Uranium Biogeochemistry in the Rhizosphere of a Contaminated Wetland.

The objective of this study was to determine if U sediment concentrations in a U-contaminated wetland located within the Savannah River Site, South Carolina, were greater in the rhizosphere than in the nonrhizosphere. U concentrations were as much as 1100% greater in the rhizosphere than in the nonrhizosphere fractions; however and importantly, not all paired samples followed this trend. Iron (but not C, N, or S) concentrations were significantly enriched in the rhizosphere. XAS analyses showed that in both sediment fractions, U existed as UO22+ coordinated with iron(III)-oxides and organic matter. A key difference between the two sediment fractions was that a larger proportion of U was adsorbed to Fe(III)-oxides, not organic matter, in the rhizosphere, where significantly greater total Fe concentrations and greater proportions of ferrihydrite and goethite existed. Based on 16S rRNA analyses, most bacterial sequences in both paired samples were heterotrophs, and population differences were consistent with the generally more oxidizing conditions in the rhizosphere. Finally, U was very strongly bound to the whole (unfractionated) sediments, with an average desorption Kd value (Usediment/Uaqueous) of 3972 ± 1370 (mg-U/kg)/(mg-U/L). Together, these results indicate that the rhizosphere can greatly enrich U especially in wetland areas, where roots promote the formation of reactive Fe(III)-oxides.

Molecular Interaction of Aqueous Iodine Species with Humic Acid Studied by I and C K-Edge X-ray Absorption Spectroscopy.

Iodine-129 is one of three key risk drivers at several US Department of Energy waste management sites. Natural organic matter (NOM) is thought to play important roles in the immobilization of aqueous iodide (I-) and iodate (IO3-) in the environment, but molecular interactions between NOM and iodine species are poorly understood. In this work, we investigated iodine and carbon speciation in three humic acid (HA)-I systems using I K-edge XANES and EXAFS and C K-edge XANES spectroscopy: (1) I- in the presence of laccase (an oxidase enzyme) and a mediator, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) in a pH 4 buffer, (2) I- in the presence of lactoperoxidase (LPO) and H2O2 in a pH 7 buffer, and (3) IO3- in a pH 3 groundwater. Both oxidase and peroxidase systems could oxidize I- to I2 or hypoiodide (HOI) leading to organo-I formation. However, the laccase-ABTS mediator was the most effective and enhanced I- uptake by HA up to 13.5 mg/g, compared to 1.9 mg/g for the LPO-H2O2. IO3- was abiotically reduced to I2 or HOI leading to an organo-I formation. Pathways for HA iodination include covalent modification of aromatic-type rings by I2 / HOI or iodine incorporation into newly formed benzoquinone species arising from the oxidation of phenolic C species. This study improves our molecular-level understanding of NOM-iodine interactions and stresses the important role that mediators may play in the enzymatic reactions between iodine and NOM.

Rapid Degradation of Oil in Mesocosm Simulations of Marine Oil Snow Events.

Following the Deepwater Horizon oil spill in the Gulf of Mexico, natural marine snow interacted with oil and dispersants forming marine oil snow (MOS) that sank from the water column to sediments. Mesocosm simulations demonstrate that Macondo surrogate oil incorporates into MOS and can be isolated, extracted, and analyzed via Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Up to 47% of the FTICR-MS signal from MOS extracts can be attributed to formulas also found in Macondo surrogate oil demonstrating extensive oil incorporation. Additionally, oxygenation patterns for MOS extracts provide evidence for degraded oil compounds. Formulas having similar double bond equivalents but higher oxygen content (MOS CHO: CHO2-9, DBE2-16, MOS CHON: CHO0-7N1, DBE9-18; Macondo CHO: CHO1-4, DBE2-15, CHON: CHO0-3N1, DBE9-21) were found in MOS extracts generating isoabundance distributions similar to those of environmentally aged oil. Such shifts in molecular composition are consistent with the transformation of high DBE oil components, unobservable by FTICR-MS until oxygenation in the mesocosms. Low light conditions and the rapid proliferation of hydrocarbon-degraders observed in parallel studies suggest biological activity as the primary cause of oil degradation. MOS may thus represent an important microenvironment for oil degradation especially during its long transit below the euphotic zone to sediments.

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.

Substructural Components of Organic Colloids from a Pu-Polluted Soil with Implications for Pu Mobilization.

