Ion microprobe analysis of oxygen isotope ratios in granulite facies magnetites: diffusive exchange as a guide to cooling history

Ion microprobe analysis of magnetites from the Adirondack Mountains, NY, yields oxygen isotope ratios with spatial resolution of 2–8 m and precision in the range of 1 (1 sigma). These analyses represent 11 orders of magnitude reduction in sample size compared to conventional analyses on this material and they are the first report of routinely reproducible precision in the 1 per mil range for analysis of ¹⁸O at this scale. High precision micro-analyses of this sort will permit wide-ranging new applications in stable isotope geochemistry. The analyzed magnetites form nearly spherical grains in a calcite matrix with diopside and monticellite. Textures are characteristic of granulite facies marbles and show no evidence for retrograde recrystallization of magnetite. Magnetites are near to Fe₃O₄ in composition, and optically and chemically homogeneous. A combination of ion probe plus conventional BrF₅ analysis shows that individual grains are homogeneous with ¹⁸O=8.9±1 SMOW from the core to near the rim of 0.1–1.2 mm diameter grains. Depth profiling into crystal growth faces of magnetites shows that rims are 9 depleted in ¹⁸O. These low ¹⁸O values increase in smooth gradients across the outer 10 m of magnetite rims in contact with calcite. These are the sharpest intracrystalline gradients measured to date in geological materials. This discovery is confirmed by bulk analysis of 150–350 m diameter magnetites which average 1.2 lower in ¹⁸O than coarse magnetites due to low ¹⁸O rims. Conventional analysis of coexisting calcite yields °¹⁸O=18.19, suggesting that bulk ¹⁸O (Cc-Mt)=9.3 and yielding an apparent equilibration temperature of 525° C, over 200° C below the temperature of regional metamorphism. Consideration of experimental diffusion data and grain size distribution for magnetite and calcite suggests two contrasting cooling histories. The data for oxygen in calcite under hydrothermal conditions at high P(H₂O) indicates that diffusion is faster in magnetite and modelling of the low ¹⁸O rims on magnetite would suggest that the Adirondacks experienced slow cooling after Grenville metamorphism, followed by a brief period of rapid cooling, possibly related to uplift. Conversely, the data for calcite at low P(H₂O) show slower oxygen diffusion than in magnetite. Modelling based on these data is consistent with geochronology that shows slow cooling through the blocking temperature of both minerals, suggesting that the low ¹⁸O rims form by exchange with late, low temperature fluids similar to those that infiltrated the rock to serpentinize monticellite and which infiltrated adjacent anorthosite to form late calcite veinlets. In either case, the ion microprobe results indicate that two distinct events are recorded in the post-metamorphic exchange history of these magnetites. Recognition of these events is only possible through microanalysis and has important implications for geothermometry.     

Mono- and dicyclic unsaturated triterpenoid hydrocarbons in sediments from Lake Masoko (Tanzania) widely extend the botryococcene family

A mixture of C₃₃–C₃₇ botryococcenes and partially reduced derivatives was isolated from ca. 32,000 year old sediment from Lake Masoko, a freshwater crater lake in the Rungwe Range area (Tanzania). Botryococcenes and derivatives accounted for 246 μg/g dry sediment and for >92% of the hydrocarbon fraction; 1D and 2D nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry allowed the structure of the dominant botryococcene (43% of hydrocarbon fraction) to be established, after purification using high performance liquid chromatography (HPLC). The compound is a novel tetraunsaturated dicyclic C₃₄ botryococcene and is named C₃₄ masokocene. Overall, the structures of six other novel botryococcenes and four partially reduced derivatives were tentatively assigned. The structures of the new biomarkers, three dicyclic C₃₄–C₃₆ botryococcenes (or masokocenes) and seven monocyclic C₃₄–C₃₇ analogues are discussed along with their biosynthetic relationship. The high abundance of such polyunsaturated compounds preserved in 32,000 year old sediment from the lake indicates an aquatic ecosystem dominated at the time by the green alga Botryococcus braunii, as well very good preservation of the organic matter.     

