Seasonal and topographic variations in porewaters of a southeastern USA salt marsh as revealed by voltammetric profiling†

We report electrochemical profiles from unvegetated surficial sediments of a Georgia salt marsh. In creek bank sediments, the absence of ΣH(2)S or FeS(aq )and the presence of Fe(III)–organic complexes suggest that Mn and Fe reduction dominates over at least the top ca. 5 cm of the sediment column, consistent with other recent results. In unvegetated flats, accumulation of ΣH(2)S indicates that SO(4)(2- )reduction dominates over the same depth. A summer release of dissolved organic species from the dominant tall form Spartina alterniflora, together with elevated temperatures, appears to result in increased SO(4)(2- )reduction intensity and hence high summer concentrations of ΣH(2)S in flat sediments. However, increased bioturbation and/or bioirrigation seem to prevent this from happening in bank sediments. Studies of biogeochemical processes in salt marshes need to take such spatial and temporal variations into account if we are to develop a good understanding of these highly productive ecosystems. Furthermore, multidimensional analyses are necessary to obtain adequate quantitative pictures of such heterogeneous sediments

Promoting uranium immobilization by the activities of microbial phophatases

The following is a summary of progress in our project ''Promoting uranium immobilization by the activities of microbial phosphatases'' during the second year of the project. (1). Assignment of microbial phosphatases to molecular classes. One objective of this project is to determine the relationship of phosphatase activity to metal resistance in subsurface strains and possible contributions of horizontal gene transfer (HGT) to the dissemination of nonspecific acid phosphatase genes. Non-specific acid phosphohydrolases are a broad group of secreted microbial phosphatases that function in acidic-to-neutral pH ranges and utilize a wide range of organophosphate substrates. To address this objective we have designed a collection of PCR primer sets based on known microbial acid phosphatase sequences. Genomic DNA is extracted from subsurface FRC isolates and amplicons of the expected sizes are sequenced and searched for conserved signature motifs. During this reporting period we have successfully designed and tested a suite of PCR primers for gram-positive and gram-negative groups of the following phosphatase classes: (1) Class A; (2) Class B; and (3) Class C (gram negative). We have obtained specific PCR products for each of the classes using the primers we have designed using control strains as well as with subsurface isolates

Potential Role of Inorganic Polyphosphate in the Cycling of Phosphorus Within the Hypoxic Water Column of Effingham Inlet, British Columbia

[1] The upper basin of Effingham Inlet possesses permanently anoxic bottom waters, with a water column redox transition zone typically occurring at least 40 m above the sediment‐water interface. During our sampling campaign in April and July 2007, this redox transition zone was associated with sharp peaks in a variety of parameters, including soluble reactive phosphorus (SRP) and total particulate phosphorus (TPP). Based on sequential extraction results, TPP maxima exhibited preferential accumulation of an operationally defined class of loosely adsorbed organic phosphorus (P), which may contain a substantial fraction of polyphosphate (poly‐P). This poly‐P may furthermore be involved in the redox‐dependent remobilization of SRP. For example, direct fluorometric analysis of poly‐P content revealed that particulate inorganic poly‐P was present at concentrations ranging from 1 to 9 nM P within and several meters above the TPP maximum. Below the depth of 1% oxygen saturation, however, particulate inorganic poly‐P was undetectable

