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Forecasting the long-term fate of plutonium (Pu) is becoming increasingly important as more worldwide military and nuclear-power waste is being generated. Nagasaki sediments containing bomb-derived Pu that was deposited in 1945 provided a unique opportunity to explore the long-term geochemical behavior of Pu. Through a combination of selective extractions and molecular characterization via electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS), we determined that 55 ± 3% of the bomb-derived 239,240Pu was preferentially associated with more persistent organic matter compounds in Nagasaki sediments, particularly those natural organic matter (NOM) stabilized by Fe oxides (NOMFe-oxide). Other organic matter compounds served as a secondary sink of these bomb-derived 239,240Pu (31 ± 2% on average), and

Silver-impregnated zeolite (AgIZ) has been used for removing radioiodine from contaminated groundwater and nuclear waste streams and the worldwide inventory of such secondary waste is rapidly increasing. The objective of this study was to 1) quantify the effectiveness of two grout waste forms for disposing of the used AgIZ, and 2) determine the I speciation leached from AgIZ encapsulated in grout. A 60-day kinetics batch experiment demonstrated that AgIZ encapsulated in slag-free grout was extremely effective at immobilizing I and Ag, a potential non-radioactive carcinogen. However, AgIZ encapsulated in slag-containing grout, the most common type of grout used for low-level radioactive waste disposal, was entirely ineffective at immobilizing I. While the slag-free grout with AgIZ released only 3.3 μg/L Itotal into the contact solution, the slag-containing grout released 19,269 μg/L Itotal. Based on thermodynamic calculations, the strongly reducing conditions of the slag-containing system (Eh was −392 mV) promoted the reductive dissolution of the AgI, forming Ag0(aq) and releasing iodide (I−) into the aqueous phase. The slag-free grout system was maintained under more oxidizing conditions (Eh was 439 mV) and a minimal amount of I was released from the grout. In both grout systems, the aqueous I, originally added to the AgZ as iodide, was composed primarily of iodide and org-I, and essentially no iodate was detected. More organo-I was detected in the slag-free than the slag-containing grout system because the high redox potential of the former system was more conducive to the formation of oxidized I species, such as I2, which may be intermediates in the covalent bonding of I with organic C in grout. Iodine K-edge XANES analysis indicated that I existed exclusively as silver iodide in both AgIZ-grout samples. Together, these results indicate that subsurface grout disposal of AgIZ waste should be done under oxidizing conditions and that radioiodide released from AgIZ can undergo speciation transformations that have important implications on subsequent mobility and estimated risk. Keywords: Iodine speciation, Cement, Slag, Immobilization, Redox, Silver-impregnated zeolite

Iodine-129 is a key risk driver in most low-level waste cementitious waste repositories. Objectives of this study were to determine iodine speciation in cementitious materials with slag (Grout+slag) and without slag (Grout–slag) and its impact on iodine immobilization. Irrespective of which iodine species was amended to the aqueous phase, there were no significant differences in uptake-Kd values (∼3 L/kg). However, when the various iodine species were hydrated with the grout, the release-Kd values (6.1–121.8 L/kg) were significantly greater than the uptake-Kd values, and the amended iodine speciation (I− ≪ org-I ≤ IO3−) and grout formulation (Grout–slag

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 interactions influence nearly one-half of the global biogeochemical flux of major elements of the marine ecosystem. Despite their ecological importance, microbial interactions remain poorly understood and even less is known regarding the effects of anthropogenic perturbations on these microbial interactions. The Deepwater Horizon oil spill exposed the Gulf of Mexico to ∼4.9 million barrels of crude oil over 87 days. We determined the effects of oil exposure on microbial interactions using short- and long-term microcosm experiments with and without Macondo surrogate oil. Microbial activity determined using radiotracers revealed that oil exposure negatively affected substrate uptake by prokaryotes within 8 h and by eukaryotes over 72 h. Eukaryotic uptake of heterotrophic exopolymeric substances (EPS) was more severely affected than prokaryotic uptake of phototrophic EPS. In addition, our long-term exposure study showed severe effects on photosynthetic activity. Lastly, changes in microbial relative abundances and fewer co-occurrences among microbial species were mostly driven by photosynthetic activity, treatment (control vs. oil), and prokaryotic heterotrophic metabolism. Overall, oil exposure affected microbial co-occurrence and/or interactions possibly by direct reduction in abundance of one of the interacting community members and/or indirect by reduction in metabolism (substrate uptake or photosynthesis) of interacting members.