Depths of Partial Crystallization of H2O-bearing MORB: Phase Equilibria Simulations of Basalts at the MAR near Ascension Island (7 11{degrees}S)

Phase equilibria simulations were performed on naturally quenchedbasaltic glasses to determine crystallization conditions priorto eruption of magmas at the Mid-Atlantic Ridge (MAR) east ofAscension Island (7–11°S). The results indicate thatmid-ocean ridge basalt (MORB) magmas beneath different segmentsof the MAR have crystallized over a wide range of pressures(100–900 MPa). However, each segment seems to have a specificcrystallization history. Nearly isobaric crystallization conditions(100–300 MPa) were obtained for the geochemically enrichedMORB magmas of the central segments, whereas normal (N)-MORBmagmas of the bounding segments are characterized by polybariccrystallization conditions (200–900 MPa). In addition,our results demonstrate close to anhydrous crystallization conditionsof N-MORBs, whereas geochemically enriched MORBs were successfullymodeled in the presence of 0·4–1 wt% H₂O in theparental melts. These estimates are in agreement with direct(Fourier transform IR) measurements of H₂O abundances in basalticglasses and melt inclusions for selected samples. Water contentsdetermined in the parental melts are in the range 0·04–0·09and 0·30–0·55 wt% H₂O for depleted and enrichedMORBs, respectively. Our results are in general agreement (within±200 MPa) with previous approaches used to evaluate pressureestimates in MORB. However, the determination of pre-eruptiveconditions of MORBs, including temperature and water contentin addition to pressure, requires the improvement of magma crystallizationmodels to simulate liquid lines of descent in the presence ofsmall amounts of water. KEY WORDS: MORB; Mid-Atlantic Ridge; depth of crystallization; water abundances; phase equilibria calculations; cotectic crystallization; pressure estimates; polybaric fractionation     

Recruitment patterns of Serpula vermicularis L. (Polychaeta, Serpulidae) in Loch Creran, Scotland

This study aimed to contribute to conservation management of reefs of Serpula vermicularis by increasing understanding of the factors influencing larval settlement. The study was carried out in Loch Creran, which supports the most extensive known development of S. vermicularis reefs in the world. Settlement plates were deployed to examine the influence of season, depth, reef density, substrate type and orientation. Monthly deployment of plates revealed settlement of S. vermicularis to occur predominantly from mid-June to mid-October, peaking in late August to early September. Settlement of Pomatoceros spp. peaked much earlier, in late May to early June. Deployment of plates at different depths revealed a marked reduction in S. vermicularis settlement intensity between 6 and 12 m. As this corresponds with the deeper limit of the peripheral fringe of serpulid reefs in the loch, it is suggested that this limit is imposed by a depth-correlated settlement response, rather than reduction in available substrata. Comparisons of various substrata showed a preference by S. vermicularis larvae for a slate over a scallop substrate and no evidence of enhanced recruitment to occupied or unoccupied tubes of S. vermicularis, suggesting that gregarious attraction is unlikely to be a factor causing reef formation. Settlement onto the upper side of a horizontal scallop substrate was found to be insignificant in comparison with the underside or a vertically orientated scallop. Evidence for the role of light in controlling the depth and substrate-orientation preferences of S. vermicularis larvae is discussed. Based on the results of this study, recommendations are made regarding remediation of areas suffering reef damage.     

Effects of prolonged exposure to 4-tert-octylphenol on toxicity and indices of oestrogenic exposure in the sand goby (Pomatoschistus minutus, Pallas)

Alkylphenolic compounds are present in estuarine and marine environments. They are moderately bioaccumulative, and oestrogenic to fish following three week, in vivo, exposures. The effects of prolonged exposure are, as yet, unclear. Sand goby (Pomatoschistus minutus) were exposed to measured concentrations of 4-tert-octylphenol (OP) in a 28-day, dose-ranging study, and a six month temporal response study. Following 28-days exposure to measured 31+/-6 or 101+/-47 microg l(-1) OP (mean+/-SD), immature male sand goby showed elevated vitellogenin (VTG) mRNA expression. Plasma alkali-labile phosphate concentrations were elevated in both sexes and were higher in females than males. Although measured OP concentrations were variable, they were significantly different for each treatment and a range of concentration-dependent effects were observed. The LC(50) for chronic OP exposure (8 weeks) was 29+/-6 microg l(-1), and both sexes demonstrated concentration and duration dependent increases in VTG mRNA expression. Exposure to 28+/-20 microg l(-1) OP (median+/-95% CI) for 6 months inhibited development of male nuptial colouration and sperm duct glands. These findings are discussed in relation to environmental concentrations of alkylphenols and ecological concerns.     

