Kathy A. Schwehr

The algal toxicity of silver engineered nanoparticles and detoxification by exopolymeric substances

In this study, we report that silver ions (Ag(+)) from the oxidative dissolution of silver engineered nanoparticles (Ag-ENs) determined the EN toxicity to the marine diatom Thalassiosira weissflogii. Most of the Ag-ENs formed non-toxic aggregates (>0.22 microm) in seawater. When the free Ag(+) concentration ([Ag(+)](F)) was greatly reduced by diafiltration or thiol complexation, no toxicity was observed, even though the Ag-ENs were better dispersed in the presence of thiols with up to 1.08 x 10(-5) M Ag-ENs found in the <0.22 microm fraction, which are orders of magnitude higher than predicted for the natural aquatic environment. The secretion of polysaccharide-rich algal exopolymeric substances (EPS) significantly increased at increasing [Ag(+)](F). Both dissolved and particulate polysaccharide concentrations were higher for nutrient-limited cells, coinciding with their higher Ag(+) tolerance, suggesting that EPS may be involved in Ag(+) detoxification.

A novel approach for the simultaneous determination of iodide, iodate and organo-iodide for 127I and 129I in environmental samples using gas chromatography-mass spectrometry.

In aquatic environments, iodine mainly exists as iodide, iodate, and organic iodine. The high mobility of iodine in aquatic systems has led to (129)I contamination problems at sites where nuclear fuel has been reprocessed, such as the F-area of Savannah River Site. In order to assess the distribution of (129)I and stable (127)I in environmental systems, a sensitive and rapid method was developed which enables determination of isotopic ratios of speciated iodine. Iodide concentrations were quantified using gas chromatography-mass spectrometry (GC-MS) after derivatization to 4-iodo-N,N-dimethylaniline. Iodate concentrations were quantified by measuring the difference of iodide concentrations in the solution before and after reduction by Na(2)S(2)O(5). Total iodine, including inorganic and organic iodine, was determined after conversion to iodate by combustion at 900 °C. Organo-iodine was calculated as the difference between the total iodine and total inorganic iodine (iodide and iodate). The detection limits of iodide-127 and iodate-127 were 0.34 nM and 1.11 nM, respectively, whereas the detection limits for both iodide-129 and iodate-129 was 0.08 nM (i.e., 2pCi (129)I/L). This method was successfully applied to water samples from the contaminated Savannah River Site, South Carolina, and more pristine Galveston Bay, Texas.

Concentration-Dependent Mobility, Retardation, and Speciation of Iodine in Surface Sediment from the Savannah River Site

Iodine occurs in multiple oxidation states in aquatic systems in the form of organic and inorganic species. This feature leads to complex biogeochemical cycling of stable iodine and its long-lived isotope, (129)I. In this study, we investigated the sorption, transport, and interconversion of iodine species by comparing their mobility in groundwaters at ambient concentrations of iodine species (10(-8) to 10(-7) M) to those at artificially elevated concentrations (78.7 μM), which often are used in laboratory analyses. Results demonstrate that the mobility of iodine species greatly depends on, in addition to the type of species, the iodine concentration used, presumably limited by the number of surface organic carbon binding sites to form covalent bonds. At ambient concentrations, iodide and iodate were significantly retarded (K(d) values as high as 49 mL g(-1)), whereas at concentrations of 78.7 μM, iodide traveled along with the water without retardation. Appreciable amounts of iodide during transport were retained in soils due to iodination of organic carbon, specifically retained by aromatic carbon. At high input concentration of iodate (78.7 μM), iodate was found to be reduced to iodide and subsequently followed the transport behavior of iodide. These experiments underscore the importance of studying iodine geochemistry at ambient concentrations and demonstrate the dynamic nature of their speciation during transport conditions.

Evaluation of a Radioiodine Plume Increasing in Concentration at the Savannah River Site

Field and laboratory studies were carried out to understand the cause for steady increases in (129)I concentrations emanating from radiological basins located on the Savannah River Site, South Carolina. The basins were closed in 1988 by adding limestone and slag and then capping with a low permeability engineered cover. Groundwater (129)I concentrations in a well near the basins in 1993 were 200 pCi L(-1) and are presently between 400 and 1000 pCi L(-1). Iodine speciation in the plume contained wide ranges of iodide, iodate, and organo-iodine concentrations. First-order calculations based on a basin sediment desorption study indicate that the modest increase of 0.7 pH units detected in the study site groundwater over the last 17 years since closure of the basins may be sufficient to produce the observed increased groundwater (129)I concentrations near the basins. Groundwater monitoring of the plume at the basins has shown that the migration of many of the high risk radionuclides originally present at this complex site has been attenuated. However, (129)I continues to leave the source at a rate that may have been exacerbated by the initial remediation efforts. This study underscores the importance of identifying the appropriate in situ stabilization technologies for all source contaminants, especially if their geochemical behaviors differ.

