Martial Taillefert

Chemical speciation drives hydrothermal vent ecology.

The physiology and biochemistry of many taxa inhabiting deep-sea hydrothermal vents have been elucidated; however, the physicochemical factors controlling the distribution of these organisms at a given vent site remain an enigma after 20 years of research. The chemical speciation of particular elements has been suggested as key to controlling biological community structure in these extreme aquatic environments. Implementation of electrochemical technology has allowed us to make in situ measurements of chemical speciation at vents located at the East Pacific Rise (9° 50′ N) and on a scale relevant to the biology. Here we report that significant differences in oxygen, iron and sulphur speciation strongly correlate with the distribution of specific taxa in different microhabitats. In higher temperature (> 30 °C) microhabitats, the appreciable formation of soluble iron-sulphide molecular clusters markedly reduces the availability of free H2S/HS- to vent (micro)organisms, thus controlling the available habitat.

Sulfur speciation monitored in situ with solid state gold amalgam voltammetric microelectrodes: polysulfides as a special case in sediments, microbial mats and hydrothermal vent waters{{

Sulfur speciation was determined in real time in salt marsh microbial mats, subtidal sediments and hydrothermal vent diffuse flow waters using solid state gold-amalgam voltammetric microelectrodes. Chemical species were measured in situ without any sample manipulation or processing. The partially oxidized sulfur species detected were polysulfides, thiosulfate, elemental sulfur and tetrathionate. Fe(III) oxidation of hydrogen sulfide does not occur within the mats where microbially mediated processes are responsible for oxidation of H2S. In sediments and diffuse flow vent waters, Fe(III) phases are the direct oxidant of H2S. Sulfur speciation determined in this work is due to in situ biogeochemical processes and is not due to artefacts of sample manipulation. The voltammetric data show that polysulfides are the first detectable intermediate during sulfide oxidation which is consistent with previous laboratory studies.

Benthic biogeochemistry: state of the art technologies and guidelines for the future of in situ survey

Sediment and water can potentially be altered, chemically, physically and biologically as they are sampled at the seafloor, brought to the surface, processed and analysed. As a result, in situ observations of relatively undisturbed systems have become the goal of a growing body of scientists. Our understanding of sediment biogeochemistry and exchange fluxes was revolutionized by the introduction of benthic chambers and in situ micro-electrode profilers that allow for the direct measurement of chemical fluxes between sediment and water at the sea floor and for porewater composition. Since then, rapid progress in the technology of in situ sensors and benthic chambers (such as the introduction of gel probes, voltammetric electrodes or one- and two-dimensional optodes) have yielded major breakthroughs in the scientific understanding of benthic biogeochemistry. This paper is a synthesis of discussions held during the workshop on sediment biogeochemistry at the “Benthic Dynamics: in situ surveillance of the sediment–water interface” international conference (Aberdeen, UK—March 25–29, 2002). We present a review of existing in situ technologies for the study of benthic biogeochemistry dynamics and related scientific applications. Limitations and possible improvement (e.g., technology coupling) of these technologies and future development of new sensors are discussed. There are countless important scientific and technical issues that lend themselves to investigation using in situ benthic biogeochemical assessment. While the increasing availability of these tools will lead research in yet unanticipated directions, a few emerging issues include greater insight into the controls on organic matter (OM) mineralization, better models for the understanding of benthic fluxes to reconcile microelectrode and larger-scale chamber measurements, insight into the impacts of redox changes on trace metal behavior, new insights into geochemical reaction pathways in surface sediments, and a better understanding of contaminant fate in nearshore sediments.

Speciation, reactivity, and cycling of Fe and Pb in a meromictic lake

organic matter, hydrous iron oxides, and particulate Pb suggest that Pb is scavenged by Fe-rich particles formed at the oxic-anoxic transition. Transmission electron microscopy shows that particles of hydrous iron oxides form complex aggregates with natural organic matter at and below the oxic-anoxic transition. Experiments with batch reactors show that these organo-mineral moieties remove Pb rapidly during their formation. Thermodynamic calculations predict that FeS and PbS are respectively saturated and oversaturated in the monimolimnion, although the presence of neither FeS nor PbS was observed. This suggests that the solubilities of Fe and Pb are influenced by complexation. Voltammetric experiments on filtered samples show that Pb is weakly complexed in the mixolimnion and strongly complexed in the monimolimnion. A conditional stability constant for Pb complexation is determined using metal titration curves assuming a simple 1:1 stoichiometry and gives logKcond 5 9.4 6 0.8 M 21 in the monimolimnion. These speciation results are confirmed by ion exchange chromatography, which demonstrates that more than 98% of Pb is complexed by natural organic matter. Copyright

