Kinetic oxygen isotope effects during dissimilatory sulfate reduction: A combined theoretical and experimental approach

Kinetic isotope effects related to the breaking of chemical bonds drive sulfur isotope fractionation during dissimilatory sulfate reduction (DSR), whereas oxygen isotope fractionation during DSR is dominated by exchange between intercellular sulfur intermediates and water. We use a simplified biochemical model for DSR to explore how a kinetic oxygen isotope effect may be expressed. We then explore these relationships in light of evolving sulfur and oxygen isotope compositions (δ³⁴S_SO4 and δ¹⁸O_SO4) during batch culture growth of twelve strains of sulfate-reducing bacteria. Cultured under conditions to optimize growth and with identical δ¹⁸O_H2O and initial δ¹⁸O_SO4, all strains show ³⁴S enrichment, whereas only six strains show significant ¹⁸O enrichment. The remaining six show no (or minimal) change in δ¹⁸O_SO4 over the growth of the bacteria. We use these experimental and theoretical results to address three questions: (i) which sulfur intermediates exchange oxygen isotopes with water, (ii) what is the kinetic oxygen isotope effect related to the reduction of adenosine phosphosulfate (APS) to sulfite (SO₃²⁻), (iii) does a kinetic oxygen isotope effect impact the apparent oxygen isotope equilibrium values? We conclude that oxygen isotope exchange between water and a sulfur intermediate likely occurs downstream of APS and that our data constrain the kinetic oxygen isotope fractionation for the reduction of APS to sulfite to be smaller than 4‰. This small oxygen isotope effect impacts the apparent oxygen isotope equilibrium as controlled by the extent to which APS reduction is rate-limiting.     

Géomorphologie de Tromelin,océan Indien

Tromelin is a small coral reef island (1 km²) located in the Indian Ocean, approximately 440 km east of Madagascar and 580 km north of La Réunion. Despite the presence of a permanent Météo France weather station on Tromelin since the 1950 s, a detailed geomorhological study of the island has never been undertaken. In this paper, we describe results from the 2008 field season, which enabled us to map and describe seven geomorphological zones on the atoll. (1) Tromelin's bathymetry is characterised by a pronounced submarine slope, which attains depths of 1000 m at only 2.5 km from the island's coastline. This geomorphology is typical of volcanic hotspots. (2) A coral platform borders the emerged crown of the island. This platform is exposed at low tide and has been fashioned in an ancient Pleistocene substratum. The substratum has been eroded by abrasive marine action to its present shape since the stabilisation of relative sea level around 6000 years ago. Erosion of the reef yields most of the biogenic sediment supply to the island. (3) The upper foreshore is characterised by outcrops of beachrock. These formations show a stratfication in slabs and dip gently towards the sea in the same manner as the contemporary clastic sediments. (4) Tromelin's beaches are divided into three sub-units, which reflect the different energy dynamics around the island, in addition to the transfer of sediment from the windward to the leeward side: (i) the southern storm beaches are characterised by coral blocks reworked during episodic high-energy events; they form boulder ramparts. Four perched rampart ridges have been recorded at ∼1 m, ∼3 m, ∼4.5 m and ∼7 m above mean sea level; (ii) transitional beaches are observed between the south and the north, constituting storm blocks and coarse sands and gravels; and (iii) sandy beaches are noted on the northern leeward side, comprising rounded gravels and coarse sands. The northern tip of the island is characterised by a sand spit (∼125 × ∼225 m), whose geometry varies based on the seasonal and meteo-marine contexts. (5) On Tromelin, a number of dune formations are observed. These are best developed in the north of the island due to the south-north translation of clastic sediments by aeolian wind action, and the trapping of sands by the well-developed vegetation. The height of the dunes varies between 10 cm (the southern micro-dunes) to 250 cm in the Northeast of Tromelin. (6) Exceptional waves have deposited storm tracts up to 250 m from the foreshore zone, comprising coarse gravels and coral blocks. The storm tract deposits are most prevalent on the windward side of the island, due not only to the high-energy dynamics, but also to the absence of vegetation cover in this area. (7) The southern depression covers an area of ∼40,000 m². At its lowest point it is only 1.2 m above sea level.     

Element signatures of subduction-zone fluids. An experimental study of the element partitioning (Dfluid/rock) of natural partly altered igneous rocks from the ODP drilling site 1,256

The trace element signatures of fluids were investigated by leaching experiments on natural samples of partly altered mafic igneous rocks recovered from the drilling site 1,256 of ODP Leg 206 on the Cocos plate (Central America). Experiments with ultrapure water were performed at 400 °C/0.4 GPa and 500 °C/0.7 GPa. Both fluids and residual solids were examined to obtain the partition coefficients (D^fluid/rock) of various trace elements. Element partition coefficients (D^fluid/rock) obtained at 500 °C/0.7 GPa are significantly lower compared to results obtained at 400 °C/0.4 GPa, which is in contrast to observations at higher pressures (2.2–6 GPa) and temperatures between 700 and 1,400 °C (Kessel et al. in Earth Planet Sci Lett 237: 873–892, 2005a; Spandler et al. in Chem Geol 239: 228–249, 2007). This finding may indicate a considerable pressure effect on the leaching processes and strongly divergent fluid–rock interactions in the upper part of a subduction zone at 0.4–0.7 GPa compared to deeper subduction areas with higher pressures. Furthermore, this may be interpreted as one of the earliest fractionation processes during the subduction of crustal material.     