Radioiodine Biogeochemistry and Prevalence in Groundwater

129I is commonly either the top or among the top risk drivers, along with 99Tc, at radiological waste disposal sites and contaminated groundwater sites where nuclear material fabrication or reprocessing has occurred. The risk stems largely from 129I having a high toxicity, a high bioaccumulation factor (90% of all the bodys iodine concentrates in the thyroid), a high inventory at source terms (due to its high fission yield), an extremely long half-life (16M years), and rapid mobility in the subsurface environment. Another important reason that 129I is a key risk driver is that there is uncertainty regarding its biogeochemical fate and transport in the environment. We typically can define 129I mass balance and flux at sites, but cannot predict accurately its response to changes in the environment. As a consequence of some of these characteristics, 129I has a very low drinking water standard, which is set at 1 pCi/L, the lowest of all radionuclides in the Federal Register. Recently, significant advancements have been made in detecting iodine species at ambient groundwater concentrations, defining the nature of the organic matter and iodine bond, and quantifying the role of naturally occurring sediment microbes to promote iodine oxidation and reduction. These recent studies have led to a more mechanistic understanding of radioiodine biogeochemistry. The objective of this review is to describe these advances and to provide a state of the science of radioiodine biogeochemistry relevant to its fate and transport in the terrestrial environment and provide information useful for making decisions regarding the stewardship and remediation of 129I contaminated sites. As part of this review, knowledge gaps were identified that would significantly advance the goals of basic and applied research programs for accelerating 129I environmental remediation and reducing uncertainty associated with disposal of 129I waste. Together the information gained from addressing these knowledge gaps will not alter the observation that 129I is primarily mobile, but it will likely permit demonstration that the entire 129I pool in the source term is not moving at the same rate and some may be tightly bound to the sediment, thereby smearing the modeled 129I peak and reducing maximum calculated risk.

Iodide Accumulation by Aerobic Bacteria Isolated from Subsurface Sediments of a 129I-Contaminated Aquifer at the Savannah River Site, South Carolina

ABSTRACT 129I is of major concern because of its mobility in the environment, excessive inventory, toxicity (it accumulates in the thyroid), and long half-life (∼16 million years). The aim of this study was to determine if bacteria from a 129I-contaminated oxic aquifer at the F area of the U.S. Department of Energys Savannah River Site, SC, could accumulate iodide at environmentally relevant concentrations (0.1 μM I−). Iodide accumulation capability was found in 3 out of 136 aerobic bacterial strains isolated from the F area that were closely related to Streptomyces/Kitasatospora spp., Bacillus mycoides, and Ralstonia/Cupriavidus spp. Two previously described iodide-accumulating marine strains, a Flexibacter aggregans strain and an Arenibacter troitsensis strain, accumulated 2 to 50% total iodide (0.1 μM), whereas the F-area strains accumulated just 0.2 to 2.0%. Iodide accumulation by FA-30 was stimulated by the addition of H2O2, was not inhibited by chloride ions (27 mM), did not exhibit substrate saturation kinetics with regard to I− concentration (up to 10 μM I−), and increased at pH values of <6. Overall, the data indicate that I− accumulation likely results from electrophilic substitution of cellular organic molecules. This study demonstrates that readily culturable, aerobic bacteria of the F-area aquifer do not accumulate significant amounts of iodide; however, this mechanism may contribute to the long-term fate and transport of 129I and to the biogeochemical cycling of iodine over geologic time.

Superoxide production by a manganese-oxidizing bacterium facilitates iodide oxidation.

ABSTRACT The release of radioactive iodine (i.e., iodine-129 and iodine-131) from nuclear reprocessing facilities is a potential threat to human health. The fate and transport of iodine are determined primarily by its redox status, but processes that affect iodine oxidation states in the environment are poorly characterized. Given the difficulty in removing electrons from iodide (I−), naturally occurring iodide oxidation processes require strong oxidants, such as Mn oxides or microbial enzymes. In this study, we examine iodide oxidation by a marine bacterium, Roseobacter sp. AzwK-3b, which promotes Mn(II) oxidation by catalyzing the production of extracellular superoxide (O2 −). In the absence of Mn2+, Roseobacter sp. AzwK-3b cultures oxidized ∼90% of the provided iodide (10 μM) within 6 days, whereas in the presence of Mn(II), iodide oxidation occurred only after Mn(IV) formation ceased. Iodide oxidation was not observed during incubations in spent medium or with whole cells under anaerobic conditions or following heat treatment (boiling). Furthermore, iodide oxidation was significantly inhibited in the presence of superoxide dismutase and diphenylene iodonium (a general inhibitor of NADH oxidoreductases). In contrast, the addition of exogenous NADH enhanced iodide oxidation. Taken together, the results indicate that iodide oxidation was mediated primarily by extracellular superoxide generated by Roseobacter sp. AzwK-3b and not by the Mn oxides formed by this organism. Considering that extracellular superoxide formation is a widespread phenomenon among marine and terrestrial bacteria, this could represent an important pathway for iodide oxidation in some environments.

