Synthesis and thermal stability of 2 \frac{1}{2}-octahedral sodium mica,NaMg2.5 (OH)2∫i4O10]

A new 2 \(\frac{1}{2}\) -octahedral sheet silicate, NaMg_2.5 Si₄O₁₀ (OH)₂, has been synthesized from oxide mixtures in the temperature range 500–600°C at pressures between 1 and 5 kb. The lattice parameters are a ₀ = 5.298 Å, b ₀ = 9.047 Å, c ₀ = 9.479 Å and ß=99.55°. X-ray data are given in the text. At temperatures above 605° C/1 kb and 630° C/5 kb, it decomposes to magnesiorichterite plus quartz.     

Evidence for enhanced hydration on the northern flank of Olympus Mons, Mars

In this paper we report about a small region on the northern scarp of Olympus Mons showing an increase of the 3 μm hydration band in the OMEGA spectra, together with low superficial temperatures. Although water ice clouds can occurs on the flank of big martian volcanoes, radiative transfer modeling indicates that atmospheric water ice alone cannot justify the shape of the observed band. A fit of the 1.9–3 μm absorption features is obtained by hypothesizing that the study region consists of a mixture of dust and water ice covered by an optically thin (τ=0.08 at 3 μm) layer of dust. Thermal modeling also suggests that water ice in this region may be stable during most of the martian year due to the saturation of the atmosphere. If water ice is responsible for the observed spectral behavior, it might consist of a number of ice or snow patches possibly deposited in small depressions.     

Mineralization of vestimentiferan tubes at methane seeps on the Congo deep-sea fan

Vestimentiferan tube worms are prominent members of modern methane seep communities and are totally reliant as adults on symbiotic sulphide-oxidizing bacteria for their nutrition. The sulphide is produced in the sediment by a biochemical reaction called the anaerobic oxidation of methane (AOM). A well-studied species from the Gulf of Mexico shows that seep vestimentiferans ‘mine’ sulphide from the sediment using root-like, thin walled, permeable posterior tube extensions, which can also be used to pump sulphate and possibly hydrogen ions from the soft tissue back into the sediment to increase the local rate of AOM. The ‘root-balls’ of exhumed seep vestimentiferans are intimately associated with carbonate nodules, which are a result of AOM. We have studied vestimentiferan specimens and associated carbonates from seeps at the Kouilou pockmark field on the Congo deep-sea fan and find that some of the posterior ‘root’ tubes of living specimens are enclosed with carbonate indurated sediment and other, empty examples are partially or completely replaced by the carbonate mineral aragonite. This replacement occurs from the outside of the tube wall inwards and leaves fine-scale relict textures of the original organic tube wall. The process of mineralization is unknown, but is likely a result of post-mortem microbial decay of the tube wall proteins by microorganisms or the precipitation from locally high flux of AOM derived carbonate ions. The aragonite-replaced tubes from the Kouilou pockmarks show similar features to carbonate tubes in ancient seep deposits and make it more likely that many of these fossil tubes are those of vestimentiferans. These observations have implications for the supposed origination of this group, based on molecular divergence estimates.     

Experimental evidence for an effect of early-diagenetic interaction between labile and refractory marine sedimentary organic matter on nitrogen dynamics

In most natural sedimentary systems labile and refractory organic material (OM) occur concomitantly. Little, however, is known on how different kinds of OM interact and how such interactions affect early diagenesis in sediments. In a simple sediment experiment, we investigated how interactions of OM substrates of different degradability affect benthic nitrogen (N) dynamics. Temporal evolution of a set of selected biogeochemical parameters was monitored in sandy sediment over 116 days in three experimental set-ups spiked with labile OM (tissue of Mytilus edulis), refractory OM (mostly aged Zostera marina and macroalgae), and a 1:1 mixture of labile and refractory OM. The initial amounts of particulate organic carbon (POC) were identical in the three set-ups. To check for non-linear interactions between labile and refractory OM, the evolution of the mixture system was compared with the evolution of the simple sum of the labile and refractory systems, divided by two. The sum system is the experimental control where labile and refractory OM are virtually combined but not allowed to interact. During the first 30 days there was evidence for net dissolved-inorganic-nitrogen (DIN) production followed by net DIN consumption. (Here ‘DIN’ is the sum of ammonium, nitrite and nitrate.) After  30 days a quasi steady state was reached. Non-linear interactions between the two types of OM were reflected by three main differences between the early-diagenetic evolutions of nitrogen dynamics of the mixture and sum (control) systems: (1) In the mixture system the phases of net DIN production and consumption commenced more rapidly and were more intense. (2) The mixture system was shifted towards a more oxidised state of DIN products [as indicated by increased (nitrite + nitrate)/(ammonium) ratios]. (3) There was some evidence that more OM, POC and particulate nitrogen were preserved in the mixture system. That is, in the mixture system more particulate OM was preserved while a higher proportion of the decomposed particulate N was converted into inorganic N. It can be concluded that during the first days and weeks of early diagenesis the magnitude and composition of the flux of decompositional dissolved N-compounds from sediments into the overlying water was influenced by non-linear interactions of OM substrates of different degradability. Given these experimental results it is likely that the relative spatial distributions of OM of differing degradability in sediments control the magnitude and composition of the return flux of dissolved N-bearing compounds from sediments into the overlying water column.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.     

