Interstitial water chemistry of the inner continental shelf sediments off the gironde estuary

The interstitial water composition ( , alkalinity, Ca²⁺, Mg²⁺, Sr²⁺, Na⁺, K⁺) and the cation exchange capacity (CEC) were determined for the muddy sediments of the continental shelf off the Gironde Estuary (France), in the area where the sediment represents the deposit of the muddy suspension of the river. In comparison with seawater concentrations, the pore waters below 10 cm depth, show depletions of and Ca²⁺ and below a 30 cm depth show depletions of Mg²⁺. Inversely, the upper 10 cm an enrichment of Ca²⁺ concentration, and an increase of K⁺ concentration to a 40 cm depth. High values of are observed at the top 4 cm. Alkalinity enrichment is observed along the length of the core. Applying the alkalinity models for the sediment below a 10 cm depth demonstrates generally that calculated alkalinities are higher than the measured ones. Ca²⁺ dissolution occurs at the first 10 cm and authigenic carbonate precipitation starts beneath that level. Mg²⁺ depletion is accompanied by bicarbonate loss. This proves that Mg²⁺ depletion is due to a Mg-silicate reaction. The result of the CEC does not confirm the Mg²⁺ uptake by clay minerals in exchangeable site, under reducing conditions. Diffusion and bioturbation play an important role in the pore water concentration at the top of the core.     

低硼氢氧化镁的制备及热分解动力学参数

本文以水合氯化镁、工业氨水为原料制备出了低硼含量的纯度 >99%的氢氧化镁和氧化镁。利用差热 -热重 (DTA- TG)、X-射线衍射 (XRD)、透射电子显微镜 (TEM)等手段 ,对氢氧化镁的热稳定性、相结构、表观状态以及脱水动力学参数进行了分析。结果为 :氢氧化镁以束状纤维和片状粉末共存 ,在 6 2 3K基本完成脱水反应生成氧化镁 ,其脱水反应的表观活化能 E为135 .4 k J· mol-1,指前因子 A为 5 .15× 10 10 ,反应级数 n为 1.10     

Growth Aspects and Magnesium Carbonate Concentrations of the Reef Building Octocoral Heliopora coerulea (Pallas) after Transplantation

Abstract. An experiment to test C have's hypothesis on temperature dependent MgCO₃ concentrations in marine calcareous skeletons was undertaken by transplanting colonies of Heliopora coerulea. The corals were transferred from a shallow lagoon with high average temperatures to the outer bottom of a fringing reef, 16 m depth, with low average temperatures. Against expectation, a statistically significant increase of average mol % concentrations from 0.48 to 0.54 % for upper growth regions and from 0.49 to 0.62% for lower growth regions was obtained. Temperature records during the experimentation period and the above data indicate that the mol% MgCO₃ concentration in the skeleton of living Heliopora colonies increases when transplanted to an environment with a lower temperature average than that of their original growth site, and with seasonal temperature fluctuations which are smaller in the experimental site than in the control site. Temperature fluctuations at the control site were up to 2.5 times greater than at the experimental site for most of the observation months. This supports the conclusion that the parameters a) minimum temperature and b) temperature stability of the environment are essential for the incorporation of Mg into the carbonate skeleton matrix of marine organisms. Within this study the results of a quantitative chemical analysis of the carbonate skeleton of H. coerulea are presented and growth data of transplanted colonies compared with those from the control site.     

Synchrotron IR study of hydrous ringwoodite (γ-Mg2SiO4) up to 30 GPa

High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm⁻¹ at ambient temperature for hydrous Mg-ringwoodite (γ-Mg₂SiO₄) up to 30 GPa. The main feature in the OH⁻ stretching region is an extremely broad band centred at 3,150 cm⁻¹. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm⁻¹ and an absorption plateau persist with a maximum wavenumber of 3,800 cm⁻¹. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.     

微波消解-火焰原子吸收光谱法测定石英砂中的氧化钙和氧化镁

采用微波消解-硼酸络合-火焰原子吸收光谱法测定石英砂中的氧化钙和氧化镁。样品在MK-Ⅲ型实验室微波炉上消解,消解压力为2.0 MPa、消解时间为5 m in,以硼酸络合消除氢氟酸的影响。方法已用于实际样品的测定,7次测定的相对标准偏差(RSD)小于5%,加标回收率为95.0%~104.2%。     

Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.     

