Experimental formation of massive hydrate deposits from accumulation of CH4 gas bubbles within synthetic and natural sediments

In order for methane to be economically produced from the seafloor, prediction and detection of massive hydrate deposits will be necessary. In many cases, hydrate samples recovered from seafloor sediments appear as veins or nodules, suggesting that there are strong geologic controls on where hydrate is likely to accumulate. Experiments have been conducted examining massive hydrate accumulation from methane gas bubbles within natural and synthetic sediments in a large volume pressure vessel through temperature and pressure data, as well as visual observations. Observations of hydrate growth suggest that accumulation of gas bubbles within void spaces and at sediment interfaces likely results in the formation of massive hydrate deposits. Methane hydrate was first observed as a thin film forming at the gas/water interface of methane bubbles trapped within sediment void spaces. As bubbles accumulated, massive hydrate growth occurred. These experiments suggest that in systems containing free methane gas, bubble pathways and accumulation points likely control the location and habit of massive hydrate deposits.     

Ecohydrographic constraints on biodiversity and distribution of phytoplankton and zooplankton in coral reefs of the Red Sea,Saudi Arabia

An integral concept of ecological research is the constraint of biodiversity along latitudinal and environmental gradients. The Red Sea features a natural example of a latitudinal gradient of salinity, temperature and nutrient richness. Coral reefs along the Red Sea coasts are supported with allochthonous resources such as oceanic and neritic phytoplankton and zooplankton; however, relatively little is known about how the ecohydrography correlates with plankton biodiversity and abundance. In this article we present the biodiversity of phytoplankton and zooplankton in Red Sea coral reefs. Oceanographic data (temperature, salinity), water samples for nutrient analysis, particulate organic matter, phytoplankton and zooplankton, the latter with special reference to Copepoda (Crustacea), were collected at nine coral reefs over ~1500 km distance along the Red Sea coast of Saudi Arabia. The trophic state of ambient waters [as indicated by chlorophyll a (Chl a)] changed from strong oligotrophy in the north to mesotrophy in the south and was associated with increasing biomasses of Bacillariophyceae, picoeukaryotes and Synechococcus as indicated by pigment fingerprinting (CHEMTAX) and flow cytometry. Net‐phytoplankton microscopy revealed a Trichodesmium erythraeum (Cyanobacteria) bloom north of the Farasan Islands. Several potentially harmful algae, including Dinophysis miles and Gonyaulax spinifera (Dinophyceae), were encountered in larger numbers in the vicinity of the aquaculture facilities at Al Lith. Changes in zooplankton abundance were mainly correlated to the phytoplankton biomass following the latitudinal gradient. The largest zooplankton abundance was observed at the Farasan Archipelago, despite high abundances of copepodites, veligers (Gastropoda larvae) and Chaetognatha at Al Lith. Although the community composition changed over latitude, biodiversity indices of phytoplankton and zooplankton did not exhibit a systematic pattern. As this study constitutes the first current account of the plankton biodiversity in Red Sea coral reefs at a large spatial scale, the results will be informative for ecosystem‐based management along the coastline of Saudi Arabia.     

Boron abundances and isotopic ratios of olivine grains on Itokawa returned by the Hayabusa spacecraft

We report the B abundances and isotopic ratios of two olivine grains from the S‐type asteroid Itokawa sampled by the Hayabusa spacecraft. Olivine grains from the Dar al Gani (DaG) 989 LL6 chondrite were used as a reference. Since we analyzed polished thin sections in both cases, we expect the contribution from the solar wind B (rich in ¹⁰B) to be minimal because the solar wind was implanted only within very thin layers of the grain surface. The Itokawa and DaG 989 olivine grains have homogeneous B abundances (~400 ppb) and ¹¹B/¹⁰B ratios compatible with the terrestrial standard and bulk chondrites. The observed homogeneous B abundances and isotopic ratios of the Itokawa olivine grains are likely the result of thermal metamorphism which occurred in the parent asteroid of Itokawa, which had a similar composition as LL chondrites. The chondritic B isotopic ratios of the Itokawa samples suggest that they contain little cosmogenic B (from cosmic‐ray spallation reactions) rich in ¹⁰B. This observation is consistent with the short cosmic‐ray exposure ages of Itokawa samples inferred from the small concentrations of cosmogenic ²¹Ne. If other Itokawa samples have little cosmogenic B as well, the enrichment in ¹⁰B found previously on the surface of another Itokawa particle (as opposed to the bulk grain study here) may be attributed to implanted solar wind B.     

