A thermodynamic investigation of barium and calcium sulfate stability in sediments at an oceanic ridge axis (Juan de Fuca, ODP legs 139 and 169)

We have used a new thermodynamic model of barium and calcium sulfate solubilities in multicomponent electrolyte solutions (Monnin, 1999) to investigate the stabilities of barite and anhydrite in seawater or in marine sediment porewaters at high temperature and pressure. As a further test supplementing those previously carried out during model development, we have calculated the temperature at which standard seawater becomes saturated with respect to anhydrite. The model predicts that, upon heating at 500 bars, standard seawater becomes saturated with respect to anhydrite at 147 ± 5°C, which compares well with the literature value of 150°C (Bishoff and Seyfried, 1978). At 20 bars the calculated saturation temperature is 117 ± 3°C. This points to a non negligible pressure effect even at moderate pressures.We have calculated the barite and anhydrite saturation indices for the in situ temperatures and pressures, from the composition of porewaters collected at ODP Sites 855, 856, 857, 858, 1035 and 1036 during ODP Legs 139 and 169 (Juan de Fuca and Gorda ridges, NE Pacific). Calculated saturation indices for porewater samples collected at depths corresponding to temperatures between 70° and 110-120°C at an in situ pressure of about 260 bars yield equilibrium values for anhydrite and barite. Saturation indices of samples collected at depths where the temperature exceeds 110-120°C, however, yield values indicating supersaturation with respect to anhydrite and undersaturation with respect to barite. This result is consistent with the redissolution of anhydrite during cooling, leading to the well documented sampling artifact affecting porewater compositions in high temperature marine sediments: anhydrite dissolution increases the porewater sulfate content, which in turn induces a loss of barium from solution through barite precipitation (the common ion effect). We postulate that this redissolution occurs in sediment samples for which the in situ temperature exceeds 110-120°C: below this limit anhydrite remains at equilibrium or does not have time to significantly dissolve before porewaters are sampled.     

Determination of the bulk temperature from NOAA/AVHRR satellite data in a midlatitude lake

The spatial and temporal variability of the bulk temperature gives important insights into biological and hydrodynamic processes. However, standard algorithms for satellite data only provide information of the surface temperature. The comparison of current and new split-window coefficients applied on NOAA-14/AVHRR brightness temperatures of Lake Constance showed that a regional adaption was most promising. To derive the bulk temperature information, a priori progression from a weather station was included into the AVHRR analysis. Among the weather is data, the mean temperature of the three preceding days and the day of the year were the most relevant additional information. By a multiple regression approach the bulk temperature in the upper 4 m of Lake Constance could be determined with an accuracy of ±1.20 °C. The training of a neural network improved the determination of the bulk temperature to ±1.04 °C.An extended field campaign demonstrated that the algorithm is also applicable to other sensors with the same spectral band settings (in this case NOAA-16/AVHRR) with an acceptable error and that it is equally accurate over the entire lake.     

3D Geographic Reconstruction and Visualization Techniques Applied to Land Resource Management

Optimized land resource management depends on reliable and detailed information describing the spatial distribution of soils, geology, topography, and land use. Soil–landscapes are three–dimensional (3D) systems commonly represented using 2D maps utilizing geographic information systems. Addressing 3D soil–landscape reality is crucial for land resource management in terms of crop growth and transport processes (e.g. nitrate leaching) that are driving soil and water quality. Our objective was to investigate the usefulness of 3D geographic information technology (GIT) applied to land resource management. Our approach is based on 2D and 3D ordinary kriging interpolating surface and subsurface attributes to reconstruct soil–landscapes. We used Virtual Reality Modeling Language, which is a web–based 3D graphics language, to visualize objects (e.g. voxels, polyhedrons) representing soil and landscape attributes. We produced a 3D block model showing the spatial distribution of bulk densities and relief for a site in southern Wisconsin and a 3D stratigraphic model showing the spatial distribution of soil horizons and relief for a site in northern Florida. Emerging GIT was used to develop 3D soil–landscape models describing continuous changes of soil and landscape attributes. Combining multimedia elements (e.g. WWW, 3D visualization, and interactivity) can produce insight that would not arise from use of the elements alone. Three–dimensional scientific visualization is a powerful tool to help us see what is invisible from above the ground.     