Tortoises and hares: dissolution,erosion and isostasy in landscape evolution

Denudation mechanisms differ fundamentally between limestone and silicate rock types, which are subject to very different rate thresholds and enhancers/inhibitors. Silicates are removed largely by erosion, the mechanical entrainment and transport of particles. This is a relatively high energy, and highly episodic, process which occurs only when a minimum threshold ?ow velocity is exceeded; it is inhibited by vegetation cover and favoured by strongly seasonal runoff. Limestone is removed largely by chemical dissolution at a rate directly proportional to runoff. Dissolution is a relatively low energy process that can occur at any ?ow velocity or in static water; in general it is enhanced by vegetation cover and non‐seasonality of runoff. These contrasting factors in the denudation of silicates versus limestone can produce strikingly uneven rates of surface lowering across a landscape, sometimes akin to the well known ‘tortoise and hare race’, where the slow and steady denudation of limestones may in the long term exceed the sometimes rapid, but often localized and episodic, erosion of silicates. Prolonged exposure of limestone to a humid temperate climate in a tectonically stable environment produces low‐relief corrosion plains in which limestone uplands are anomalous and, in most instances, due to recent unroo?ng from beneath a siliciclastic cover. In a highly seasonal or semi‐arid climate almost the exact inverse may develop, with ‘?ashy’ runoff and sparse vegetation favouring erosion rather than dissolution. Even under a constant humid climate progressive unroo?ng of a thick limestone unit within folded siliciclastics may lead to a topographic inversion over time, with the limestone outcrop always forming a topographic low ?anked by siliciclastic uplands. Valleys will be initiated on anticlinal crests, where the limestone is ?rst unroofed, but progressive lowering of the limestone causes these valleys to migrate to their ?nal position in the synclinal troughs. In humid climates isostatic compensation in response to slow, but continuous, denudation of extensive limestone outcrops may be a signi?cant factor in the development of relief on adjacent, more slowly eroding, silicate outcrops. Copyright © 2004 John Wiley & Sons, Ltd.     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Experimental and theoretical study of stability of dense hydrous magnesium silicates in the deep upper mantle

Fluid-undersaturated experiments were conducted to determine the phase relations in the simplified peridotite system MgO-SiO₂-H₂O (MSH) at 11.0-14.5 GPa and 800-1400 °C. Stability relations of dense hydrous magnesium silicates (DHMSs) under fluid-undersaturated conditions were experimentally examined. From the fluid-absent experimental results, we retrieved thermodynamic data for clinohumite, phase A, phase E, and hydrous wadsleyite, consistent with the published data set for dry mantle minerals. With this new data set, we have calculated phase equilibria in the MSH system including dehydration reactions. The dehydration reactions calculated with lower water activities of 0.68-0.60 match the fluid-present experiments of this study above 11.0 GPa and 1000 °C, indicating that considerable amounts of silicate component were dissolved into the fluid phase. The calculated phase equilibria illustrate the stability of the post-antigorite phase A-bearing assemblages. In the cold subducting slab peridotite, phase A + enstatite assemblage survives into the transition zone, whereas phase A + forsterite + enstatite assemblage forms hydrous wadsleyite at a much shallower depth of about 360-km. The slab is subducted with no dehydration reactions occurring when entering the transition zone. The phase equilibria also show the high temperature stability of phase E. Phase E is stable up to 1200 °C at 13.5 GPa, a plausible condition in the mantle of relatively low temperature, i.e., beneath subduction zones. Phase E is a possible water reservoir in the mantle as well as wadsleyite and ringwoodite.     

Mise au point d'un milieu de culture pour l'étude de l'altération de silicates en présence de Pseudomonas aeruginosa

The influence of microorganisms on mineral alteration is not easy to determine in environmental conditions, because of the difficulty to raise for comparison purposes an identical but abiotic system. Another problem in this context is the choice of reliable tracers to evaluate the alteration rate of materials during in vitro experiments. To face such difficulties, we elaborated a defined medium allowing both the growth of Pseudomonas aeruginosa and a precise measurement of the elements solubilized from the minerals. Thanks to this medium, we were able to quantitatively determine the amounts of major elements solubilized from the materials in the presence of bacterial growth, compared to a sterile system. Moreover, the analysis by ICP-MS of trace elements was possible after a chromatographic treatment, which selectively eliminated 99% of the sodium content of the medium. To cite this article: G. Aouad et al., C. R. Geoscience 337 (2005).