Analytical Procedures for the Measurement of Boron Isotope Compositions by Ion Microprobe in Meteorites and Mantle Rocks

An analytical procedure has been developed to measure in situ the ¹¹ B/¹⁰ B ratio in terrestrial basaltic rocks and meteoritic chondrules having B concentration of less than 1 μg g^?1 using a small radius ims3f ion microprobe. The central difficulties for these measurements are (i) the removal of the trace amount of B contamination introduced in the sample during polishing, (ii) the precise calibration of instrumental mass fractionation of B isotopes and (iii) the low count rates of ¹⁰ B and ¹¹ B. Contamination experiments conducted with isotopically labelled B enriched in ¹⁰ B showed that ultrasonic cleaning in bi-distilled water (< 1 ng g^?1 B) and pre-sputtering of the analysed area decrease B contamination to the level of 0.01 μg g^?1. Analyses of isotope standards spanning a range of ¹¹ B/¹⁰ B between 3.93 and 4.20 showed that instrumental mass fractionation was constant within? during one session of analyses. Repeated analyses of a standard glass showed a reproducibility of instrumental mass fractionation between February 1991 and October 1996 of 1.3. Taking into account all sources of error, boron isotope measurements are accurate to within 5 for meteoritic samples having B contents in the range 0.1 to 1 μg g^?1. A slightly better accuracy of 1.5 can be achieved for basaltic glasses which can be sputtered with very intense primary beams.     

Linking a linear pockmark train with a buried Palaeozoic structure: a case study from the St. Lawrence Estuary

The 15-km-long Matane pockmark train belongs to a series of NNE-striking alignments of pockmarks mapped on the seafloor of the St. Lawrence Estuary. It includes 109 pockmarks that show a complete transition from well-defined, relatively deep (up to 8.6 m), crater-like depressions to subtle, partly buried morphological features, suggesting that pockmarks have formed at different periods along the whole alignment and that the location of fluid release has changed through time. On seismic profiles, pockmarks are characterized by vertical seismic chimneys that root in the (fractured?) hinge zone of an open anticline within the autochthonous Palaeozoic rocks of the St. Lawrence Platform. In absence of a geochemical characterization of expelled gas, the relationship between the Matane pockmark train and the anticline in a domain characterized by mature source rocks is the strongest evidence for the genetic link between pockmarks and the release of gas from an active hydrocarbon system or a reservoir located in the Palaeozoic succession.

A coarse-scale compositional model

In subsurface flow modeling, compositional simulation is often required to model complex recovery processes, such as gas/CO ₂ injection. However, compositional simulation on fine-scale geological models is still computationally expensive and even prohibitive. Most existing upscaling techniques focus on black-oil models. In this paper, we present a general framework to upscale two-phase multicomponent flow in compositional simulation. Unlike previous studies, our approach explicitly considers the upscaling of flow and thermodynamics. In the flow part, we introduce a new set of upscaled flow functions that account for the effects of compressibility. This is often ignored in the upscaling of black-oil models. In the upscaling of thermodynamics, we show that the oil and gas phases within a coarse block are not at chemical equilibrium. This non-equilibrium behavior is modeled by upscaled thermodynamic functions, which measure the difference between component fugacities among the oil and gas phases. We apply the approach to various gas injection problems with different compositional features, permeability heterogeneity, and coarsening ratios. It is shown that the proposed method accurately reproduces the averaged fine-scale solutions, such as component overall compositions, gas saturation, and density solutions in the compositional flow.     

Pulsed export of carbon in the north-western Mediterranean Sea

The short term (hourly scale) variability of heterotrophic prokaryote (HP) vertical distribution and respiratory activity, was investigated in the north-western (NW) Mediterranean Sea. HP vertical distribution was determined on board by flow cytometry analysis of seawater samples collected by series of CTD casts. Cell counts and viability were determined for all samples. HP respiratory rates were determined later in the laboratory from filtered seawater samples (23 dm³) from 300–1 150-m depth. The average cell viability was 94.8%±2.2% (n=240). There was no accumulation of dead cells, due to quick decay of damaged cells. In the epipelagic layer, three HP groups were distinguished, two (HNA1, HNA2) whose cells exhibited a high nucleic acid content and one (LNA) with low nucleic acid content cells. HNA2 was most populated at 50 m but not detected at 90 m and below, presumably aerobic anoxygenic photoheterotrophic bacteria (AAPs). The variability in HP abundance was mainly confined in the upper 80 m. A few secondary peaks of HP abundance were observed (80–150 m) in connection with abundance troughs in the surface layer. HP cells were continuously present in a wide layer around 500 m (mean 191×10³ cells/cm³). Below this layer, HP abundance randomly exhibited peaks, coupled to respiratory rate peaks. The HP abundance and variability in the water column was suppressed during a strong wind event. The observed sporadic variability was tentatively interpreted through a pulsed carbon-export mechanism induced by the microorganism production of dissolved polysaccharides, followed by flocculation and rapid sinking. This mechanism would thus contribute to (i) preventing organic matter accumulation in the epipelagic layer, (ii) seeding the water column with live HP cells, and (iii) supplying the aphotic water column with fresh and labile organic matter. This important vertical flux mechanism needs further observations and modelling.