Cooperite and braggite from the Bushveld Complex: implications for the miscibility gap and identification

Analyses of the Pt-Pd-Ni sulphides cooperite, braggite, and vysotskite reported from worldwide occurrences seem to imply a continuum of compositions between vysotskite and cooperite, with no obvious miscibility gap. This is contrary to the experimentally confirmed miscibility gap between cooperite and braggite, and the established compositional gap between co-existing cooperite and braggite from the Merensky Reef. Although the only unambiguous way of distinguishing between cooperite and braggite is to obtain structural information through X-ray diffraction or equivalent techniques, most identification of Pt-Pd-Ni sulphides is based on microanalytical techniques due to the small grain size of most platinum-group minerals. Ni contents also have to be considered because a classification based on the Pt/Pd ratio alone can be very misleading. Naming of Pt-Pd-Ni sulphide compositions with high Pt contents based on qualitative or semi-quantitative analyses should be avoided. Natural Pt-Pd-Ni sulphides which project into the compositional gap (established by experimental work) cannot be named without supporting structural information. Compositions of grains, which plot inside the gap, are considered to be metastable and to result from the loss of Pd through interaction with hydrothermal fluids.     

Genetic sequence stratigraphy of cool water slope carbonates (Pleistocene Eucla Shelf, southern Australia)

The south Australian Eucla Shelf belongs to the world's largest cool-water carbonate sedimentary system. During the Pleistocene, it exported large amounts of sediment to the shelf edge and upper slope resulting in an expanded sedimentary wedge. Wedge-internal clinoforming seismic reflectors suggest a stacking of the deposits into genetic sequences. High-resolution stable oxygen and carbon isotope, point counting, grain size, and carbonate mineralogical XRD analyses were carried out to characterize these genetic sequences along a dip-parallel transect of three ODP Leg 182 drill holes located between the shelf edge and upper slope. Oxygen and carbon isotope fluctuations show that the genetic sequences formed as a response to sea level fluctuations. Within the genetic sequences, facies differentiation and sediment volume partitioning occur along the transect. Lowstand deposits are fine grained and contain more sponge spicules and micrite. Highstand deposits are coarse grained with tunicate spicules, brown bioclasts, as well as bryozoan and corallinacean debris. Boundaries separating highstand and lowstand deposits are triggered by sea level fall, and are expressed as abrupt grain size changes or as turning points in grain-size trends. Analyzed components vary in abundance along the transect. Genetic sequences show dip-parallel variations in thickness combined with changing relative proportions of lowstand versus highstand deposits.     

Volcanisme de l'ı̂le aux Pingouins,archipel Crozet,témoin de l'hétérogénéité du manteau fertile au sud de l'océan IndienPenguins Island,Crozet archipelago,volcanic evidence for a heterogeneous mantle in the southern Indian Ocean

Despite its small area (5.6 km²), the Penguins Island brings magmatic information concerning mantle geochemical heterogeneities in southwestern Indian Ocean. The volcanism that built the island was firstly associated with marine deposits, and secondly with aerial, giving then abundant volcanic breccias and lava flows. The rocks are weakly differentiated and result of magmatic fractionation from picritic to tephritic types. KAr ages are near 1.1 Ma. The magmatic source may be related to a HIMU reservoir or to EMI ± EMII ones, depending on the geochemical evidences that are taken into account. However, comparisons with the Marion Island, on the same oceanic plateau and far to the west, as well as with Kerguelen Islands, far to the east, suggest a very heterogeneous mantle source. To cite this article: A. Giret et al., C. R. Geoscience 334 (2002) 481–488.     

Cross-section through the frontal Japan Trench subduction zone: Geochemical evidence for fluid flow and fluid–rock interaction from DSDP and ODP pore waters and sediments

