Density of alkyl esters and its mixtures

Biodiesel density is a key parameter in biodiesel simulations and process development. In this work we selected, evaluated and improved two density models, one theoretical (Rackett-Soave) and one empirical (Lapuerta's method) for methanol based biodiesels (FAME) and ethanol based biodiesel (FAEE). For this purpose, biodiesel was produced from vegetable oils (sunflower, rapeseed, soybean, olive, safflower and other two commercial mixtures of vegetable oils) and animal fats (edible and crude pork fat and beef tallow) using both methanol and ethanol for the transesterification reactions, and blended to get 21 FAME and 21 FAEE, reporting their density and detailed composition. Bibliographic data have also been used. The Rackett-Soave method has been improved by the use of a new acentric factor correlation, whereas the parameters of the empirical one are improved by considering a bigger density data bank. Results show that the evaluated models could be used to estimate the biodiesel density with a good grade of accuracy but the performed modifications improve the accuracy of the models: ARD (%) for FAME; 0.33, and FAEE; 0.26, both calculated with the modification of Rackett-Soave method and ARD (%) for FAME; 0.40 calculated with the modification of the Lapuerta's method).

Seawater carbonate chemistry and calcification rates of Porites rus and Hydrolithon onkodes in experiments of Moorea

Central to evaluating the effects of ocean acidification (OA) on coral reefs is understanding how calcification is affected by the dissolution of CO2 in sea water, which causes declines in carbonate ion concentration [CO3]2- and increases in bicarbonate ion concentration [HCO3]-. To address this topic, we manipulated [CO3]2- and [HCO3]- to test the effects on calcification of the coral Porites rus and the alga Hydrolithon onkodes, measured from the start to the end of a 15-day incubation, as well as in the day and night. [CO3]2- played a significant role in light and dark calcification of P. rus, whereas [HCO3]- mainly affected calcification in the light. Both [CO3]2- and [HCO3]- had a significant effect on the calcification of H. onkodes, but the strongest relationship was found with [CO3]2-. Our results show that the negative effect of declining [CO3]2- on the calcification of corals and algae can be partly mitigated by the use of [HCO3]- for calcification and perhaps photosynthesis. These results add empirical support to two conceptual models that can form a template for further research to account for the calcification response of corals and crustose coralline algae to OA.

Rare-earth elements and isotope ratios at DSDP Leg 82 Holes

We report 48 analyses of rare-earth elements (REE) and 15 143Nd/144Nd and 87Sr/86Sr analyses for basalts from the eight holes drilled during Leg 82. Discrete and distinct REE patterns and 143Nd/144Nd ratios characterize the eight holes, with little variation observed downhole except in Holes 561 and 558, thus suggesting dominantly long-term temporal and large-scale spatial variations in the mantle source of these basalts beneath the Mid-Atlantic Ridge over the last 35 Ma of its spreading activity. There is a good inverse correlation between 143Nd/144Nd and (La/Sm)EF with one exception in Hole 558 (approximately 35 Ma), the latter suggesting a recent (35 Ma) light REE depletion event, perhaps caused by dynamic or fractional melting. Short-term temporal and small-scale spatial mantle source variability is also evident in Hole 561 (approximately 18 Ma), which has rapid fluctuations in REE patterns and 143Nd/144Nd ratios (suggesting rapid transfer of magma from the time of melting) and is evidence contrary to the presence of a well-mixed magma chamber at this particular site and time. The mantle source variations noted can be interpreted within two extreme models. The first model invokes a convecting mantle depleted in large ion lithophile elements (LILE) and containing lumps (or veins) of LILE-enriched material of various shapes and sizes, passively and randomly distributed throughout. A second more restrictive model considers the interaction of fixed mantle plumes and the LILE-depleted asthenosphere flowing towards a migrating Mid- Atlantic Ridge (MAR) axis. With the exception of Hole 558 and the uncertainties of reconstructions of absolute plate movements in the region, the observed variations can be explained by two hot spots; the nearly ridge-centered Azores hot spot (plume) and another hot spot located beneath the African plate that may be affecting the source of basalts currently erupting at the MAR axis at 35°N and which, in the past, would have produced the New England chain of seamounts on the North American plate and (later) the Atlantis-Great Meteor chain on the African plate. Basalts erupted south of the Hayes Fracture Zone have not been affected by either of these two hot spots over the last 35 Ma and appear to have been continuously derived from the LILE-depleted source. Subaxial flow downridge from the Azores plume appears to have started 9 Ma, on the basis of the southward converging V-shaped time-transgressive ridges branching from the Pico and Corves Island, or not earlier than 16 Ma, on the basis of the geochemical results. Variations within Hole 558 remains unexplained by the latter model, unless we hypothesize a third hot spot.

