Robin Brinkmeyer

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.

Factors controlling mobility of 127I and 129I species in an acidic groundwater plume at the Savannah River Site

In order to quantify changes in iodine speciation and to assess factors controlling the distribution and mobility of iodine at an iodine-129 ((129)I) contaminated site located at the U.S. Department of Energys Savannah River Site (SRS), spatial distributions and transformation of (129)I and stable iodine ((127)I) species in groundwater were investigated along a gradient in redox potential (654 to 360 mV), organic carbon concentration (5 to 60 μmol L(-1)), and pH (pH 3.2 to 6.8). Total (129)I concentration in groundwater was 8.6±2.8 Bq L(-1) immediately downstream of a former waste seepage basin (well FSB-95DR), and decreased with distance from the seepage basin. (127)I concentration decreased similarly to that of (129)I. Elevated concentrations of (127)I or (129)I were not detected in groundwater collected from wells located outside of the mixed waste plume of this area. At FSB-95DR, the majority (55-86%) of iodine existed as iodide for both (127)I and (129)I. Then, as the iodide move down gradient, some of it transformed into iodate and organo-iodine. Considering that iodate has a higher K(d) value than iodide, we hypothesize that the production of iodate in groundwater resulted in the removal of iodine from the groundwater and consequently decreased concentrations of (127)I and (129)I in downstream areas. Significant amounts of organo-iodine species (30-82% of the total iodine) were also observed at upstream wells, including those outside the mixed waste plume. Concentrations of groundwater iodide decreased at a faster rate than organo-iodine along the transect from the seepage basin. We concluded that removal of iodine from the groundwater through the formation of high molecular weight organo-iodine species is complicated by the release of other more mobile organo-iodine species in the groundwater.

Bacterial Production of Organic Acids Enhances H2O2-Dependent Iodide Oxidation

To develop an understanding of the role that microorganisms play in the transport of (129)I in soil-water systems, bacteria isolated from subsurface sediments were assessed for iodide oxidizing activity. Spent liquid medium from 27/84 bacterial cultures enhanced iodide oxidation 2-10 fold in the presence of H(2)O(2). Organic acids secreted by the bacteria were found to enhance iodide oxidation by (1) lowering the pH of the spent medium, and (2) reacting with H(2)O(2) to form peroxy carboxylic acids, which are extremely strong oxidizing agents. H(2)O(2)-dependent iodide oxidation increased exponentially from 8.4 to 825.9 μM with decreasing pH from 9 to 4. Organic acids with ≥2 carboxy groups enhanced H(2)O(2)-dependent iodide oxidation (1.5-15-fold) as a function of increasing pH above pH 6.0, but had no effect at pH ≤ 5.0. The results indicate that as pH decreases (≤5.0), increasing H(2)O(2) hydrolysis is the driving force behind iodide oxidation. However, at pH ≥ 6.0, spontaneous decomposition of peroxy carboxylic acids, generated from H(2)O(2) and organic acids, contributes significantly to iodide oxidation. The results reveal an indirect microbial mechanism, organic acid secretion coupled to H(2)O(2) production, that could enhance iodide oxidation and organo-iodine formation in soils and sediments.

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.

Ecosystem under pressure: ballast water discharge into Galveston Bay, Texas (USA) from 2005 to 2010.

Ballast water exchange processes facilitate the dispersal and unnatural geographic expansion of phytoplankton, including harmful algal bloom species. From 2005 to 2010, over 45,000 vessels (≈ 8000 annually) travelled across Galveston Bay (Texas, USA) to the deep-water ports of Houston (10th largest in the world), Texas City and Galveston. These vessels (primarily tankers and bulkers) discharged ≈ 1.2 × 10(8) metrictons of ballast water; equivalent to ≈ 3.4% of the total volume of the Bay. Over half of the ballast water discharged had a coastwise origin, 96% being from US waters. Galveston Bay has fewer non-indigenous species but receives a higher volume of ballast water discharge, relative to the highly invaded Chesapeake and San Francisco Bays. Given the magnitude of shipping traffic, the role of Galveston Bay, both as a recipient and donor region of non-indigenous phytoplankton species is discussed here in terms of the invasibility risk to this system by way of ballast water.

All aboard! A biological survey of ballast water onboard vessels spanning the North Atlantic Ocean.