Jason-1: Assessment of the System Performances

On 7 December 2001, Jason-1 was successfully launched by a Boeing Delta II rocket from the Vandenberg Air Force Base, California. The Jason-1 satellite will maintain the high accuracy altimeter service provided since 1992 by TOPEX/Poseidon (T/P), ensuring the continuity in observing and monitoring the Ocean Dynamics (intraseasonal to interannual changes, mean sea level, tides, etc.). Despite one-fourth the mass and power, the Jason-1 system has been designed to have basically the same performance as T/P, measuring sea surface topography at a centimetric level. This new CNES/NASA mission also provides near real-time data for sea state and ocean forecast. The first two months of the Jason-1 mission have been dedicated to the assessment of the overall system. The goals of this assessment phase were:

1. To assess the behavior of the spacecraft at the platform and payload levels (Jason-1 being the first program to call on the PROTEUS versatile multimission platform for Low and Medium Earth Orbit Missions developed in partnership between Alcatel Space and CNES);

2. To verify that platform performance requirements are met with respect to Jason-1 requirements;

3. To verify that payload instruments performance requirements evaluated at instrument level are met;

4. To assess the performance of the Jason-1 Ground System.

This article will display the main outputs of the assessment of the system. It will demonstrate that all the elements of the onboard and ground systems are within the specifications. Provision of data to the Jason-1 Science Working Team started at the end of March 2002. This is the goal of a six-month phase after closure of the initial assessment phase to derive the error budget of the system in terms of altimetry user products.     

Investigation and sensitivity analysis of a mechanistic phytoplankton model implemented in a new modular numerical tool (Eco3M) dedicated to biogeochemical modelling

A new class of phytoplankton models with a mechanistic basis has been presented in a companion paper (Baklouti, M., Diaz, F., Pinazo, C., Faure, V., Queguiner, B., 2006. Investigation of mechanistic formulations depicting phytoplankton dynamics for models of marine pelagic ecosystems. Progress in Oceanography). It is the default class of models implemented in our new numerical tool Eco3M, which is dedicated to Ecological, Mechanistic and Modular Modelling. A brief overview of its main features is given in Section 2 of the present paper. In the next sections, a particular phytoplankton model among the aforementioned class has been tested with special emphasis on the mechanistic photosynthesis component relating the photosynthetic rate to the proportion of open photosystems II. The present study encompasses several essential steps that are inherent to any modelling, including model reduction, model sensitivity analysis and comparison of model outputs with experiments. The global sensitivity analysis of the plankton model for one-at-a-time parameter perturbations revealed a restricted set of parameters having major influence on the model outputs. Sensitivity tests involving simultaneous parameter perturbations within the range actually encountered in the literature provided a confidence interval for the outputs. Chemostat experiments performed on nitrate-limited diatoms grown under low (LL) and high-light (HL) conditions have been used for comparison with model outputs. The good fit between measured data and model outputs using the same parameter values in both the LL and HL cases demonstrates the ability of our model to represent the main features of phytoplankton dynamics including photoacclimation. Finally, Eco3M is ultimately intended to include explicit bacterial and zooplankton compartments, as well as to be coupled with ocean circulation models, but the intrinsic behavior of the phytoplankton model has been investigated first, independently of physical forcing.     

Experimental survey of the hydrodynamic performance of a small spar buoy

The objective in this experimental work is to evaluate the capability of several cylindrical buoys to follow and measure waves. Eleven configurations have been studied, eight among which were furnished with disks of different diameters at the waterline. The experiments took place in the test basin at ISITV. On the one hand, we have obtained a set of transfer coefficients for each frequency and each configuration in regular waves. On the other hand, we have determined the corresponding transfer functions, then we have used the latter to measure irregular waves. The time signals as measured by the buoys with and without corrections have been compared with wave gage measurements and subjected to a wave-by-wave analysis. The results allow the conclusion that the buoy with a medium size disk constitutes the best compromise. In fact, it permits the buoy to follow the free surface while minimizing parasitic motions.