Contaminated soil organic matter from the Rocky Flats Environmental Technology Site (RFETS) has been previously shown to accumulate plutonium (Pu) in a colloidal subfraction and is hypothesized to contain cutin-like chemical structures cross-linked with hydroxamate functionality. The present study further characterizes this high Pu affinity subfraction using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) and discovers additional substructural components. The Pu-enriched fraction was extracted and purified through a series of ultrafiltration and isoelectric focusing (IEF) electrophoresis steps. Predominantly low H/C and high double-bond equivalence (DBE) aromatic and condensed aromatic molecular formulas were detected, 66% of which are included in a COO Kendrick mass defect (KMD) homologous series. This suggests the existence of polycarboxylated aromatic and condensed aromatic formulas, with CHON-type COO KMD formulas relatively more abundant in the purified subfraction where Pu had been observed than in the crude soil fractions which had successively lower Pu concentrations. Nitrogen contents increased with the progression of purification (bulk soil → crude colloid → IEF colloid) and coincided with the trend of Pu concentration; thus, we propose that these nitrogen and carboxyl functionalities of aromatic compounds may also impart significant Pu chelation character to the colloid.

Plutonium Partitioning Behavior to Humic Acids from Widely Varying Soils Is Related to Carboxyl-Containing Organic Compounds.

In order to examine the influence of the HA molecular composition on the partitioning of Pu, ten different kinds of humic acids (HAs) of contrasting chemical composition, collected and extracted from different soil types around the world were equilibrated with groundwater at low Pu concentrations (10-14 M). Under mildly acidic conditions (pH ∼ 5.5), 29 ± 24% of the HAs were released as colloidal organic matter (>3 kDa to <0.45 µm), yet this HA fraction accounted for a vast majority of the bound Pu, 76 ± 13% on average. In comparison, the particulate HA fraction bound only 8 ± 4% on average of the added Pu. The truly dissolved Pu fraction was typically <1%. Pu binding was strongly and positively correlated with the concentrations of organic nitrogen in both particulate (>0.45 µm) and colloidal phases in terms of activity percentage and partitioning coefficient values (logKd). Based on molecular characterization of the HAs by solid state 13C nuclear magnetic resonance (NMR) and elemental analysis, Pu binding was correlated to the concentration of carboxylate functionalities and nitrogen groups in the particulate and colloidal phases. The much greater tendency of Pu to bind to colloidal HAs than to particulate HA has implications on whether NOM acts as a Pu source or sink during natural or man-induced episodic flooding.

Unique Organic Matter and Microbial Properties in the Rhizosphere of a Wetland Soil.

Wetlands attenuate the migration of many contaminants through a wide range of biogeochemical reactions. Recent research has shown that the rhizosphere, the zone near plant roots, in wetlands is especially effective at promoting contaminant attenuation. The objective of this study was to compare the soil organic matter (OM) composition and microbial communities of a rhizosphere soil (primarily an oxidized environment) to that of the bulk wetland soil (primarily a reduced environment). The rhizosphere had elevated C, N, Mn, and Fe concentrations and total bacteria, including Anaeromyxobacter, counts (as identified by qPCR). Furthermore, the rhizosphere contained several organic molecules that were not identified in the nonrhizosphere soil (54% of the >2200 ESI-FTICR-MS identified compounds). The rhizosphere OM molecules generally had (1) greater overall molecular weights, (2) less aromaticity, (3) more carboxylate and N-containing COO functional groups, and (4) a greater hydrophilic character. These latter two OM properties typically promote metal binding. This study showed for the first time that not only the amount but also the molecular characteristics of OM in the rhizosphere may in part be responsible for the enhanced immobilization of contaminants in wetlands. These finding have implications on the stewardship and long-term management of contaminated wetlands.

Evidence for Hydroxamate Siderophores and Other N-Containing Organic Compounds Controlling (239,240)Pu Immobilization and Remobilization in a Wetland Sediment.