Marine snow was implicated in the transport of oil to the seafloor during the Deepwater Horizon oil spill, but the exact processes remain controversial. In this study, we investigated the concentrations and distributions of the 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs) in marine snow aggregates collected during a mesocosm experiment. Seawater only, oil in a water accommodated fraction (WAF), and Corexit-enhanced WAF (DCEWAF) were incubated for 16 d. Both WAF and DCEWAF aggregates were enriched in heavy molecular weight PAHs but depleted in naphthalene. DCEWAF aggregates had 2.6 times more total 16 PAHs than the WAF (20.5 vs. 7.8 &micro, g/g). Aggregates in the WAF and DCEWAF incorporated 4.4% and 19.3%, respectively of the total PAHs in the mesocosm tanks. Our results revealed that marine snow sorbed and scavenged heavy molecular weight PAHs in the water column and the application of Corexit enhanced the incorporation of PAHs into the sinking aggregates.

Large amounts of mucous-rich oil-containing marine snow formed in surface waters adjacent to the Deepwater Horizon spill. This marine oil snow (MOS) was implicated in oil delivery to the seafloor. Whether the use of chemical dispersants increased or decreased MOS sedimentation remains controversial. We conducted mesocosm experiments testing the effects of oil and oil plus a dispersant on MOS formation and sedimentation, in coastal seawater . The four treatments used were a surrogate Macondo oil water accommodated fraction (“WAF”), two concentrations of chemically-enhanced WAF (“CEWAF” and diluted CEWAF, “DCEWAF”) containing a dispersant and oil, and Controls (no additions). Based on radiocarbon and 13 C NMR results, the presence of dispersants enhanced the amounts of petro-carbon being incorporated into the sinking oil-carrying aggregates (aka MOS). However, most of the chemically-dispersed oil preferentially partitioned into the colloidal and suspended particulate fractions rather than into the rapidly forming MOS. Thus the oil and non-petro-carbon sedimentation efficiency in treatments with a dispersant was much lower, compared to those in the Control and WAF treatments, during the four-day mesocosm experiment. Formation of MOS and its subsequent sinking sequestered the oil in two stages: first via terrestrial-derived detritus containing humic compounds, and subsequently via freshly produced material, such as exopolymeric substances produced by phytoplankton and bacteria.

Large-scale exopolymeric substances (EPS) formation was observed in contaminated surface waters of the Gulf of Mexico , after the Deepwater Horizon oil spill. The conditions under which EPS are produced can cause variations in their physico-chemical properties , affecting the fate of the oil through either emulsification or coagulation with particles, followed by aggregation and marine oil snow (MOS) sedimentation . Here, we report results from a four-day mesocosm experiment that examined EPS production, the change in the bulk chemical composition (mainly polysaccharides and proteins), as well as the partitioning into different size fractions (suspended particulate matter (SPM), colloidal fraction, and sinking MOS). The treatments included 1) natural coastal seawater (Control), 2) a water accommodated fraction of oil (WAF), 3) a chemically-enhanced WAF with addition of oil dispersant Corexit (CEWAF), and 4) a diluted CEWAF (DCEWAF). Generally, the presence of WAF stimulated more extracellular polysaccharide production, whereas the addition of Corexit promoted more protein production. Moreover, marine aggregates changed from a terrestrial signature (higher aromaticity, lower EPS content and more uniform monosaccharide distribution) in the early stages of the experiment, to a fresher autochthonous signature (less aromatic, higher EPS content and glucose-dominated monosaccharide distribution) in the later stage of the mesocosm experiment. Corexit promoted the association between oil and proteins, assisting to emulsify the oil in colloids and SPM and delay the settling of EPS and oil (MOS) for the duration of the mesocosm. Furthermore, when oil, especially Corexit-dispersed oil, was present, extracellular polysaccharides were preferentially incorporated into sinking MOS relative to proteins, as evidenced from a lower protein-C/carbohydrate-C ratio of the sinking MOS than those of SPM and colloidal fraction in WAF, CEWAF and DCEWAF, respectively. This is in contrast to a higher protein-C/carbohydrate-C ratio in the sinking marine snow than those of SPM and colloidal fraction in the control. Likely, microbially-mediated extracellular polysaccharides are the key component that anchors the mineral ballast until the aggregates become dense enough and overcome the buoyancy added to the aggregates as a result of their association with oil/Corexit. We conclude that interactions between Corexit and EPS components regulate petroleum hydrocarbon distribution between the water column and sinking MOS.