In situ U–Pb dating of micro-baddeleyite by secondary ion mass spectrometry

We introduce a technique for U–Pb dating of baddeleyite using secondary ion mass spectrometry (SIMS) in situ analysis of ng-mass crystals that cannot be efficiently extracted by conventional mineral separation techniques. Average ²⁰⁷Pb/²⁰⁶Pb ages for Precambrian baddeleyite crystals are within < 0.3% of the respective isotope dilution thermal ionization mass spectrometry (ID-TIMS) ages. ²⁰⁶Pb/²³⁸U ratios are corrected for instrumental fractionation calibrated through linear regression in a Pb/U relative sensitivity vs. UO₂⁺/U⁺ calibration plot. Calibration is performed on separated baddeleyite crystals (～ 100–200 μm in maximum dimension) mounted in random crystallographic orientation. ²⁰⁶Pb/²³⁸U ages for baddeleyite from Duluth gabbro (FC4b) and Kovdor are accurate within 1–2% when averaging 15–30 individual spot analyses and relative sensitivities calibrated on Phalaborwa baddeleyite. The relative difference of ²⁰⁶Pb/²³⁸U between large crystals and micro-baddeleyite from FC4b is within ～ 1%. Comparison between silicate glass and baddeleyite, as well as replicate analysis of the same grains in different orientations relative to the incidence direction of the primary beam support previous evidence for bias in Pb/U sensitivity in baddeleyite due to variable crystal orientations. We successfully utilized oxygen flooding and a UO₂⁺/U⁺-based calibration to significantly reduce orientation dependent bias.     

In situ U–Pb SIMS (IN-SIMS) micro-baddeleyite dating of mafic rocks: Method with examples

An in situ U–Pb SIMS (IN-SIMS) method to date micro-baddeleyite crystals as small as 3 μm is presented with results from three samples that span a variety of ages and geologic settings. The method complements ID-TIMS geochronology by extending the range of dateable crystals to sizes smaller than can be recovered by physical separation. X-ray mapping and BSE imaging are used to locate target grains in thin section, followed by SIMS analysis on a CAMECA ims 1270, using the field aperture in the transfer column to screen out ions from host phases. Internal age precisions for the method are anticipated to range from 0.1% for Precambrian rocks to 3–7% for Phanerozoic rocks. Results establish a 2689 ± 5 Ma age for mafic dikes in the Wyoming craton, USA, a 1540 ± 30 Ma age for a subaerial lava flow from the Thelon Basin of northern Canada, and a 457 ± 34 Ma age for mafic dikes in the platform sequence of southeastern Siberia. The method is ideal for relatively non-destructive dating of small samples such as extraterrestrial rocks and precious terrestrial samples.     

Complete recycling of a magmatic arc: evidence from chemical and isotopic composition of Quaternary trench sediments in Chile (36°–40°S)

Marine Quaternary trench and slope sediments were sampled along the margin of the Southern Andes, Chile between 36° and 40°S. Major and trace element contents indicate only minor influence of weathering and transport fractionation. The whole rock composition of the sediments is similar to the average rock of the Cretaceous to Holocene magmatic arc of this section of the southern volcanic zone. Sr, Nd, and Pb isotope composition of the sediments also resembles closely the average composition of the magmatic arc. The contribution of compositionally distinct Palaeozoic crust, which makes up most of the volume of the forearc, is ~0–20% crustal Sr, Nd, and Pb according to the isotope record of the trench and slope sediments. Input of sediments from the continent into the subduction system was dominated by detritus from the magmatic arc at least for the last 20 My on the basis of the Oligocene to Holocene exhumation history of the margin.