Pu concentrations in wetland surface sediments collected downstream of a former nuclear processing facility in F-Area of the Savannah River Site (SRS), USA, were ∼2.5 times greater than those measured in the associated upland aquifer sediments; similarly, the Pu concentration solid/water ratios were orders of magnitude greater in the wetland than in the low-organic matter content aquifer soils. Sediment Pu concentrations were correlated to total organic carbon and total nitrogen contents and even more strongly to hydroxamate siderophore (HS) concentrations. The HS were detected in the particulate or colloidal phases of the sediments but not in the low molecular weight fractions (<1000 Da). Macromolecules which scavenged the majority of the potentially mobile Pu were further separated from the bulk mobile organic matter fraction ("water extract") via an isoelectric focusing experiment (IEF). An electrospray ionization Fourier-transform ion cyclotron resonance ultrahigh resolution mass spectrometry (ESI FTICR-MS) spectral comparison of the IEF extract and a siderophore standard (desferrioxamine; DFO) suggested the presence of HS functionalities in the IEF extract. This study suggests that while HS are a very minor component in the sediment particulate/colloidal fractions, their concentrations greatly exceed those of ambient Pu, and HS may play an especially important role in Pu immobilization/remobilization in wetland sediments.

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.

Temporal variation of iodine concentration and speciation (127I and 129I) in wetland groundwater from the Savannah River Site, USA.

(129)I derived from a former radionuclide disposal basin located on the Savannah River Site (SRS) has concentrated in a wetland 600 m downstream. To evaluate temporal environmental influences on iodine speciation and mobility in this subtropical wetland environment, groundwater was collected over a three-year period (2010-2012) from a single location. Total (127)I and (129)I showed significant temporal variations, ranging from 68-196 nM for (127)I and <5-133 pCi/L for (129)I. These iodine isotopes were significantly correlated with groundwater acidity and nitrate, two parameters elevated within the contaminant plume. Additionally, (129)I levels were significantly correlated with those of (127)I, suggesting that biogeochemical controls on (127)I and (129)I are similar within the SRS aquifer/wetland system. Iodine speciation demonstrates temporal variations as well, reflecting effects from surface recharges followed by acidification of groundwater and subsequent formation of anaerobic conditions. Our results reveal a complex system where few single ancillary parameters changed in a systematic manner with iodine speciation. Instead, changes in groundwater chemistry and microbial activity, driven by surface hydrological events, interact to control iodine speciation and mobility. Future radiological risk models should consider the flux of (129)I in response to temporal changes in wetland hydrologic and chemical conditions.

Plutonium immobilization and remobilization by soil mineral and organic matter in the far-field of the Savannah River Site, U.S.

To study the effects of natural organic matter (NOM) on Pu sorption, Pu(IV) and (V) were amended at environmentally relevant concentrations (10(-14) M) to two soils of contrasting particulate NOM concentrations collected from the F-Area of the Savannah River Site. More Pu(IV) than (V) was bound to soil colloidal organic matter (COM). A de-ashed humic acid (i.e., metals being removed) scavenged more Pu(IV,V) into its colloidal fraction than the original HA incorporated into its colloidal fraction, and an inverse trend was thus observed for the particulate-fraction-bound Pu for these two types of HAs. However, the overall Pu binding capacity of HA (particulate + colloidal-Pu) decreased after de-ashing. The presence of NOM in the F-Area soil did not enhance Pu fixation to the organic-rich soil when compared to the organic-poor soil or the mineral phase from the same soil source, due to the formation of COM-bound Pu. Most importantly, Pu uptake by organic-rich soil decreased with increasing pH because more NOM in the colloidal size desorbed from the particulate fraction in the elevated pH systems, resulting in greater amounts of Pu associated with the COM fraction. This is in contrast to previous observations with low-NOM sediments or minerals, which showed increased Pu uptake with increasing pH levels. This demonstrates that despite Pu immobilization by NOM, COM can convert Pu into a more mobile form.

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.

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.

Presence of aromatic-rich organic matter and its characterization in grout materials: Implications for radionuclide immobilization.