Decline in growth of foraminifer Marginopora rossi under eutrophication and ocean acidification scenarios

The combination of global and local stressors is leading to a decline in coral reef health globally. In the case of eutrophication, increased concentrations of dissolved inorganic nitrogen (DIN) and phosphorus (DIP) are largely attributed to local land use changes. From the global perspective, increased atmospheric CO2 levels are not only contributing to global warming but also ocean acidification (OA). Both eutrophication and OA have serious implications for calcium carbonate production and dissolution among calcifying organisms. In particular, benthic foraminifera precipitate the most soluble form of mineral calcium carbonate (high-Mg calcite), potentially making them more sensitive to dissolution. In this study, a manipulative orthogonal two-factor experiment was conducted to test the effects of dissolved inorganic nutrients and OA on the growth, respiration and photophysiology of the large photosymbiont-bearing benthic foraminifer, Marginopora rossi. This study found the growth rate of M. rossi was inhibited by the interaction of eutrophication and acidification. The relationship between M. rossi and its photosymbionts became destabilized due to the photosymbiont's release from nutrient limitation in the nitrate-enriched treatment, as shown by an increase in zooxanthellae cells per host surface area. Foraminifers from the OA treatments had an increased amount of Chl a per cell, suggesting a greater potential to harvest light energy, however, there was no net benefit to the foraminifer growth. Overall, this study demonstrates that the impacts of OA and eutrophication are dose dependent and interactive. This research indicates an OA threshold at pH 7.6, alone or in combination with eutrophication, will lead to a decline in M. rossi calcification. The decline in foraminifera calcification associated with pollution and OA will have broad ecological implications across their ubiquitous range and suggests that without mitigation it could have serious implications for the future of coral reefs.

Chemistry and boron isotope ratios of Izu arc front volcanic rocks

The process of fluid release from the subducting slab beneath the Izu arc volcanic front (Izu VF) was examined by measuring B concentrations and B isotope ratios in the Neogene fallout tephra (ODP Site 782A). Both were measured by secondary ion mass spectrometry, in a subset of matrix glasses and glassy plagioclase-hosted melt inclusions selected from material previously analyzed for major and trace elements (glasses) and radiogenic isotopes (Sr, Nd, Pb; bulk tephra). These tephra glasses have high B abundances (~10-60 ppm) and heavy delta11B values (+4.5? to +12.0?), extending the previously reported range for Izu VF rocks (delta11B, +7.0? to +7.3?). The glasses show striking negative correlations of delta11B with large ion lithophile element (LILE)/Nb ratios. These correlations cannot be explained by mixing two separate slab fluids, originating from the subducting sediment and the subducting basaltic crust, respectively (model A). Two alternative models (models B and C) are proposed. Model B proposes that the inverse correlations are inherited from altered oceanic crust (AOC), which shows a systematic decrease of B and LILE with increasing depth (from basaltic layer 2A to layer 3), paralleled by an increase in delta11B (from ~ +1? to +10? to +24?). In this model, the contribution of sedimentary B is insignificant (<4% of B in the Izu VF rocks). Model C explains the correlation as a mixture of a low-delta11B (~ +1?) 'composite' slab fluid (a mixture of metasediment- and metabasalt-derived fluids) with a metasomatized mantle wedge containing elevated B (~1-2 ppm) and heavy delta11B (~ +14?). The mantle wedge was likely metasomatized by 11B-rich fluids beneath the outer forearc, and subsequently down dragged to arc front depths by the descending slab. Pb-B isotope systematics indicate that, at arc front depths, ~ 53% of the B in the Izu VF is derived from the wedge. This implies that the heavy delta11B values of Izu VF rocks are largely a result of fluid fractionation, and do not reflect variations in slab source provenance (i.e. subducting sediment vs. basaltic crust). Since the B content of the peridotite at the outer forearc (7-58 ppm B, mean 24 +/- 16 ppm) is much higher than beneath the arc front (~1-2 ppm B), the hydrated mantle wedge must have released a B-rich fluid on its downward path. This 'wedge flux' can explain (1) the across-arc decrease in B and delta11B (e.g. Izu, Kuriles), without requiring a progressive decrease in fluid flux from the subducting slab, and (2) the thermal structure of volcanic arcs, as reflected in the B and delta11B variations of volcanic arc rocks.

Grain size distribution analysis of prominent beds on Southern Central Chilean seamounts

Gravity cores obtained from isolated seamounts located within, and rising up to 300 m from the sediment-filled Peru-Chile Trench off Southern Central Chile (36°S-39°S) contain numerous turbidite layers which are much coarser than the hemipelagic background sedimentation. The mineralogical composition of some of the beds indicates a mixed origin from various source terrains while the faunal assemblage of benthic foraminifera in one of the turbidite layers shows a mixed origin from upper shelfal to middle-lower bathyal depths which could indicate a multi-source origin and therefore indicate an earthquake triggering of the causing turbidity currents. The bathymetric setting and the grain size distribution of the sampled layers, together with swath echosounder and sediment echosounder data which monitor the distribution of turbidites on the elevated Nazca Plate allow some estimates on the flow direction, flow velocity and height of the causing turbidity currents. We discuss two alternative models of deposition, both of which imply high (175-450 m) turbidity currents and we suggest a channelized transport process as the general mode of turbidite deposition. Whether these turbidites are suspension fallout products of thick turbiditic flows or bedload deposits from sheet-like turbidity currents overwhelming elevated structures cannot be decided upon using our sedimentological data, but the specific morphology of the seamounts rather argues for the first option. Oxygen isotope stratigraphy of one of the cores indicates that the turbiditic sequences were deposited during the last Glacial period and during the following transition period and turbiditic deposition stopped during the Holocene. This climatic coupling seems to be dominant, while the occurrence of megathrust earthquakes provides a trigger mechanism. This seismic triggering takes effect only during times of very high sediment supply to the shelf and slope.