Islamic Crossed-Arch Domes in Cordoba: Geometry and Structural Analysis of the “Capilla de Villaviciosa”

Crossed-arch domes are a singular type of ribbed vaults. Their characteristic feature is that the ribs that form the vault are intertwined, forming polygons or stars, leaving an empty space in the centre. The earliest known vaults of this type are found in the Great Mosque of Córdoba, built ca. 960 a.C. The type spread through Spain, and the north of Africa in the 10th to the 16th Centuries, and was used by Guarini and Vittone in the 17th and 18th Centuries in Italy. However, it was used only in a few buildings. Though the literature about the structural behaviour of ribbed Gothic vaults is extensive, so far no structural analysis of crossed arch domes has been made. The purpose of this work is, first to show the way to attack such an analysis within the frame of Modern Limit Analysis of Masonry Structures (Heyman 1995), and then to apply the approach to study the stability of the dome of the Capilla de Villaviciosa. The work may give some clues to art and architectural historians to understand better the origin and development of Islamic dome architecture.

Clean Coal Technologies Scenario and Evaluation of Present CO2 Dwindling Initiatives to Approach Zero Emission Power Stations By Coal Combustion. Deployment Situation and Evaluation Study

In the present uncertain global context of reaching an equal social stability and steady thriving economy, power demand expected to grow and global electricity generation could nearly double from 2005 to 2030. Fossil fuels will remain a significant contribution on this energy mix up to 2050, with an expected part of around 70% of global and ca. 60% of European electricity generation. Coal will remain a key player. Hence, a direct effect on the considered CO2 emissions business-as-usual scenario is expected, forecasting three times the present CO2 concentration values up to 1,200ppm by the end of this century. Kyoto protocol was the first approach to take global responsibility onto CO2 emissions monitoring and cap targets by 2012 with reference to 1990. Some of principal CO2emitters did not ratify the reduction targets. Although USA and China spur are taking its own actions and parallel reduction measures. More efficient combustion processes comprising less fuel consuming, a significant contribution from the electricity generation sector to a CO2 dwindling concentration levels, might not be sufficient. Carbon Capture and Storage (CCS) technologies have started to gain more importance from the beginning of the decade, with research and funds coming out to drive its come in useful. After first researching projects and initial scale testing, three principal capture processes came out available today with first figures showing up to 90% CO2 removal by its standard applications in coal fired power stations. Regarding last part of CO2 reduction chain, two options could be considered worthy, reusing (EOR & EGR) and storage. The study evaluates the state of the CO2 capture technology development, availability and investment cost of the different technologies, with few operation cost analysis possible at the time. Main findings and the abatement potential for coal applications are presented. DOE, NETL, MIT, European universities and research institutions, key technology enterprises and utilities, and key technology suppliers are the main sources of this study. A vision of the technology deployment is presented.

Transfer of the HIV-1 cyclophilin-binding site to simian immunodeficiency virus from Macaca mulatta can confer both cyclosporin sensitivity and cyclosporin dependence

HIV-1 specifically incorporates the peptidyl prolyl isomerase cyclophilin A (CyPA), the cytosolic receptor for the immunosuppressant cyclosporin A (CsA). HIV-1 replication is inhibited by CsA as well as by nonimmunosuppressive CsA analogues that bind to CyPA and interfere with its virion association. In contrast, the related simian immunodeficiency virus SIVmac, which does not interact with CyPA, is resistant to these compounds. The incorporation of CyPA into HIV-1 virions is mediated by a specific interaction between the active site of the enzyme and the capsid (CA) domain of the HIV-1 Gag polyprotein. We report here that the transfer of HIV-1 CA residues 86–93, which form part of an exposed loop, to the corresponding position in SIVmac resulted in the efficient incorporation of CyPA and conferred an HIV-1-like sensitivity to a nonimmunosuppressive cyclosporin. HIV-1 CA residues 86–90 were also sufficient to transfer the ability to efficiently incorporate CyPA, provided that the length of the CyPA-binding loop was preserved. However, the resulting SIVmac mutant required the presence of cyclosporin for efficient virus replication. The results indicate that the presence or absence of a type II tight turn adjacent to the primary CyPA-binding site determines whether CyPA incorporation enhances or inhibits viral replication. By demonstrating that CyPA-binding-site residues can induce cyclosporin sensitivity in a heterologous context, this study provides direct in vivo evidence that the exposed loop between helices IV and V of HIV-1 CA not merely constitutes a docking site for CyPA but is a functional target of this cellular protein.

Social transmission of reproductive behavior increases frequency of inherited disorders in a young-expanding population

The observation of high frequencies of certain inherited disorders in the population of Saguenay–Lac Saint Jean can be explained in terms of the variance and the correlation of effective family size (EFS) from one generation to the next. We have shown this effect by using the branching process approach with real demographic data. When variance of EFS is included in the model, despite its profound effect on mutant allele frequency, any mutant introduced in the population never reaches the known carrier frequencies (between 0.035 and 0.05). It is only when the EFS correlation between generations is introduced into the model that we can explain the rise of the mutant alleles. This correlation is described by a c parameter that reflects the dependency of children’s EFS on their parents’ EFS. The c parameter can be considered to reflect social transmission of demographic behavior. We show that such social transmission dramatically reduces the effective population size. This could explain particular distributions in allele frequencies and unusually high frequency of certain inherited disorders in some human populations.

Bimodal regulation of Na+–Ca2+ exchanger by β-adrenergic signaling pathway in shark ventricular myocytes

In shark heart, the Na+–Ca2+ exchanger serves as a major pathway for both Ca2+ influx and efflux, as there is only rudimentary sarcoplasmic reticulum in these hearts. The modulation of the exchanger by a β-adrenergic agonist in whole-cell clamped ventricular myocytes was compared with that of the Na+–Ca2+ exchanger blocker KB-R7943. Application of 5 μM isoproterenol and 10 μM KB-R7943 suppressed both the inward and the outward Na+–Ca2+ exchanger current (INa−Ca). The isoproterenol effect was mimicked by 10 μM forskolin. Isoproterenol and forskolin shifted the reversal potential (Erev) of INa−Ca by approximately −23 mV and −30 mV, respectively. An equivalent suppression of outward INa−Ca by KB-R7943 to that by isoproterenol produced a significantly smaller shift in Erev of about −4 mV. The ratio of inward to outward exchanger currents was also significantly larger in isoproterenol- than in control- and KB-R7943-treated myocytes. Our data suggest that the larger ratio of inward to outward exchanger currents as well as the larger shift in Erev with isoproterenol results from the enhanced efficacy of Ca2+ efflux via the exchanger. The protein kinase A-mediated bimodal regulation of the exchanger in parallel with phosphorylation of the Ca2+ channel and enhancement of its current may have evolved to satisfy the evolutionary needs for accelerated contraction and relaxation in hearts of animals with vestigial sarcoplasmic Ca2+ release stores.