The Application of Electrochemical Tools for In Situ Measurements in Aquatic Systems

Analytical Instrument Systems, Inc., P.O. Box 458, Flemington, NJ 08822–0458, USAReceived: September 30, 1999Final version: November 22, 1999AbstractSince the 1970’s, when the first in situ measurements of oxygen in the oceans were reported, the development of electrochemical sensors forin situ measurements in aquatic systems has significantly intensified. A synthesis of the progress made in limnology and oceanography tomeasure chemical species in situ is presented. From amperometric and potentiometric sensors that can measure a single analyte to volt-ammetric sensors that can measure several species during the same scan, a variety of electrodes have been used in situ to better understandthe nature of the biogeochemical processes occurring in aquatic systems. The advantages and disadvantages of each technique, the technicalimprovements over the years, and some recommendations are presented together with representative data reported in the literature over thelast two decades.

Association of cobalt and manganese in aquatic systems: Chemical and microscopic evidence

Abstract The distributions of cobalt and manganese in the water column of Paul Lake, a small meromictic lake located in the upper Michigan peninsula, follow remarkably Similar patterns. At the oxycline, these elements show pronounced concentration gradients. In May 1994, Co and Mn increase from detection limits to 6 nM and 3 μM, respectively. The association between Co and Mn can be attributed to the sorption of cobalt to manganese hydrous oxides, and the redox-driven interconversion between dissolved Mn and particulate Mn-oxides species, which is often mediated by micro-organisms. In this paper, we have used a multi-method approach to the study of Co:Mn association in an aquatic system. First, using equilibrium calculations, we discuss the chemical speciation of dissolved Co and Mn in the water column. Second, we present a Transmission Electron Microscopic (TEM) characterization of individual Mn-rich micro-particles. These particles were primarily observed at the oxic/anoxic transition. Micrographs confirm the biological origin of the hydrous manganese oxides. Analytical Electron Microscopy clearly establishes that Co and Fe are scavenged by micro-organisms bearing a Mn-oxide crust. Co:Mn ratios were determined on individual particles by Energy Dispersive Spectrometry (EDS). The comparison of the average Co:Mn ratio in particles to the one in solution shows that Co is enriched in the Mn-oxides overgrowths. High resolution TEM-EDS analyses of environmental particles proves to be a powerful tool to unveil chemical associations that are difficult to deduce from changes in the water chemistry.

The effect of tidal forcing on biogeochemical processes in intertidal salt marsh sediments

BackgroundEarly diagenetic processes involved in natural organic matter (NOM) oxidation in marine sediments have been for the most part characterized after collecting sediment cores and extracting porewaters. These techniques have proven useful for deep-sea sediments where biogeochemical processes are limited to aerobic respiration, denitrification, and manganese reduction and span over several centimeters. In coastal marine sediments, however, the concentration of NOM is so high that the spatial resolution needed to characterize these processes cannot be achieved with conventional sampling techniques. In addition, coastal sediments are influenced by tidal forcing that likely affects the processes involved in carbon oxidation.ResultsIn this study, we used in situ voltammetry to determine the role of tidal forcing on early diagenetic processes in intertidal salt marsh sediments. We compare ex situ measurements collected seasonally, in situ profiling measurements, and in situ time series collected at several depths in the sediment during tidal cycles at two distinct stations, a small perennial creek and a mud flat. Our results indicate that the tides coupled to the salt marsh topography drastically influence the distribution of redox geochemical species and may be responsible for local differences noted year-round in the same sediments. Monitoring wells deployed to observe the effects of the tides on the vertical component of porewater transport reveal that creek sediments, because of their confinements, are exposed to much higher hydrostatic pressure gradients than mud flats.ConclusionOur study indicates that iron reduction can be sustained in intertidal creek sediments by a combination of physical forcing and chemical oxidation, while intertidal mud flat sediments are mainly subject to sulfate reduction. These processes likely allow microbial iron reduction to be an important terminal electron accepting process in intertidal coastal sediments.

