Iodide uptake by forest soils is principally related to the activity of extracellular oxidases.

129I is a nuclear fission decay product of concern because of its long half-life (16 Ma) and propensity to bioaccumulate. Microorganisms impact iodine mobility in soil systems by promoting iodination (covalent binding) of soil organic matter through processes that are not fully understood. Here, we examined iodide uptake by soils collected at two depths (0-10 and 10-20 cm) from 5 deciduous and coniferous forests in Japan and the United States. Autoclaved soils, and soils amended with an enzyme inhibitor (sodium azide) or an antibacterial agent (bronopol), bound significantly less 125I tracer (93%, 81%, 61% decrease, respectively) than the untreated control soils, confirming a microbial role in soil iodide uptake. Correlation analyses identified the strongest significant correlation between 125I uptake and three explanatory variables, actinobacteria soil biomass (p = 6.04E-04, 1.35E-02 for Kendall-Tau and regression analysis, respectively), soil nitrogen content (p = 4.86E-04, 4.24E-03), and soil oxidase enzyme activity at pH 7.0 using the substrate L-DOPA (p = 2.83E-03, 4.33E-04) and at pH 5.5 using the ABTS (p = 5.09E-03, 3.14E-03). Together, the results suggest that extracellular oxidases, primarily of bacterial origin, are the primary catalyst for soil iodination in aerobic, surface soils of deciduous and coniferous forests, and that soil N content may be indicative of the availability of binding sites for reactive iodine species.

Microbial Transformation of Iodine: From Radioisotopes to Iodine Deficiency.

Iodine is a biophilic element that is important for human health, both as an essential component of several thyroid hormones and, on the other hand, as a potential carcinogen in the form of radioiodine generated by anthropogenic nuclear activity. Iodine exists in multiple oxidation states (-1, 0, +1, +3, +5, and +7), primarily as molecular iodine (I2), iodide (I-), iodate [Formula: see text] , or organic iodine (org-I). The mobility of iodine in the environment is dependent on its speciation and a series of redox, complexation, sorption, precipitation, and microbial reactions. Over the last 15years, there have been significant advances in iodine biogeochemistry, largely spurred by renewed interest in the fate of radioiodine in the environment. We review the biogeochemistry of iodine, with particular emphasis on the microbial processes responsible for volatilization, accumulation, oxidation, and reduction of iodine, as well as the exciting technological potential of these fascinating microorganisms and enzymes.

Radioiodine sorption/desorption and speciation transformation by subsurface sediments from the Hanford Site.

During the last few decades, considerable research efforts have been extended to identify more effective remediation treatment technologies to lower the (129)I concentrations to below federal drinking water standards at the Hanford Site (Richland, USA). Few studies have taken iodate into consideration, though recently iodate, instead of iodide, was identified as the major species in the groundwater of 200-West Area within the Hanford Site. The objective of this study was thus to quantify and understand aqueous radioiodine species transformations and uptake by three sediments collected from the semi-arid, carbonate-rich environment of the Hanford subsurface. All three sediments reduced iodate (IO3(-)) to iodide (I(-)), but the loamy-sand sediment reduced more IO3(-) (100% reduced within 7 days) than the two sand-textured sediments (∼20% reduced after 28 days). No dissolved organo-iodine species were observed in any of these studies. Iodate uptake Kd values ([Isolid]/[Iaq]; 0.8-7.6 L/kg) were consistently and appreciably greater than iodide Kd values (0-5.6 L/kg). Furthermore, desorption Kd values (11.9-29.8 L/kg) for both iodate and iodide were consistently and appreciably greater than uptake Kd values (0-7.6 L/kg). Major fractions of iodine associated with the sediments were unexpectedly strongly bound, such that only 0.4-6.6 % of the total sedimentary iodine could be exchanged from the surface with KCl solution, and 0-1.2% was associated with Fe or Mn oxides (weak NH2HCl/HNO3 extractable fraction). Iodine incorporated into calcite accounted for 2.9-39.4% of the total sedimentary iodine, whereas organic carbon (OC) is likely responsible for the residual iodine (57.1-90.6%) in sediments. The OC, even at low concentrations, appeared to be controlling iodine binding to the sediments, as it was found that the greater the OC concentrations in the sediments, the greater the values of uptake Kd, desorption Kd, and the greater residual iodine concentrations (non-exchangeable, non-calcite-incorporated and non-Mn, Fe-oxide associated). This finding is of particular interest because it suggests that even very low OC concentrations, <0.2%, may have an impact on iodine geochemistry. The findings that these sediments can readily reduce IO3(-), and that IO3(-) sorbs to a greater extent than I(-), sheds light into earlier unexplained Hanford field data that demonstrated increases in groundwater (127)I(-)/(127)IO3(-) ratios and a decrease groundwater (129)IO3(-) concentrations along a transect away from the point sources, where iodine was primarily introduced as IO3(-). While a majority of the radioiodine does not bind to these alkaline sediments, there is likely a second smaller iodine fraction in the Hanford subsurface that is strongly bound, presumably to the sediment OC (and carbonate) phases. This second fraction may have an impact on establishing remediation goals and performance assessment calculations.

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

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 Mn(2+), 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.

Iodine-129 and iodine-127 speciation in groundwater at the Hanford site, US: iodate incorporation into calcite.

The geochemical transport and fate of radioiodine depends largely on its chemical speciation that is greatly affected by environmental factors. This study reports, for the first time, the speciation of stable and radioactive iodine in the groundwater from the Hanford Site. Iodate was the dominant species and accounted for up to 84% of the total iodine present. The alkaline pH (pH ∼ 8) and predominantly oxidizing environment may have prevented reduction of the iodate. In addition, groundwater samples were found to have large amounts of calcite precipitate which were likely formed as a result of CO2 degassing during removal from the deep subsurface (>70m depth). Further analyses indicated that between 7 and 40% of the dissolved (127)I and (129)I that was originally in the groundwater had coprecipitated in the calcite. Iodate was the main species incorporated into calcite and this incorporation process could be impeded by elevating the pH and decreasing ionic strength in groundwater. This study provides critical information for predicting the long-term fate and transport of (129)I. Furthermore, the common sampling artifact resulting in the precipitation of calcite by degassing CO2, had the unintended consequence of providing insight into a potential solution for the in situ remediation of groundwater (129)I.