Biogenic manganese oxides facilitate iodide oxidation at pH ≤ 5

ABSTRACT Radioactive 129I, a byproduct of nuclear power generation, can pose risks to human health if released into the environment, where its mobility is highly dependent on speciation. Based on thermodynamic principles, 129I should exist primarily as iodide (I−) in most terrestrial environments; however, organo-129I and 129iodate are also commonly detected in contaminated soils and groundwater. To investigate the capability of biogenic manganese oxides to influence iodide speciation, 17 manganese-oxidizing bacterial strains, representing six genera, were isolated from soils of the Savannah River Site, South Carolina. The isolates produced between 2.6 and 67.1 nmole Mn oxides (ml−1 media after 25 days, pH 6.5). Results from inhibitor assays targeting extracellular enzymes and reactive oxygen species indicated that both play a role in microbe-induced Mn(II) oxidation among the strains examined. Iodide oxidation was not observed in cultures of the most active Mn-oxidizing bacteria, Chryseobacterium sp. strain SRS1 and Chromobacterium sp. strain SRS8, or the fungus, Acremonium strictum strain KR21–2. While substantial amounts of Mn(III/IV) oxides were only generated in cultures at ≥pH 6, iodide oxidation was only observed in the presence of Mn(III/IV) oxides when the pH was ≤5. Iodide oxidation was promoted to a greater extent by synthetic Mn(IV)O2 than biogenic Mn(III/IV) oxides under these low pH conditions (≤pH 5). These results indicate that the influence of biogenic manganese oxides on iodide oxidation and immobilization is primarily limited to low pH environments.

Recent advances in the detection of specific natural organic compounds as carriers for radionuclides in soil and water environments, with examples of radioiodine and plutonium

Among the key environmental factors influencing the fate and transport of radionuclides in the environment is natural organic matter (NOM). While this has been known for decades, there still remains great uncertainty in predicting NOM-radionuclide interactions because of lack of understanding of radionuclide interactions with the specific organic moieties within NOM. Furthermore, radionuclide-NOM studies conducted using modelled organic compounds or elevated radionuclide concentrations provide compromised information related to true environmental conditions. Thus, sensitive techniques are required not only for the detection of radionuclides, and their different species, at ambient and/or far-field concentrations, but also for potential trace organic compounds that are chemically binding these radionuclides. GC-MS and AMS techniques developed in our lab are reviewed here that aim to assess how two radionuclides, iodine and plutonium, form strong bonds with NOM by entirely different mechanisms; iodine tends to bind to aromatic functionalities, whereas plutonium binds to N-containing hydroxamate siderophores at ambient concentrations. While low-level measurements are a prerequisite for assessing iodine and plutonium migration at nuclear waste sites and as environmental tracers, it is necessary to determine their in-situ speciation, which ultimately controls their mobility and transport in natural environments. More importantly, advanced molecular-level instrumentation (e.g., nuclear magnetic resonance (NMR) and Fourier-transform ion cyclotron resonance coupled with electrospray ionization (ESI-FTICRMS) were applied to resolve either directly or indirectly the molecular environments in which the radionuclides are associated with the NOM.

Extracellular Enzyme Activity Profile in a Chemically Enhanced Water Accommodated Fraction of Surrogate Oil: Toward Understanding Microbial Activities After the Deepwater Horizon Oil Spill

Extracellular enzymes and extracellular polymeric substances (EPS) play a key role in overall microbial activity, growth and survival in the ocean. EPS, being amphiphilic in nature, can act as biological surfactant in an oil spill situation. Extracellular enzymes help microbes to digest and utilize fractions of organic matter, including EPS, which can stimulate growth and enhance microbial activity. These natural processes might have been altered during the 2010 Deepwater Horizon oil spill due to the presence of hydrocarbon and dispersant. This study aims to investigate the role of bacterial extracellular enzymes during exposure to hydrocarbons and dispersant. Mesocosm studies were conducted using a water accommodated fraction of oil mixed with the chemical dispersant, Corexit (CEWAF) in seawater collected from two different locations in the Gulf of Mexico and corresponding controls (no additions). Activities of five extracellular enzymes typically found in the EPS secreted by the microbial community – α- and β-glucosidase, lipase, alkaline phosphatase, leucine amino-peptidase – were measured using fluorogenic substrates in three different layers of the mesocosm tanks (surface, water column and bottom). Enhanced EPS production and extracellular enzyme activities were observed in the CEWAF treatment compared to the Control. Higher bacterial and micro-aggregate counts were also observed in the CEWAF treatment compared to Controls. Bacterial genera in the order Alteromonadaceae were the most abundant bacterial 16S rRNA amplicons recovered. Genomes of Alteromonadaceae commonly have alkaline phosphatase and leucine aminopeptidase, therefore they may contribute significantly to the measured enzyme activities. Only Alteromonadaceae and Pseudomonadaceae among bacteria detected here have higher percentage of genes for lipase. Piscirickettsiaceae was abundant; genomes from this order commonly have genes for leucine aminopeptidase. Overall, this study provides insights into the alteration to the microbial processes such as EPS and extracellular enzyme production, and to the microbial community, when exposed to the mixture of oil and dispersant.