Nonreductive Biomineralization of Uranium(VI) Phosphate Via Microbial Phosphatase Activity in Anaerobic Conditions

The remediation of uranium from soils and groundwater at Department of Energy (DOE) sites across the United States represents a major environmental issue, and bioremediation has exhibited great potential as a strategy to immobilize U in the subsurface. The bioreduction of U(VI) to insoluble U(IV) uraninite has been proposed to be an effective bioremediation process in anaerobic conditions. However, high concentrations of nitrate and low pH found in some contaminated areas have been shown to limit the efficiency of microbial reduction of uranium. In the present study, nonreductive uranium biomineralization promoted by microbial phosphatase activity was investigated in anaerobic conditions in the presence of high nitrate and low pH as an alternative approach to the bioreduction of U(VI). A facultative anaerobe, Rahnella sp. Y9602, isolated from soils at DOEs Oak Ridge Field Research Center (ORFRC), was able to respire anaerobically on nitrate as a terminal electron acceptor in the presence of glycerol-3-phosphate (G3P) as the sole carbon and phosphorus source and hydrolyzed sufficient phosphate to precipitate 95% total uranium after 120 hours in synthetic groundwater at pH 5.5. Synchrotron X-ray diffraction and X-ray absorption spectroscopy identified the mineral formed as chernikovite, a U(VI) autunite-type mineral. The results of this study suggest that in contaminated subsurfaces, such as at the ORFRC, where high concentrations of nitrate and low pH may limit uranium bioreduction, the biomineralization of U(VI) phosphate minerals may be a more attractive approach for in situ remediation providing that a source of organophosphate is supplied for bioremediation.

The Influence of Sulfides on Soluble Organic-Fe(III) in Anoxic Sediment Porewaters

Solid and colloidal iron oxides are commonly involved in early diagenesis. More readily available soluble Fe(III) should accelerate the cycling of iron (Fe) and sulfur (S) in sediments. Experiments with synthetic solutions (Taillefert et al. 2000) showed that soluble Fe(III) (i.e., <50 nm diameter) reacts at a mercury voltammetric electrode at circumneutral pH if it is complexed by an organic ligand. The reactivity of soluble organic-Fe(III) with sulfide is greatly increased compared to its solid equivalent (e.g., amorphous hydrous iron oxides or goethite). We report here data from two different creeks of the Hackensack Meadowlands District (New Jersey) collected with solid state Au/Hg voltammetric microelectrodes and other conventional techniques, which confirm the existence of soluble organic-Fe(III) in sediments and its interaction with sulfide. Chemical profiles in these two anoxic sediments show the interaction between iron and sulfur during early diagenesis. Soluble organic-Fe(III) and Fe(II) are dominant in a creek where sulfide is negligible. This dominance suggests that the reductive dissolution of iron oxides goes through the dissolution of solid Fe(III), then reduction to Fe(II), or that soluble organic-Fe(III) is formed by chemical or microbial oxidation of organic-Fe(II) complexes. In a creek sediment where sulfide occurs in significant concentration, the reductive dissolution of Fe(III) is followed by formation of FeS(aq), which further precipitates. Dissolved sulfide may influence the fate of soluble organic-Fe(III), but the pH may be the key variable behind this process. The high reactivity of soluble organic-Fe(III) and its mobility may result in the shifting of local reactions, at depths where other electron acceptors are used. These data also suggest that estuarine and coastal sediments may not always be at steady state.

Shewanella oneidensis MR‐1 mutants selected for their inability to produce soluble organic‐Fe(III) complexes are unable to respire Fe(III) as anaerobic electron acceptor

Recent voltammetric analyses indicate that Shewanella putrefaciens strain 200 produces soluble organic-Fe(III) complexes during anaerobic respiration of sparingly soluble Fe(III) oxides. Results of the present study expand the range of Shewanella species capable of producing soluble organic-Fe(III) complexes to include Shewanella oneidensis MR-1. Soluble organic-Fe(III) was produced by S. oneidensis cultures incubated anaerobically with Fe(III) oxides, or with Fe(III) oxides and the alternate electron acceptor fumarate, but not in the presence of O(2), nitrate or trimethylamine-N-oxide. Chemical mutagenesis procedures were combined with a novel MicroElectrode Screening Array (MESA) to identify four (designated Sol) mutants with impaired ability to produce soluble organic-Fe(III) during anaerobic respiration of Fe(III) oxides. Two of the Sol mutants were deficient in anaerobic growth on both soluble Fe(III)-citrate and Fe(III) oxide, yet retained the ability to grow on a suite of seven alternate electron acceptors. The rates of soluble organic-Fe(III) production were proportional to the rates of iron reduction by the S. oneidensis wild-type and Sol mutant strains, and all four Sol mutants retained wild-type siderophore production capability. Results of this study indicate that the production of soluble organic-Fe(III) may be an important intermediate step in the anaerobic respiration of both soluble and sparingly soluble forms of Fe(III) by S. oneidensis.