Grout materials are commonly used to immobilize low-level radioactive waste. Organic moieties can be unintentionally present in common ingredients used to make these grout waste forms, which may result in the formation of organo-radionuclide species. These species can positively or negatively affect the immobilization efficiency. However, the presence of organic carbon compounds is rarely considered in models or characterized chemically. Here, we quantify the organic pool of grout formulations with and without slag, as well as the individual dry ingredients used to make the grout samples (ordinary Portland cement (OPC), slag and fly ash), including total organic carbon (TOC) and black carbon, followed by aromaticity evaluation and molecular characterization via Electro Spray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICRMS). All dry grout ingredients contained significant amounts of organic carbon, ranging from 550 mg/kg to 6250 mg/kg for the TOC pool, with an averaged abundance of 2933 ± 2537 mg/kg, of which 60 ± 29% was composed of black carbon. The significant abundance of a black carbon pool implies the presence of the aromatic-like compounds, which was further identified by both phosphate buffer-assisted aromaticity evaluation (e.g., >1000 mg-C/kg as aromatic-like carbon in the OPC) and dichloromethane (DCM) extraction with ESI-FTICRMS analysis. Besides aromatic-like compounds, other organic moieties were also detected in the OPC, such as carboxyl-containing aliphatic molecules. While the organic compound only consists of minor fractions of the grout materials investigated, our observations of the presence of various radionuclide-binding organic moieties suggests the potential formation of organo-radionuclides, such as radioiodine, which might be present at lower molar concentrations than TOC. Evaluating the role of organic carbon complexation in controlling the disposed radionuclides, especially for those radionuclides with strong association with organic carbon, has important implications for the long-term immobilization of radioactive waste in grout systems.

Carbon capture by macroalgae Sarcodia suae using aquaculture wastewater and solar energy for cooling in subtropical regions.

Rapid growth in the aquaculture industry and corresponding increases in nutrient and organic carbon levels in coastal regions can lead to eutrophication and increased greenhouse gas emissions. Macroalgae are the organisms primarily responsible for the capture of CO2 and removal of nutrients from coastal waters. In the current study, we developed a novel wastewater treatment system in which the red macroalga, Sarcordia suae, is used to capture CO2 under thermostatic conditions in subtropical regions. In 2020 (without temperature control), the carbon capture rate (CCR) of Sarcordia suae varied considerably with the season: winter/spring (2.1-3.9 g-C m-2 d-1) and summer (0.09 g-C m-2 d-1). In 2021, solar powered cooling reduced summer seawater temperatures from 31 to 33 °C to 23-25 °C with a corresponding increase in the mean CCR: winter/spring (2-7 g-C m-2 d-1) and summer (1.33 g-C m-2 d-1). The proposed aquaculture wastewater system proved highly efficient in removing nitrogen (20.7 mg-N g-1 DW d-1, DW = dry weight) and phosphorus (4.4 mg-P g-1 DW d-1). Furthermore, the high density of Sarcodia (1.10 ± 0.03 g cm-3) would permit the harvesting and subsequent dumping of Sarcodia in deep off-shore waters. This study demonstrated a low-cost land-based seaweed cultivation system for capturing CO2 and excess nutrients from aquaculture wastewater year-round under temperature controlled environments in subtropical regions.

Aggregation, dissolution, and stability of quantum dots in marine environments: importance of extracellular polymeric substances.

There is an increasing concern that a considerable fraction of engineered nanoparticles (ENs), including quantum dots (QDs), will eventually find their way into the marine environment and have negative impacts on plankton. As ENs enter the ocean, they will encounter extracellular polymeric substances (EPS) from microbial sources before directly interacting with plankton cells. In this study, EPS harvested from four phytoplankton species, Amphora sp., Dunaliella tertiolecta, Phaeocystis globosa, and Thalassiosira pseudonana, were examined for potential interactions with CdSe nonfunctionalized and functionalized (carboxyl- and amine-) QDs in artificial seawater. Our results show that EPS do not reduce the solubility of QDs but rather decrease their stability. The degradation rate of QDs was positively correlated to the protein composition of EPS (defined by the ratio of protein/carbohydrate). Two approaches showed significant inhibition to the degradation of carboxyl-functionalized QDs: (1) the presence of an antioxidant, such as N-acetyl cysteine, and (2) absence of light. Owing to the complexity in evaluating integrated effects of QDs intrinsic properties and the external environmental factors that control the stability of QDs, conclusions must be based on a careful consideration of all these factors when attempting to evaluate the bioavailability of QDs and other ENs in the marine environments.

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.

Collection of lanthanides and actinides from natural waters with conventional and nanoporous sorbents.