Shock experiments on anhydrite and new constraints on the impact‐induced SOx release at the K‐Pg boundary

Abstract– We have performed six shock experiments at nominal peak‐shock pressures of 12.5, 20, 33, 46.5, 64, and 85 GPa using polycrystalline anhydrite discs embedded in ARMCO‐Fe sample containers and the shock reverberation technique. The recovered samples were analyzed using X‐ray powder diffraction and transmission electron microscopy (TEM). The X‐ray diffraction patterns recorded on all samples are compatible with the anhydrite structure; extra‐peaks have not been observed. Peak intensities decrease and peak broadening increases progressively in the pressure range from 0 to 46.5 GPa. At higher pressures, peak broadening diminishes and the X‐ray diffraction pattern of the 85 GPa sample resembles essentially that of unshocked, well‐crystallized anhydrite. Related structural changes at the nanoscale include in the pressure regime up to 20 GPa “cold” deformation phenomena such as cracks and deformation twins. Dislocation density increases up to 33 GPa and the strain increases up to 46.5 GPa. In the pressure range from 46.5 to 85 GPa, high postshock temperatures caused annealing of the deformation features. Increasing density and size of voids in the anhydrite samples shocked at 64 and 85 GPa indicate partial decomposition of anhydrite. Recalculation of the peak‐shock pressure in the experiments to a more realistic natural loading path indicates the onset of degassing of anhydrite in the pressure range of 30–41 GPa.     

Search for extinct aluminum‐26 and titanium‐44 in nanodiamonds from the Allende CV3 and Murchison CM2 meteorites

Abstract– We report Mg‐Al and Ca‐Ti isotopic data for meteoritic nanodiamonds separated from the Allende CV3 and Murchison CM2 meteorites. The goal of this study was to search for excesses in ²⁶Mg and ⁴⁴Ca, which can be attributed to the in situ decay of radioactive and now extinct ²⁶Al and ⁴⁴Ti, respectively. Previous work on presolar SiC and graphite had shown that ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios in presolar grains can be used to discriminate between different types of stellar sources. Aluminum and Ti concentrations are low in the meteoritic nanodiamonds of this study. Murchison nanodiamonds have higher Al and Ti concentrations than the Allende nanodiamonds. This can be attributed to contamination and the presence of presolar SiC in the Murchison nanodiamond samples. ²⁶Mg/²⁴Mg and ⁴⁴Ca/⁴⁰Ca ratios are close to normal in Allende nanodiamonds with upper limits on the initial ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios of approximately 1 × 10^?3. These ratios are factors of 10–1000 and, respectively, 1–1000 lower than those of presolar SiC and graphite grains from supernovae. The ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti data for nanodiamonds are compatible with an asymptotic giant branch star or solar system origin, but not with a supernova origin of a major fraction of meteoritic nanodiamonds. The latter possibility cannot be excluded, though, as the diamond separates may contain significant amounts of contaminating Al and Ti, which would lower the inferred ²⁶Al/²⁷Al and ⁴⁴Ti/⁴⁸Ti ratios considerably.     

Heavily fractionated noble gases in an acid residue from the Klein Glacier 98300 EH3 chondrite

Noble gases were measured both in bulk samples (stepped pyrolysis and total extraction) and in a HF/HCl residue (stepped pyrolysis and combustion) from the Klein Glacier (KLE) 98300 EH3 chondrite. Like the bulk meteorite and as seen in previous studies of bulk type 3 E chondrites (“sub-Q”), the acid residue contains elementally fractionated primordial noble gases. As we show here, isotopically these are like those in phase-Q of primitive meteorites, but elementally they are heavily fractionated relative to these. The observed noble gases are different from “normal” Q noble gases also with respect to release patterns, which are similar to those of Ar-rich noble gases in anhydrous carbonaceous chondrites and unequilibrated ordinary chondrites (with also similar isotopic compositions). While we cannot completely rule out a role for parent body processes such as thermal and shock metamorphism (including a later thermal event) in creating the fractionated elemental compositions, parent body processes in general seem not be able to account for the distinct release patterns from those of normal Q noble gases. The fractionated gases may have originated from ion implantation from a nebular plasma as has been suggested for other types of primordial noble gases, including Q, Ar-rich, and ureilite noble gases. With solar starting composition, the corresponding effective electron temperature is about 5000 K. This is lower than inferred for other primordial noble gases (10,000-6000 K). Thus, if ion implantation from a solar composition reservoir was a common process for the acquisition of primordial gas, electron temperatures in the early solar system must have varied spatially or temporally between 10,000 and 5000 K.Neon and xenon isotopic ratios of the residue suggest the presence of presolar silicon carbide and diamond in abundances lower than in the Qingzhen EH3 and Indarch EH4 chondrites. Parent body processes including thermal and shock metamorphism and a late thermal event also cannot be responsible for the low abundances of presolar grains. KLE 98300 may have started out with smaller amounts of presolar grains than Qingzhen and Indarch.     