Amphiphilic substances can interact with oil in the water to form emulsions and aggregates; dispersants are designed to form emulsions to prevent oil droplets from coalescing and stabilize them in a suspension. Amphiphilic extracellular polymeric substances (EPS) concentrated at the air-water interface where surface tension was measured to determine their propensity for formation of emulsions and/or aggregates. Here we investigated mechanisms governing the self-assembly and phase separation for protein-polysaccharide-oil-dispersant interactions through measurements of surface tension, chemical composition, and confocal microscopy. EPS colloid fractions from treatments of WAF (water accommodated fraction of oil), CEWAF (chemically enhanced WAF using the dispersant Corexit), and a control mesocosm were examined. In analyzing the size fractions of water column samples, it was found that treatments with oil and/or Corexit showed EPS with enhanced protein:polysaccharide carbon-based ratios and lower surface tension (SFT), suggesting the effective bioemulsifying effects of proteins. In addition, EPS model constituents of protein slightly increased SFT at low concentrations of less than a few mg/L, but decreased it at higher concentrations of 8 mg/L or more. These model molecules appear to be more efficient than Corexit in inducing the self-assembly of micelles in the seawater even when only very low concentrations of these constituents are present. Our results suggest that EPS are more efficient than Corexit at forming micelles. Results from this study provides mechanistic insights into the fate and distribution of oil in the surface ocean.

Mercury (Hg) was discharged in the late 1960s into the Penobscot River by the Holtra-Chem chlor-alkali production facility, which was in operation from 1967 to 2000. To assess the transport and distribution of total Hg, and recovery of the river and estuary system from Hg pollution, physical and radiochemical data were assembled from sediment cores collected from 58 of 72 coring stations sampled in 2009. These stations were located throughout the lower Penobscot River, and included four principal study regions, the Penobscot River (PBR), Mendall Marsh (MM), the Orland River (OR), and the Penobscot estuary (ES). To provide the geochronology required to evaluate sedimentary total Hg profiles, 58 of 72 sediment cores were dated using the atmospheric radionuclide tracers 137Cs, 210Pb, and 239,240Pu. Sediment cores were assessed for depths of mixing, and for the determination of sediment accumulation rates using both geochemical (total Hg) and radiochemical data. At most stations, evidence for significant vertical mixing, derived from profiles of 7Be (where possible) and porosity, was restricted to the upper ~1-3cm. Thus, historic profiles of both total Hg and radionuclides were only minimally distorted, allowing a reconstruction of their depositional history. The pulse input tracers 137Cs and 239,240Pu used to assess sediment accumulation rates agreed well, while the steady state tracer 210Pb exhibited weaker agreement, likely due to irregular lateral sediment inputs.

During the Deepwater Horizon oil spill, a large amount of marine oil snow (MOS) was formed in surface waters of the Gulf of Mexico (GOM) that eventually settled to the bottom. MOS consists of a microbially colonized matrix of extracellular polymeric substances (EPS), to which cells, and both ionic (e.g., trace nutrients, Ca 2+ ) and non-ionic (e.g., toxic oil) substances can attach. The secretion of EPS is one of the microbial defense strategies against harmful or stressful environmental situations. In the surface waters, the toxicity of oil can be enhanced by elevated oxidative stress through UV radiation . To test the effects of sunlight on the composition and secretion of EPS and the subsequent aggregation process, we conducted short-term irradiation experiments in three treatments, i.e., control (GOM coastal seawater), water accommodated fraction of oil (WAF), and chemically-enhanced WAF (CEWAF). EPS composition (mainly carbohydrates and proteins) was quantified in the colloidal and aggregate fractions. In addition, bacterial abundance, live/dead cell ratio, particle size distribution , and the ambient hydroxyl radical ( OH) formation rate were measured under these conditions. We found that in the presence of oil, natural sunlight stimulated polysaccharide secretion, coinciding with increased reactive oxygen species (ROS; i.e. OH) production. Moreover, formation of larger sized aggregates (>10 μm) was observed in the irradiated WAF treatments. The results support the hypothesis that sunlight plays an important role in MOS formation during an oil spill.