Exploring the effects of data quality,data worth,and redundancy of CO2 gas pressure and saturation data on reservoir characterization through PEST inversion

This study examined the impacts of reservoir properties on carbon dioxide (CO₂) migration after subsurface injection and evaluated the possibility of characterizing reservoir properties using CO₂ monitoring data such as spatial–temporal distributions of gas pressure, which can be reasonably monitored in practice. The injection reservoir was assumed to be located 1,400–1,500 m below the ground surface such that CO₂ remained in the supercritical state. The reservoir was assumed to contain layers with alternating conductive and resistive properties, which is analogous to actual geological formations such as the Mount Simon Sandstone unit. The CO₂ injection simulation used a cylindrical grid setting in which the injection well was situated at the center of the domain, which extended out 8,000 m from the injection well. The CO₂ migration was simulated using the latest version of the simulator, subsurface transport over multiple phases (the water–salt–CO₂–energy module), developed by Pacific Northwest National Laboratory. A nonlinear parameter estimation and optimization modeling software package, Parameter ESTimation (PEST), is adopted for automated reservoir parameter estimation. The effects of data quality, data worth, and data redundancy were explored regarding the detectability of reservoir parameters using gas pressure monitoring data, by comparing PEST inversion results using data with different levels of noises, various numbers of monitoring wells and locations, and different data collection spacing and temporal sampling intervals. This study yielded insight into the use of CO₂ monitoring data for reservoir characterization and how to design the monitoring system to optimize data worth and reduce data redundancy. The feasibility of using CO₂ saturation data for improving reservoir characterization was also discussed.     

Settling and compaction of chromite cumulates employing a centrifuging piston cylinder and application to layered mafic intrusions

The time scales and mechanics of gravitationally driven crystal settling and compaction is investigated through high temperature (1,280–1,500 °C) centrifuge-assisted experiments on a chromite-basalt melt system at 100–1,500g (0.5 GPa). Subsequently, the feasibility of this process for the formation of dense chromite cumulate layers in large layered mafic intrusions (LMIs) is assessed. Centrifugation leads to a single cumulate layer formed at the gravitational bottom of the capsule. The experimentally observed mechanical settling velocity of a suspension of ~24 vol% chromite is calculated to be about half (~0.53) of the Stokes settling velocity, with a sedimentation exponent n of 2.35 (3). Gravitational settling leads to an orthocumulate layer with a porosity of 0.52 (all porosities as fraction). Formation times for such a layer from a magma with initial chromite contents of 0.1–1 vol% are 140–3.5 days, equal to a growth rate of 0.007–0.3 m/day for grain sizes of 1–2 mm. More compacted chromite layers form with increasing centrifugation time and acceleration through chemical compaction: An increase of grain contact areas and grain sizes together with a decrease in porosity is best explained by pressure dissolution at grain contacts, reprecipitation and grain growth into the intergranular space and a concomitant expulsion of intergranular melt. The relation between the porosity in the cumulate pile and effective pressure integrated over time (Δρ · h · a · t) is best fit with a logarithmic function, in fact confirming that a (pressure) dissolution–reprecipitation process is the dominant mechanism of compaction. The experimentally derived equation allows calculating compaction times: 70–80 % chromite at the bottom of a 1-m-thick chromite layer are reached after 9–250 years, whereas equivalent compaction times are 0.2–0.9 years for olivine (both for 2 mm grain size). The experiments allow to determine the bulk viscosities of chromite and olivine cumulates to be of magnitude 10⁹ Pa s, much lower than previously reported. As long as melt escape from the compacting cumulate remains homogeneous, fluidization does not play any role; however, channelized melt flow may lead to suspension and upward movement of cumulate crystals. In LMIs, chromitite layers are typically part of a sequence with layers of mafic minerals, compaction occurs under the additional weight of the overlying layers and can be achieved in a few years to decades.     

Prawn postlarvae fishing in coastal Bangladesh: Challenges for sustainable livelihoods

Fishing for prawn (Macrobrachium rosenbergii) postlarvae is a major contributor to the livelihoods of the coastal poor in Bangladesh, including women. A study of coastal livelihoods along the lower Pasur River in southwest Bangladesh indicates that on average 40% of total annual income comes from postlarvae fishing during the few months involved. However, indiscriminate fishing of wild postlarvae, with high levels of by-catch, has an impact on biodiversity in coastal ecosystems. This has provoked imposition of restrictions on postlarvae collection. The ban has, however, not been firmly enforced because of the lack of alternative livelihoods for coastal poor. A conceptual framework, drawn from an approach to poverty reduction known as the sustainable livelihoods approach, is applied to understanding the role of prawn postlarvae fishing. Evidence from this study suggests that postlarvae fishers faced a number of livelihood constraints, including poor livelihood assets. This paper concludes that wider livelihood options need to be found for postlarvae fishers to support their livelihoods.     

MedFlux: Investigations of particle flux in the Twilight Zone

The MedFlux project was devised to determine and model relationships between organic matter and mineral ballasts of sinking particulate matter in the ocean. Specifically we investigated the ballast ratio hypothesis, tested various commonly used sampling and modeling techniques, and developed new technologies that would allow better characterization of particle biogeochemistry. Here we describe the rationale for the project, the biogeochemical provenance of the DYFAMED site, the international support structure, and highlights from the papers published here. Additional MedFlux papers can be accessed at the MedFlux web site (http://msrc.sunysb.edu/MedFlux/).