Promoting Uranium Immobilization by the Activities of Microbial Phosphatases

The overall objective of this project is to examine the activity of nonspecific phosphohydrolases present in naturally occurring subsurface microorganisms for the purpose of promoting the immobilization of radionuclides through the production of uranium [U(VI)] phosphate precipitates. Specifically, we hypothesize that the precipitation of U(VI) phosphate minerals may be promoted through the microbial release and/or accumulation of PO4 3- as a means to detoxify radionuclides and heavy metals. An experimental approach was designed to determine the extent of phosphatase activity in bacteria previously isolated from contaminated subsurface soils collected at the ERSP Field Research Center (FRC) in Oak Ridge, TN. Screening of 135 metal resistant isolates for phosphatase activity indicated the majority (75 of 135) exhibited a phosphatase-positive phenotype. During this phase of the project, a PCR based approach has also been designed to assay FRC isolates for the presence of one or more classes of the characterized non-specific acid phophastase (NSAP) genes likely to be involved in promoting U(VI) precipitation. Testing of a subset of Pb resistant (Pbr) Arthrobacter, Bacillus and Rahnella strains indicated 4 of the 9 Pbr isolates exhibited phosphatase phenotypes suggestive of the ability to bioprecipitate U(VI). Two FRC strains, a Rahnella sp. strain Y9602 and a Bacillus sp. strain Y9-2, were further characterized. The Rahnella sp. exhibited enhanced phosphatase activity relative to the Bacillus sp. Whole-cell enzyme assays identified a pH optimum of 5.5, and inorganic phosphate accumulated in pH 5.5 synthetic groundwater (designed to mimic FRC conditions) incubations of both strains in the presence of a model organophosphorus substrate provided as the sole C and P source. Kinetic experiments showed that these two organisms can grow in the presence of 200 μM dissolved uranium and that Rahnella is much more efficient in precipitating U(VI) than Bacillus sp. The precipitation of U(VI) must be mediated by biological activity as less than 3% soluble U(VI) was removed either from the abiotic or the heat-killed cell controls. Interestingly, the pH has a strong effect on growth and U(VI) biomineralization rates by Rahnella. Thermodynamic modeling identifies autunite-type minerals [Ca(UO2)2(PO4)2] as the precipitate likely formed in the synthetic FRC groundwater conditions at all pH investigated. Extended X-ray absorption fine structure measurements have recently confirmed that the precipitate found in these incubations is an autunite and meta-autunite-type mineral. A kinetic model of U biomineralization at the different pH indicates that hydrolysis of organophosphate can be described using simple Monod kinetics and that uranium precipitation is accelerated when monohydrogen phosphate is the main orthophosphate species in solution. Overall, these experiments and ongoing soil slurry incubations demonstrate that the biomineralization of U(VI) through the activity of phosphatase enzymes can be expressed in a wide range of geochemical conditions pertaining to the FRC site

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

<p>Abstract</p> <p>Background</p> <p>Early 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.</p> <p>Results</p> <p>In 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.</p> <p>Conclusion</p> <p>Our 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.</p

Sediment pore water and solid phase geochemical analyses from samples collected on R/V Savannah cruise SAV-16-16 at the Cape Lookout Continental Shelf and Slope during May 2016

Dataset: Pore Water Depth Profiles CL2016Sediment pore water and solid phase geochemical analyses from samples collected on R/V Savannah cruise SAV-16-16 at the Cape Lookout Continental Shelf and Slope during May 2016. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/806065NSF Division of Ocean Sciences (NSF OCE) OCE-143864

Electrochemical data from sediments collected on R/V Savannah cruise SAV-15-18 at the Cape Lookout Continental Shelf and Slope during July 2015

Dataset: Electrochemical Data CL2015Electrochemistry data from sediments collected on R/V Savannah cruise SAV-15-18 at the Cape Lookout Continental Shelf and Slope during July 2015. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/786511NSF Division of Ocean Sciences (NSF OCE) OCE-143864

Sediment pore water and solid phase geochemical analyses from samples collected on R/V Savannah cruise SAV-17-15 in the Gulf of Mexico during July and August 2017

Dataset: Pore Water Depth Profiles GoM2017Sediment pore water and solid phase geochemical analyses from samples collected on R/V Savannah cruise SAV-17-15 in the Gulf of Mexico during July and August 2017. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/806105NSF Division of Ocean Sciences (NSF OCE) OCE-143864

Electrochemical data from sediments collected on R/V Savannah cruise SAV-17-15 in the Gulf of Mexico during July and August 2017

Dataset: Electrochemical Data GoM2017Electrochemical data from sediments collected on R/V Savannah cruise SAV-17-15 in the Gulf of Mexico during July and August 2017. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/806429NSF Division of Ocean Sciences (NSF OCE) OCE-143864

Electrochemical data from sediments collected on R/V Savannah cruise SAV-16-16 at the Cape Lookout Continental Shelf and Slope during May 2016

Dataset: Electrochemical Data CL2016Electrochemical data from sediments collected on R/V Savannah cruise SAV-16-16 at the Cape Lookout Continental Shelf and Slope during May 2016. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/805916NSF Division of Ocean Sciences (NSF OCE) OCE-143864