Abstract Fluids and sediments from Deep Sea Drilling Project/Ocean Drilling Program Legs (56, 57, 87 and 186) along a transect extending from the subducting plate, across the midslope and upper slope of the Japan Trench forearc were analyzed for B and B isotopes in order to assess their composition and fluid–sediment interaction. At the reference Site 436 on the subducting plate, changes in B contents and B isotopes are controlled by the lithology and diagenesis only. The midslope Sites 440 and 584 showed stronger variations in the B geochemistry, which can be related to diagenesis and tectonic dewatering along faults. The strongest changes in the B geochemistry were observed on the upper slope Sites 1150 and 1151, where profound down‐hole freshening (chlorinities as low as ～310 mmol) coincides with a B enrichment (up to 9.3 × seawater concentration). The B isotope pore fluid profile of Site 1150 displayed a bimodal variation with depth, first increasing to values more positive than seawater, then shifting to lower signatures typical for deep‐seated fluids, whereas Site 1151 showed a constant B decrease with depth. Sites 1150 and 1151 sediments showed B increases with depth to values as high as ～164 p.p.m. and isotopic compositions ranging from ～+4 to ?9‰. A linear decrease in B_solid/B_fluid ratio, suggests that B geochemistry of the upper slope sites is controlled by fluid–rock interaction and deep‐seated fluid flow, whereas constant B_solid/B_fluid ratios were observed at the reference site on the incoming plate. This fluid overprint is probably caused by normal faults in the sediment cover which might be interconnected to deep thrusts in the underlying Cretaceous accreted wedge. This suggests that the erosive Japan Trench margin is characterized by back‐flux of deep‐seated, B‐enriched fluids into the ocean, which is facilitated by extensional normal faulting as a result of tectonic erosion and subsidence.     

Bank-derived carbonate sediment transport and dissolution in the Hawaiian Archipelago

This investigation used two approaches to examine the flux of bank-derived carbonate particles and determine the potential influence of benthic carbonate particle dissolution on the carbon chemistry of the waters around the Hawaiian Archipelago. First, the particle flux near several representative carbonate banks in the Hawaiian Archipelago was measured and compared with the flux at a distal site (ALOHA) approximately 100 km north of Oahu, Hawaii. The results of four sediment trap deployments on three carbonate banks in the Hawaiian Archipelago demonstrate that the flux of bank-derived carbonate particles are consistently one to two orders of magnitude higher than the fluxes at the distal station. Furthermore, the mineralogy of the carbonate flux near the banks, which includes very soluble bank-derived aragonite and magnesian calcite particles, is distinctly different from that of the distal fluxes. Second, the chemistry of the waters at each bank station along the archipelago was characterized and compared with the chemistry of the distal waters to determine if differences in the particle flux were reflected in the carbon chemistry. Higher alkalinity and carbonate ion concentrations were observed around all of the banks studied. The saturation state of these waters suggests that the dissolution of some magnesian calcite and aragonite phases could explain the higher alkalinity values. Calculations suggest that the dissolution of benthically-derived aragonite and magnesian calcite may be an important component of the North Pacific alkalinity budget and a potential sink for anthropogenic CO₂.     

热处理低温钠长石的EPR和X射线衍射研究

利用电子顺磁共振(EPR)和X射线衍射方法研究了天然和热处理钠长石单晶。热处理在500—850℃水热条件下完成。在外加磁场B平行于晶体c~*轴的方向上,测量了加热前后Fe~(3+)的EPR谱和线宽△B随温度和加热时间的变化。结果显示,线宽随Al、Si无序的增大而增加。由此得出结论,在低温钠长石中,Fe~(3+)位于Al~(3+)占据的T_1(o)位置,在被研究的温度范围内,Fe~(3+)未参与四面体位置T间Al、Si交换。谱线的加宽主要是由在Fe~(3+)邻近位置上Al、Si无序的增大引起的,同时与观测到的晶胞参数变化有关。在Al、Si无序更强的晶体中,Fe~(3+)谱变得极宽。     

Electron paramagnetic resonance and ENDOR studies of Cr3+ - Al3+ pairs in forsterite

The electron paramagnetic resonance (EPR) spectrum of Cr³⁺ in synthetic crystals of forsterite consists primarily of lines of Cr³⁺ “isolated” at the M1 and M2 positions in a “perfect” crystal environment without local charge compensation. In addition it shows two nonequivalent superhyperfine-split sextets with different intensities which are due to strong interaction of the Cr³⁺ electron spin S (S=3/2) with an adjacent nuclear spin I(I=5/2). Electron nuclear double resonance (ENDOR) experiments revealed that the sextets result from Cr³⁺ (M1) - Al³⁺ and Cr³⁺ (M2) - Al³⁺ pairs, Al being located at adjacent tetrahedral Si sites. The g, D, A, and A′ tensor components of the Cr³⁺ - Al³⁺ pairs have been determined at room temperature. The values of the pairs are distinct although they are not very different from the corresponding data of “isolated” Cr³⁺. From the intensities of the EPR spectra the relative concentration of the Cr³⁺ - Al³⁺ pairs with respect to “isolated” Cr³⁺ has been estimated.