Arsenite sequestration at the surface of nano-Fe(OH)2, ferrous-carbonate hydroxide, and green-rust after bioreduction of arsenic-sorbed lepidocrocite by Shewanella putrefaciens

X-ray Absorption Fine Structure (XAFS) spectroscopy was used in combination with high resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), X-ray energy dispersive spectroscopy (XEDS), X-ray powder diffraction, and Mössbauer spectroscopy to obtain detailed information on arsenic and iron speciation in the products of anaerobic reduction of pure and As(V)- or As(III)-adsorbed lepidocrocite (γ-FeOOH) by Shewanella putrefaciens ATCC 12099. We found that this strain of S. putrefaciens is capable of using Fe(III) in lepidocrocite and As(V) in solution or adsorbed on lepidocrocite surfaces as electron acceptors. Bioreduction of lepidocrocite in the absence of arsenic resulted in the formation of hydroxycarbonate green rust 1 [Fe^II₄Fe^III₂(OH)₁₂CO₃: GR1(CO₃)], which completely converted into ferrous-carbonate hydroxide (Fe^II₂(OH)₂CO₃: FCH) over nine months. This study thus provides the first evidence of bacterial reduction of stoichiometric GR1(CO₃) into FCH. Bioreduction of As(III)-adsorbed lepidocrocite also led to the formation of GR1(CO₃) prior to formation of FCH, but the presence of As(III) slows down this transformation, leading to the co-occurrence of both phases after 22-month of aging. At the end of this experiment, As(III) was found to be adsorbed on the surfaces of GR1(CO₃) and FCH. After five months, bioreduction of As(V)-bearing lepidocrocite led directly to the formation of FCH in association with nanometer-sized particles of a minor As-rich Fe(OH)₂ phase, with no evidence for green rust formation. In this five-month experiment, As(V) was fully converted to As(III), which was dominantly sorbed at the surface of the Fe(OH)₂ nanoparticles as oligomers binding to the edges of Fe(OH)₆ octahedra at the edges of the octahedral layers of Fe(OH)₂. These multinuclear As(III) surface complexes are characterized by As-As pairs at a distance of 3.32 ± 0.02 Å and by As-Fe pairs at a distance of 3.50 ± 0.02 Å and represent a new type of As(III) surface complex. Chemical analyses show that the majority of As(III) produced in the experiments with As present is associated with iron-bearing hydroxycarbonate or hydroxide solids, reinforcing the idea that, at least under some circumstances, bacterial reduction can promote As(III) sequestration instead of mobilizing it into solution.     

Settling-velocity distributions and sorting processes on a longitudinal dune: A case study

The processes acting on a longitudinal dune are inferred from the response in the area size-sorting characteristics of the sediment of the active layer. The sediment size distributions are determined by settling and are best described by a log-hyperbolic model which provides the most information on size-sorting processes. Size-sorting characteristics are markedly different across the low round-crested part of the dune from cross-sections of the high more sharp-crested part. This results in changes in textural parameters along the lee-side consistent with changes in the lee-side separation vortex. This is the first time that the effect of wind speed up on the lee-side is observed to be reflected in the sediment; it can only be detected with the very sensitive log-hyperbolic parameters.     

Smallholder groundwater irrigation in sub-Saharan Africa: an interdisciplinary framework applied to the Usangu plains, Tanzania

A simple but comprehensive framework for analysing the potential for and constraints to groundwater development for irrigated agriculture in sub-Saharan Africa is proposed. The framework, based on food value chain principles, is applied to the sub-Saharan context and a specific catchment in Tanzania, the Usangu plains, where groundwater has been proposed as a strategic resource for augmenting food production and smallholder livelihoods and to alleviate seasonal water scarcity. The novel contribution of the work is the presentation of a tool that can be applied to support an interdisciplinary approach to systematically identify most significant barriers and most critical water management and development interventions for sustainable development of groundwater irrigation. The result of the case study shows that farmer economics, capacity, and pump and well drilling market constraints limit groundwater irrigation in the Usangu plains rather than hydrogeological conditions.     

The Darwin Rise demise: the western Pacific guyot heights trace the trans-Pacific Mendocino fracture zone

The Darwin Rise has been proposed so many times and in so many forms and places that the time has come to make a more comprehensive examination of the region. Lying on the NW Pacific Plate between the Geisha Guyots, the Mid-Pacific Mountains, the equator, and the trenches, the region is roughly bounded by magnetic anomaly M20 (147 Ma). It was subjected to a massive outpouring of lava about 105 to 120 Ma, which created the guyots and seamounts in that region. Guyots are excellent tools for studying events of long ago because they eroded in the same lowstand in the Cretaceous and guyot relief, therefore, is a surrogate for paleo-sealevel. The relief is derived by subtracting the break depth of the summit plateau of a guyot from the regional depth. Guyot relief would necessarily be less in the center than to the periphery if the feature formed on a pre-existing rise, as has been postulated. The existence of a paleo-Darwin Rise would give concentric contours for the region in question. Of the sixty guyots used in this study, thirty-seven of these guyots were surveyed using SASS multibeam in the Marcus-Wake seamount group. Twenty-three guyots were surveyed using random track single-beam sonar surveys. An entirely different scenario is shown. Data revealed a major fracture passing through the area coevally or after the guyots formed. Because the depths to the summit are not the same now, vertical tectonics occurred after subaerial erosion. This means the fracture formed during and after the erosion (roughly 105 Ma) and influenced the normal sequence of events in guyot formation. Depending on how one deciphers trends through the Hess Rise morass, SASS bathymetry shows a continuation of the Surveyor/Mendocino fracture zone swarm inside the M20 region to the NE of these data. The fracture swarm continues to the western Pacific trench system. Based on this information, if the Darwin Rise ever existed, it had to have done so elsewhere.     

Hydraulic roughness over simple subaqueous dunes

Detailed studies of flow over subaqueous dunes in laboratory flumes were used to suggest a virtual near-bed layer of twice the dune height in which the mean velocity is accelerated towards the crest by contraction. The mean flow velocity in this layer above the crest, transformed into friction velocity by means of the surface skin roughness, is shown to give values consistent with measured values. The resulting dimensionless shear stress due to skin friction is depth-independent, in contrast to that derived by means of often cited traditional methods. As a result of the relationship between dune height and the thickness of the near-bed layer, an expression for the expansion loss behind dunes was formulated and used to relate form resistance directly to dune height.     

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/).