     

Stratigraphy, chemistry, and eruptive dynamics of the 12.4 ka plinian eruption of Apoyeque volcano, Managua, Nicaragua

Apoyeque volcano, located 9 km northwest of Managua city, erupted explosively at 12.4 ka. The Plinian eruption deposited a widespread pumice fall deposit known as the Upper Apoyeque Tephra (UAq). The UAq is massive, reversely graded, and consists of white juvenile pumice (~78 vol.%), a variety of cognate lithics and accidental altered lithics. The whole-rock pumice composition is rhyodacitic (SiO₂?=?66.9–68.5 wt.%) with a mineral paragenesis of plagioclase, orthopyroxene, clinopyroxene, amphibole, titanomagnetite, and ilmenite in a rhyolitic glass groundmass (SiO₂?=?74.4?±?0.6 wt.%). The deposit’s dispersal axis is to the south, with the deposit covering a minimum area of 877 km² within the 50 cm isopach and has a total volume of 3 km³ (dense rock equivalent, 1.15 km³). The eruption column reached a maximum height of ca.28 km. The eruption ejected a total mass of 3?×?10¹² kg at an average rate of 2?×?10⁸ kg/s, and based on available models, we infer duration of almost 4 h. Petrographic and geochemical characteristics suggest that the eruption was triggered by magma mixing.     

GSD‐1G and MPI‐DING Reference Glasses for In Situ and Bulk Isotopic Determination

This paper contains the results of an extensive isotopic study of United States Geological Survey GSD‐1G and MPI‐DING reference glasses. Thirteen different laboratories were involved using high‐precision bulk (TIMS, MC‐ICP‐MS) and microanalytical (LA‐MC‐ICP‐MS, LA‐ICP‐MS) techniques. Detailed studies were performed to demonstrate the large‐scale and small‐scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD‐1G and the MPI‐DING glasses are suitable reference materials for microanalytical and bulk analytical purposes.     

Changes in the northern Gulf of St. Lawrence ecosystem estimated by inverse modelling: Evidence of a fishery-induced regime shift?

Mass-balance models have been constructed using inverse methodology for the northern Gulf of St. Lawrence for the mid-1980s, the mid-1990s, and the early 2000s to describe ecosystem structure, trophic group interactions, and the effects of fishing and predation on the ecosystem for each time period. Our analyses indicate that the ecosystem structure shifted dramatically from one previously dominated by demersal (cod, redfish) and small-bodied forage (e.g., capelin, mackerel, herring, shrimp) species to one now dominated by small-bodied forage species. Overfishing removed a functional group in the late 1980s, large piscivorous fish (primarily cod and redfish), which has not recovered 14 years after the cessation of heavy fishing. This has left only marine mammals as top predators during the mid-1990s, and marine mammals and small Greenland halibut during the early 2000s. Predation by marine mammals on fish increased from the mid-1980s to the early 2000s while predation by large fish on fish decreased. Capelin and shrimp, the main prey in each period, showed an increase in biomass over the three periods. A switch in the main predators of capelin from cod to marine mammals occurred, while Greenland halibut progressively replaced cod as shrimp predators. Overfishing influenced community structure directly through preferential removal of larger-bodied fishes and indirectly through predation release because larger-bodied fishes exerted top-down control upon other community species or competed with other species for the same prey. Our modelling estimates showed that a change in predation structure or flows at the top of the trophic system led to changes in predation at all lower trophic levels in the northern Gulf of St. Lawrence. These changes represent a case of fishery-induced regime shift.     

Time-resolved,defect-hosted,trace element mobility in deformed Witwatersrand pyrite

The Pb isotopic composition of rocks is widely used to constrain the sources and mobility of melts and hydrothermal fluids in the Earth's crust. In many cases, the Pb isotopic composition appears to represent mixing of multiple Pb reservoirs. However, the nature, scale and mechanisms responsible for isotopic mixing are not well known. Additionally, the trace element composition of sulphide minerals are routinely used in ore deposit research, mineral exploration and environmental studies, though little is known about element mobility in sulphides during metamorphism and deformation. To investigate the mechanisms of trace element mobility in a deformed Witwatersrand pyrite(FeS_2), we have combined electron backscatter diffraction(EBSD) and atom probe microscopy(APM). The results indicate that the pyrite microstructural features record widely different Pb isotopic compositions, covering the entire range of previously published sulphide Pb compositions from the Witwatersrand basin. We show that entangled dislocations record enhanced Pb, Sb, Ni, Tl and Cu composition likely due to entrapment and short-circuit diffusion in dislocation cores. These dislocations preserve the Pb isotopic composition of the pyrite at the time of growth(~3 Ga) and show that dislocation intersections, likely to be common in deforming minerals, limit trace element mobility. In contrast, Pb, As, Ni, Co, Sb and Bi decorate a highangle grain boundary which formed soon after crystallisation by sub-grain rotation recrystallization.Pb isotopic composition within this boundary indicates the addition of externally-derived Pb and trace elements during greenschist metamorphism at ~2 Ga. Our results show that discrete Pb reservoirs are nanometric in scale, and illustrate that grain boundaries may remain open systems for trace element mobility over 1 billion years after their formation.