Impacts of tectonic and orbital forcing on East African climate: a comparison based on global climate model simulations

A global atmosphere–ocean model has been forced with topographic and orbital scenarios in order to evaluate the relative role of both factors for the past climate of East Africa. Forcing the model with a significantly reduced topography in Eastern and Southern Africa leads to a distinct increase in moisture transport from the Indian Ocean into the eastern part of the continent and increased precipitation in Eastern Africa. Simulations with step-wise reduced height show that this climate change occurs continuously with the change in topography, i.e., an abrupt change of local climatic features with a critical height is not found. Simulations of the last interglacial (at 125,000 years before present, i.e., the Eemian interglacial) and the last glacial inception (at 115,000 years before present) are used as examples for the role of orbital-induced changes in insolation. Here, changes in meridional temperature gradients lead to modifications in moisture transport of similar order of magnitude, but with different spatial and seasonal structure. For the Eemian interglacial, a distinct increase in summer moisture transport from the Atlantic deep into the continent at around 20°N is simulated.     

Long-Term Observations of Isotope Ratio Accuracy and Reproducibility Using Quadrupole ICP-MS

High precision isotope ratio and trace element determination can be achieved with modern quadrupole ICP-MS provided that short and long-term instrument performance is accurately monitored. Here we present results for the isotope ratios ⁶Li/⁷Li, ¹⁴⁷Sm/¹⁴⁹Sm, ¹⁶⁰Dy/¹⁶¹Dy, ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁶Pb/²⁰⁴Pb and ²³⁵U/²³⁸U with which we determined long-term isotope ratio stability of relevance to both trace element and isotope determination. With respect to trace element determination, we first present long-term observations regarding oxide formation rates of Ba and Nd on light REE and heavy REE, as well as Zr on Ag. These showed good correlations and could be used to correct effectively the interference. The efficacy of this correction was demonstrated with analyses of the rock reference material BHVO-2 at both low and high oxide formation rates. Next, we studied the long-term reproducibility of a Dy isotope ratio that was measured to correct for the isobaric interference on Gd. It was found that, regardless of tuning condition, the ratio reproduced very well (0.58% RSD, 1s) and that the estimate of the Gd concentration did not suffer from the large correction (> 10%) caused by the Dy isobar. Long-term reproducibilities of Li, Sm and U isotope ratios, required for accurate mass bias correction when isotopically enriched internal standards of these elements are employed, were measured in the rock reference materials AGV-2 and JA-3 over a time period of up to 3 years. As expected, the Li isotope ratio showed the largest variability (RSD = 7%), but the other two ratios had relative external reproducibilities of only 1.01% (1s, U) and 0.67% (Sm). The mass bias-induced scatter in measurements for Sm and U was so small that the internal standard correction was effective, even for samples with high concentrations of these elements. With regard to Pb-isotope ratio determination, we also present long-term reproducibility for NIST SRM 982, run as an unknown and two accuracy tests for Pb separated from granitoids and from meteorites. It is demonstrated that the obtained ratios, including those involving ²⁰⁴Pb, are accurate relative to MC-ICP-MS determinations and of comparable precision to conventional TIMS analysis. The excellent agreement between all data sets shows the potential of modern quadrupole ICP-MS instrumentation for Pb-isotope determination, particularly for samples with very low Pb content.     

Fragility curves for masonry structures submitted to permanent ground displacements and earthquakes

Usually, the vulnerability of structures is treated considering only one single hazard, for example either seismic hazard or ground instability. However, historical monuments, cultural heritage structures or old masonry structures can be affected, over the past centuries of existence, by a succession of different hazards. The objective of this paper was to quantify the changes in the seismic vulnerability of a given structure previously damaged by quasi-static differential settlements. In view of this, a soil-structure model of the masonry building is constructed using TREMURI software by putting springs at the base of the building to account for the soil behaviour. Classical empirical relationships are used for setting the mechanical properties of these foundation springs. The chosen equations are valid for both static and dynamic situations. The soil-structure model is first submitted to differential settlements with maximum magnitudes ranging from 5 to 25 cm. Then, the damaged structures are submitted to a set of time-histories. Fragility curves taking into consideration permanent differential settlements are finally obtained, using a modified regression technique accounting for the presence of residual drift due to the prior static loading.     

Tying platform drowning to perturbations of the global carbon cycle with a δ13COrg-curve from the Valanginian of DSDP Site 416

The carbonate carbon isotope record of the Phanerozoic is marked by repeated high-amplitude excursions towards more positive values. Although the interpretation of C-isotope events remains controversial, they are regarded as a proxy of the global C-cycle. Using δ¹³C_Org-measurements of samples from DSDP Site 416, it is shown that a classic example of platform drowning coincided with the onset of the mid-Valanginian carbon-cycle excursion. Widespread carbonate platform drowning would have contributed to the observed positive shift in the C-isotope record. As choking of carbonate production was compensated by increased organic production, both processes favoured a shift in marine carbon partitioning from the oxidized to the reduced carbon reservoir. This would have resulted in an increased flux of CO₂ from the atmosphere into the marine and sedimentary carbon reservoir.