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.     

The bituminous mixtures of Tall-e Abu Chizan: A Vth millennium BC settlement in southwestern Iran

Various bituminous artifacts were excavated from the Tall-e Abu Chizan, a late prehistoric (Middle Susiana to Middle Uruk) settlement on the middle of the Curvy plain, between the Karun River and the Ram Hormoz Plain. All samples dated from the Vth millennium BC and cover three periods: 5000–4700 BC (Late Middle Susiana), 4700–4200 BC (Late Susiana 1) and 4200–3900 BC (Late Susiana 2). The bitumens were studied using the techniques of petroleum geochemistry and were compared both to the unaltered crude oils produced from the main oil fields in the area and to the famous Mamatain oil seeps. All samples are very rich in bitumen (average 46 wt%) which has been biodegraded and oxidized. Despite these alteration phenomena, δ¹³C of asphaltenes occur within a narrow range of less than 1‰ PDB. Biodegradation affected the steranes, terpanes, dibenzothiophenes and mono- and triaromatic steroids. Molecular characteristics of terpanes, especially the occurrence of 18α (H)-oleanane, suggest that the bitumen from Tall-e Abu Chizan is a mixture generated from Cretaceous Kazdhumi and Eocene Pabdeh petroleum source rocks. In that respect, bitumens from Tall-e Abu Chizan belong to the same oil family as oil from the Naft Safid field, which is in the vicinity of the archaeological site. In fact, the bitumen at Tall-e Abu Chizan likely originated from oil seepages at Naft Safid. These oil seeps have not yet been sampled or analysed.     

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.     

Accumulation of organic and inorganic carbon in Pliocene–Pleistocene sediments along the SW African margin

The Ocean Drilling Program Leg 175 recovered a unique series of stratigraphically continuous sedimentary sections along the SW African margin, an area which is presently affected by active coastal upwelling. The accumulation rates of organic and inorganic carbon are a major component of this record. Four Leg 175 sites (1082, 1084, 1085, 1087) are chosen as part of a latitudinal transect from the present northern to southern boundaries of the Benguela Current upwelling system, to decipher the Pliocene–Pleistocene history of biogenic production and its relationship with global and local changes in oceanic circulation and climate. The pattern of CaCO₃ and C_org mass accumulation rates (MARs) over 0.25-Myr intervals indicates that the evolution of carbon burial is highly variable between the northern and the southern Benguela regions, as well as between sites that have similar hydrological conditions. This, as well as the presence over most locations of high-amplitude, rapid changes of carbon burial, reflect the partitioning of biogenic production and patterns of sedimentation into local compartments over the Benguela margin. The combined mapping of CaCO₃ and C_org MARs at the study locations suggests four distinct evolutionary periods, which are essentially linked with major steps in global climate change: the early Pliocene, the mid-Pliocene warm event, a late Pliocene intensification of northern hemisphere glaciation and the Pleistocene. The early Pliocene spatially heterogeneous patterns of carbon burial are thought to reflect the occurrence of mass-gravitational movements over the Benguela slope which resulted in disruption of the recorded biogenic production. This was followed (3.5–3 Ma) by an episode of peak carbonate accumulation over the whole margin and, subsequently, by the onset of Benguela provincialism into a northern and a southern sedimentary regime near 2 Ma. This mid and late Pliocene evolution is interpreted as a direct response to changes in the ventilation of bottom and intermediate waters, as well as to dynamics of the subtropical gyral circulation and associated wind stress.