Global movement of nonindigenous species, within ballast water tanks across natural barriers, threatens coastal and estuarine ecosystem biodiversity. In 2012, the Port of Houston ranked 10th largest in the world and 2nd in the US (waterborne tonnage). Ballast water was collected from 13 vessels to genetically examine the eukaryotic microorganism diversity being discharged into the Port of Houston, Texas (USA). Vessels took ballast water onboard in North Atlantic Ocean between the Port of Malabo, Africa and Port of New Orleans, Louisiana, (USA). Twenty genera of Protists, Fungi and Animalia were identified from at least 10 phyla. Dinoflagellates were the most diverse and dominant identified (Alexandrium, Exuviaella, Gyrodinium, Heterocapsa, Karlodinium, Pfiesteria and Scrippsiella). We are reporting the first detection of Picobiliphytes, Apusozoa (Amastigomonas) and Sarcinomyces within ballast water. This study supports that global commerce by shipping contributes to long-distance transportation of eukaryotic microorganisms, increasing propagule pressure and invasion supply on ecosystems.

Impacts of Dredging Activities on the Accumulation of Dioxins in Surface Sediments of the Houston Ship Channel, Texas

Abstract The Houston Ship Channel (HSC) and upper Galveston Bay (GB), Texas, are known to be contaminated with dioxins (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans), the majority of which are associated with sediments. Since 1914, dredging operations to establish, sporadically expand, and consistently maintain a navigable channel for large ships has been and remains continuous here. The objectives of this research focus on determining if dredging activities have any significant impact on the quantities of dioxins associated with surface sediments in the HSC and GB. Four transects were sampled, located on the dredged and undredged sides of two dredge-spoil islands. Sediment samples were characterized in terms of their organic carbon contents, grain size fractions, indicator dioxin concentrations (2,3,7,8-tetrachlorinated dibenzo-p-dioxin [TCDD], 2,3,7,8-tetrachlorodibenzofuran [TCDF], and toxic equivalents), and fallout radionuclide activities. The physical and geochemical data were examined using a combination of principal components analysis and one-way analysis of variance. Results of the statistical tests show that (1) sedimentary dioxin concentrations are significantly higher adjacent to the northernmost dredge-spoil island, which is located closer to a recently identified dioxin point source (San Jacinto waste pits); and (2) while mean sedimentary dioxin concentrations were slightly higher for undredged as compared to dredged transect samples as a whole, these differences were not significant (p > 0.05). Mean fallout isotope ratio values (7Be/137Cs, 7Be/210Pbxs) were greater for the dredged sample population, indicating that dredged sediments contain more of the shorter-lived radionuclides (i.e., 7Be), as their buildup is more rapid after dredging than those isotopes with longer half-lives (210Pb) or those for which a longer time has passed since introduction into the environment (137Cs).

A Tale of Two Ports: Dinoflagellate and Diatom Communities Found in the High Ship Traffic Region of Galveston Bay, Texas (USA)

ABSTRACT Steichen, J.L.; Denby, A.; Windham, R.; Brinkmeyer, R., and Quigg, A., 2015. A tale of two ports: Dinoflagellate and diatom communities found in the high ship traffic region of Galveston Bay, Texas (USA). Ballast water (BW) discharge by shipping vessels is a known transport vector of harmful species of dinoflagellates and diatoms. With a steady growth in global commerce, ship traffic to ports worldwide has intensified, increasing the risk of invasion by nonindigenous species. From 2008–12, >140 million metric tons of BW was discharged into Galveston Bay, Texas, much more than reported in other highly invaded Bays: San Francisco (96 × 106 mt) and Chesapeake (25 × 106 mt) during the same period. Studies conducted specifically on the dinoflagellate and diatom communities within Galveston Bay have been lacking until the present effort, which used both microscopic and genetic methods. Within one year of sampling, 35 genera of dinoflagellates and diatoms were identified from the two deepwater ports of Houston and Galveston. Seven of the genera are known toxin producers, three of which have formed harmful algal blooms within the Bay: Alexandrium, Gymnodinium, and Prorocentrum. Two genera identified from the ports (Takayama and Woloszynskia) have not been previously reported. This study provides a baseline of the phytoplankton community within these major ports in Galveston Bay before foreign shipping traffic increases due to the expansion of the Panama Canal.