Probing molecular and isotopic features of meteoritic insoluble organic matter by solid‐state nuclear magnetic resonance spectroscopy with sub‐milligram sample

We recorded one‐ and two‐dimensional solid‐state nuclear magnetic resonance spectra of meteoric insoluble organic matter with unprecedented sensitivity and resolution permitting us to reveal unambiguous spectroscopic fingerprints relevant to its molecular and isotopic features. Two‐dimensional ¹H‐¹H and ¹H‐¹³C correlation experiments have unveiled the spatial proximity between aliphatic and aromatic groups proving a highly branched character of a rigid macromolecular network composed of short aliphatic chains linking together small aromatic units. One‐dimensional ²H and two‐dimensional ¹H‐²H correlation spectroscopy delivered evidence of significant reduction in the deuterium enrichment of aromatic species relevant to interstellar processes, proto‐planetary disk chemistry, and to determining the origin of the meteoritic insoluble organic matter. The experimental approach developed in this work opens new perspectives for systematic and nondestructive analysis at the molecular level of meteoritic insoluble organic matter even with a very small amount of sample from some particularly rare chondrites.     

Texture development and deformation mechanisms in ringwoodite

Ringwoodite Mg₂SiO₄ with spinel structure is an important phase in the earth's mantle transition zone. Controlled deformation experiments showed that ringwoodite underwent ductile deformation when compressed axially at 6-10 GPa and at room temperature in a multianvil D-DIA deformation apparatus. Texture evolution during cyclic compression has been recorded in situ using X-ray transparent anvils with monochromatic synchrotron X-ray diffraction and a two-dimensional detector. Quantitative analysis of the images with the Rietveld method revealed a 1 1 0 fiber texture. By comparing this texture pattern with polycrystal plasticity simulations, it is inferred that {1 1 1}〈 1 0〉 slip is the dominant deformation mechanism in ringwoodite, consistent with high temperature mechanisms observed in other spinel-structured materials. Although strong ringwoodite textures may develop in the transition zone, the contribution to bulk anisotropy is minimal due to the weak single-crystal anisotropy.     

Molecular masses and chromophoric properties of dissolved organic ligands for copper(II) in oceanic water

The distribution of molecular masses of organic ligands for copper(II) in oceanic water was investigated. The bulk dissolved organic matter (DOM) was fractionated by ultrafiltration and organic ligands were extracted from the resultant fractions by using immobilized metal ion affinity chromatography (IMAC). Contributions of total organic ligands were 2.0–4.4% of the bulk DOM in surface waters, as determined by the UV absorbance. In the distribution of molecular masses of organic ligands, relative contribution of the fraction with low molecular masses (<1000 Da) was dominant (49–62%), while 26–33% of the total organic ligands was in the 1000–10,000 Da fraction, leaving 10–19% in the >10,000 Da fraction. The distribution of molecular masses of organic ligands shifted to higher molecular masses, as compared with that of the bulk DOM. The fluorescence intensities of organic ligands were shown to be associated with carboxyl contents, based on peak excitation/emission wavelengths and the pH-dependence of fluorescence. Two ligand classes with different conditional stability constants (log K_CuL′≈7 and 9) were determined from fluorescence quenching of ligand fractions during copper(II) titration. Organic ligands in low molecular mass fractions were relatively weak and strong ligands occurred in higher molecular mass fractions. It is suggested that the weaker ligand sites would consist of two or more carboxyl groups (log K_HL′=4), whereas carboxyl groups (log =2), which are protonated at lower pH, and primary amine may additionally contribute to the formation of more stable copper(II) complexes of the stronger ligand.     

Some characteristic features of the vertical profile of organic matter in recent sediment from the Bering Sea

Sedimentary samples were collected from a site (57°02.9N, 176°57.4W: 3,650 m) in the Aleutian Basin of the Bering Sea and analyzed for organic carbon, total nitrogen and various organic materials. Organic carbon and total nitrogen were measured in the range of 0.1–1.9% and 0.01–0.2% of the dry weight of the sediment, these values tended to decrease with depth, but considerably lower values were obtained in the volcanogenic sediment layers. Carbohydrate, amino acid and protein and lipid carbons accounted for 40% of the total organic carbon on the surface of the sediment, and this value tended to decrease with depth to 20% at 10m depth from the top of the core sample. The carbon to nitrogen (C/N) ratios ranged from 6.3 to 9.0. Vertical change in the values of the ratios can be understood in terms of a higher decay rate of amino acids and proteins.Radiocarbon age determinations on five sedimentary samples yielded sedimentation rates ranging from 37 to 90cm/1,000y.     

Chemical and Biological Studies of Particulate Organic Matter in the Ocean

This paper presents a review of the past decade's highlights of research on the isolation and characterisation of particulate organic matter (POM) in the world's oceans. The emphasis is on chemical studies but, in keeping with the growing interdisciplinary nature of marine science, advances in other disciplines are also discussed, particularly those in biological sciences. Increasing evidence for the importance of picoplankton, bacteria and viruses as POM constituents is highlighted, including the recent recognition of large populations of autotrophic bacteria able to harvest light for energy. The transport of POM to bottom waters was thought to be largely confined to large, rapidly sinking faecal pellets. However, recent studies have highlighted the importance of organic aggregates and flocs formed by diatoms such as Rhizosolenia and other microalgae. Ascending particles have also been discovered, many of which are lipid-rich. Several studies have shown that resuspension of bottom sediments and lateral advection of material from continental shelves can lead to anomalously high particle fluxes measured in sediment traps moored in deep water. Many new approaches for characterizing POM have emerged, such as pyrolysis gas chromatography-mass spectrometry and direct temperature-resolved mass spectrometry for analysis of higher molecular weight materials and biopolymers. Lipid biomarker techniques have also advanced, exciting new possibilities being raised by the ability to measure stable and radioactive carbon isotopes for individual compounds. The techniques of molecular biology, such as the polymerase chain reaction (PCR), are being increasingly applied to provide complementary information to more conventional microscopy and flow cytometry on the identity of organisms in the sea. The combination of these techniques with advanced chemical analysis methods promises to greatly increase our knowledge of the origins, transport and fate of organic matter in the oceans. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermochronology and the three-dimensional cooling pattern of a granitic pluton: an example from the Toki granite,Central Japan