Effective collection of trace-level lanthanides and actinides is advantageous for recovery and recycling of valuable resources, environmental remediation, chemical separations, and in situ monitoring. Using isotopic tracers, we have evaluated a number of conventional and nanoporous sorbent materials for their ability to capture and remove selected lanthanides (Ce and Eu) and actinides (Th, Pa, U, and Np) from fresh and salt water systems. In general, the nanostructured materials demonstrated a higher level of performance and consistency. Nanoporous silica surface modified with 3,4-hydroxypyridinone provided excellent collection and consistency in both river water and seawater. The MnO(2) materials, in particular the high surface area small particle material, also demonstrated good performance. Other conventional sorbents typically performed at levels below the nanostructured sorbents and demonstrate a larger variability and matrix dependency.

Large seasonal fluctuations of groundwater radioiodine speciation and concentrations in a riparian wetland in South Carolina.

Recent studies evaluating multiple years of groundwater radioiodine (129I) concentration in a riparian wetland located in South Carolina, USA identified strong seasonal concentration fluctuations, such that summer concentrations were much greater than winter concentrations. These fluctuations were observed only in the wetlands but not in the upland portion of the plume and only with 129I, and not with other contaminants of anthropogenic origin: nitrate/nitrite, strontium-90, technecium-99, tritium, or uranium. This unexplained observation was hypothesized to be the result of strongly coupled processes involving hydrology, water temperature, microbiology, and chemistry. To test this hypothesis, an extensive historical groundwater database was evaluated, and additional measurements of total iodine and iodine speciation were made from recently collected samples. During the summer, the water table decreased by as much as 0.7 m, surface water temperature increased by as much as 15 °C, and total iodine concentrations were consistently greater (up to 680%) than the following winter months. Most of the additional iodine observed in the summer could be attributed to proportional gains in organo-iodine, and not iodide or iodate. Furthermore, 129I concentrations were observed to be two-orders-of-magnitude greater at the bottom of the upland aquifer than at the top. A coupled hydrological and biogeochemical conceptual model is proposed to tie these observations together. First, as the surface water temperature increased during the summer, microbial activity was enhanced, which in turn stimulated the formation of mobile organo-I. Hydrological processes were also likely involved in the observed iodine seasonal changes: (1) as the water table decreased in summer, the remaining upland water entering the wetland was comprised of a greater proportion of water containing elevated iodine concentrations from the low depths, and (2) water flow paths in summer changed such that the wells intercepted more of the contaminant plume and less of the diluting rainwater (due to evapotranspiration) and streamwater (as the lower levels promote a predominantly recharging system). These results underscore the importance of coupled processes influencing contaminant concentrations, and the need to assess seasonal contaminant variations to optimize long-term monitoring programs of wetlands.

1H-13C heteronuclear single quantum coherence NMR evidence for iodination of natural organic matter influencing organo-iodine mobility in the environment.

The complex biogeochemical behavior of iodine (I) isotopes and their interaction with natural organic matter (NOM) pose a challenge for transport models. Here, we present results from iodination experiments with humic acid (HA) and fulvic acid (FA) using 1H-13C heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectroscopy. Even though not a quantitative approach, 1H-13C HSQC NMR corroborated that iodination of NOM occurs primarily through aromatic electrophilic substitution of proton by I, and also revealed how iodination chemically alters HA and FA in a manner that potentially affects the mobility of iodinated NOM in the environment. Three types of iodination experiments were conducted with HA and FA: a) non-enzymatic iodination by IO3- (pH 3) and I- (pH 4 and 7), b) addition of lactoperoxidase to promote I--iodination in the presence of the co-substrate, H2O2 (pH 7), and c) addition of laccase for facilitating I--iodination in the presence of O2, with or without a mediator (pH 4). When mediators or H2O2 were present, extracellular oxidases and peroxidases enhanced I- incorporation into NOM by between 54% and 3400%. Iodination of HA, which was less than that of FA, enhanced HA's stability (inferred from increases in aliphatic compounds, decreases in carbohydrate moieties, and thus increased molecular hydrophobicity) yet reduced HA's tendency to incorporate more iodine. As such, HA is expected to act more as a sink for iodine in the environment. In contrast, iodination of FA appeared to generate additional iodine binding sites, which resulted in greater iodine uptake capability and enhanced mobility (inferred from decreases in aliphatic compounds, increases in carbohydrates, and thus decreases in molecular hydrophobicity). These results indicate that certain NOM moieties may enhance while others may inhibit radioiodine mobility in the aqueous environment.