The three-dimensional spatial variations in the cooling pattern of the Toki granitic body, a zoned pluton in Central Japan, have been evaluated quantitatively by thermochronology using cooling age determination based on the different closure temperatures for target mineral species. The Toki granite has hornblende K–Ar ages of about 74.3 ± 3.7 Ma (N = 2; closure temperature of 510 ± 25°C), biotite K–Ar ages of 78.5 ± 3.9 to 59.7 ± 1.5 Ma (N = 33; 300 ± 50°C), and zircon fission-track ages of 75.6 ± 3.3 to 52.8 ± 2.6 Ma (N = 44; 240 ± 50°C). The spatial variation in the biotite K–Ar age is similar to that in the zircon fission-track age in samples collected from 11 boreholes and seven outcrop sites in the Toki granite, indicating that cooling was effectively from the roof and also from the northwest margin. This cooling pattern shows a strong correlation with the Alumina Saturation Index (ASI) distribution of the body. Larger ASI values correspond to earlier and more rapid cooling after emplacement and smaller value to slower cooling. Toki granite was effectively cooled from the peraluminous regions where assimilation of country sedimentary rock was most extensive.     

Microstructures of olivine-plagioclase corona in meta-ultramafic rocks from Sefuri Mountains, NW Kyushu, Japan

Two types of reaction rims occur between olivine and plagioclase in ultramafic rocks from the Sefuri Mountains, NW Kyushu, Japan, which were metamorphosed under granulite-facies conditions. One occurs as a thin film of orthopyroxene along the boundary between olivine and plagioclase (orthopyroxene zone). The other is composed of two zones: symplectite of calcic amphibole and spinel on the plagioclase-side (symplectite zone) and calcic amphibole with sporadic orthopyroxene on the olivine-side (tremolite zone). In the tremolite zone, calcic amphibole shows a systematic decrease in Al content and increase in Mg/(Fe +Mg) with decreasing distance from olivine. Local equilibria maintained during the diffusion-controlled corona-forming reaction enable us to apply equilibrium thermodynamics to calcic amphibole and adjacent orthopyroxene. An integrated formulation of the Gibbs method for an Fe–Mg exchange reaction constrains the equilibrium temperature recorded in the tremolite zone to be 600–710 °C. It is significantly lower than the temperature of the granulite-facies metamorphism (800–900 °C) estimated using conventional geothermobarometry. Except for H₂O, the association of calcic amphibole and spinel in the symplectite zone is chemically equivalent to the association of olivine, plagioclase and orthopyroxene that was stable before the corona formation. This suggests that the following orthopyroxene-consuming reaction describes the paragenetic change taking place between 800–900 °C and 600–710 °C, olivine + plagioclase + orthopyroxene + aqueous fluid = calcic amphibole + spinel. In contrast, the overall reaction inferred from microstructures produces orthopyroxene as well as calcic amphibole and spinel at the expense of olivine and plagioclase. This reaction requires removal mainly of MgO that is also responsible for destabilizing the local association of olivine and plagioclase. These features suggest that the presence of orthopyroxene as a product in the corona is not always indicative of an orthopyroxene-producing reaction being responsible for the change of paragenetic relation. Microstructural features should be carefully applied to infer the reaction describing paragenetic change by which we argue the P–T path of the rocks.     

<Emphasis Type="Italic">P</Emphasis>–<Emphasis Type="Italic">V</Emphasis>–<Emphasis Type="Italic">T</Emphasis> equation of state of CaAl<Subscript>4</Subscript>Si<Subscript>2</Subscript>O<Subscript>11</Subscript> CAS phase

The thermoelastic parameters of the CAS phase (CaAl₄Si₂O₁₁) were examined by in situ high-pressure (up to 23.7 GPa) and high-temperature (up to 2,100 K) synchrotron X-ray diffraction, using a Kawai-type multi-anvil press. P–V data at room temperature fitted to a third-order Birch–Murnaghan equation of state (BM EOS) yielded: V _0,300 = 324.2 ± 0.2 Å³ and K _0,300 = 164 ± 6 GPa for K′ _0,300 = 6.2 ± 0.8. With K′ _0,300 fixed to 4.0, we obtained: V _0,300 = 324.0 ± 0.1 Å³ and K _0,300 = 180 ± 1 GPa. Fitting our P–V–T data with a modified high-temperature BM EOS, we obtained: V _0,300 = 324.2 ± 0.1 Å³, K _0,300 = 171 ± 5 GPa, K′ _0,300 = 5.1 ± 0.6 (?K _0,T /?T) _P  = ?0.023 ± 0.006 GPa K^?1, and α_0,T  = 3.09 ± 0.25 × 10^?5 K^?1. Using the equation of state parameters of the CAS phase determined in the present study, we calculated a density profile of a hypothetical continental crust that would contain ~10 vol% of CaAl₄Si₂O₁₁. Because of the higher density compared with the coexisting minerals, the CAS phase is expected to be a plunging agent for continental crust subducted in the transition zone. On the other hand, because of the lower density compared with lower mantle minerals, the CAS phase is expected to remain buoyant in the lowermost part of the transition zone.