We examined total mercury (Hg) distributions in sediments from the Penobscot River and estuary, Maine, a site of extensive Hg releases from HoltraChem (1967–2000). Our objectives were to quantify: (1) bottom sediment Hg inventories (upper ~ 1 m; 50–100 y); (2) sediment accumulation rates; and (3) contemporary Hg fluxes to bottom sediments; by sampling the Penobscot River (PBR), Mendall Marsh (MM), the Orland River (OR) and the Penobscot estuary (ES). Hg was rapidly distributed here, and the cumulative total (9.28 metric tons) associated with sediments system-wide was within the range released (6–12 metric tons). Evidence of sediment/Hg remobilization was observed in cores primarily from the PBR, and to a lesser extent the ES, whereas cores from MM, most of the OR, the ES, and half from the PBR exhibited sharp peaks in Hg concentrations at depth, followed by gradual decreases towards the surface. Based on background PBR sediment Hg concentrations (100 ng g− 1), “elevated” (300 ng g− 1), or “highly elevated” (600 ng g− 1) Hg concentrations in sediments, and resulting inventories, we assessed impact levels (“elevated” ≥ 270, or “highly elevated” ≥ 540 mg m− 2). 71% of PBR stations had “elevated”, and 29% had “highly elevated” Hg inventories; 45% of MM stations had “elevated”, and 27% had “highly elevated” inventories; 80% of OR stations had “elevated” inventories only; and 17% of ES stations had “elevated” inventories only. Most “highly elevated” stations were located within 8 km of HoltraChem, in MM, in the PBR, and in the OR. Near-surface sediments in the OR, PBR and MM were all “highly elevated”, while those in the ES were “elevated”, on average. Mean Hg fluxes to bottom sediments were greatest in the OR (554), followed by the PBR (469), then MM (452), and finally the ES (204 ng cm− 2 y− 1).

Uptake of six particle-reactive and/or redox-sensitive radionuclides (210Pb, 234Th, 7Be, 59Fe, 237Np and 233Pa) by 14 humic acids (HAs) was investigated in artificial groundwater under mildly acidic conditions (pH~5.5). In HA-groundwater slurry, Pb, Be, Fe and Pa bound strongly to particulate HA (>0.45 µm), supporting their application as tracers of soil erosion. Th bound strongly to the colloidal HA (3 kDa-0.45 µm) and as such, would not be a good candidate as a tracer for monitoring soil erosion. HAs likely reduced the oxidized neptunyl form (Np(V)O4+) to Np(IV) based on its enhanced particle-reactivity and Np uptake by particulate HAs, partially retarding the movement of anthropogenic 237Np in field polluted environments. Particulate/colloidal carbonyl/O-aryl (likely through hydroquinone/quinone) functionalities in the HA correlated to Np and Pa uptake, but only particulate O-aryl functionalities was responsible for Fe uptake. The carboxylate- and carbonyl/O-aryl-containing organic functionalities in the HA correlated strongly with Th uptake. In contrast, no significant correlations between organic parameters and Pb or Be uptake implied their predominance of uniform surface adsorption onto particles. This study provides novel insight into the binding of six radionuclides with different organic functionalities of three size fractions, as well as its possible impact on their application in the soil-tracing research.

Mercury (Hg) was discharged in the late 1960s into the Penobscot River by a chlor-alkali production facility, HoltraChem. Using total Hg concentration profiles from 56 stations (58 sediment cores) in the Penobscot River (PBR), Mendall Marsh (MM), Orland River (OR) and Penobscot Estuary (ES), and sediment accumulation rates derived using detailed profiles of total Hg concentrations and radionuclide activities ( 137 Cs, 239,240 Pu, 210 Pb), recovery from system-wide Hg pollution was assessed. Total Hg concentration profiles showed sharp maxima at depths attributed in time to a 1967 release date, and were divided into two sections: the first 21 years (1967–1988; rapid recovery), and the recent 21 years (1988–2009; slower recovery). The recent 21 years of Hg input were used to estimate ‘apparent’ recovery rates, yielding exponentially decreasing total Hg concentrations. Apparent recovery half-times (T 1/2 = ln2/α) were calculated from an exponential fit of Hg(t) = Hg(t = 21) ∗ exp(− α ∗ t) + Hg(∞) to total Hg concentration profiles over the past 21 years (assuming Hg(∞) of 0, 100, or 400 ng g − 1 ). Mean T 1/2 values were, at PBR 31 years (16 of 24 cores), at MM 22 years (9 of 11 cores), at ES 20 to 120 years (mean of 78 years; 12 of 18 cores), and at OR 69 years (3 of 5 cores). In 18 out of 57 cores, concentrations either increased towards the surface or remained the same, indicating slower or incomplete ‘communication’ with the larger system. The Penobscot River and Estuary system has recovered substantially since 1967, and top 1 cm sediment Hg concentrations (Hg(0)) from areas in rapid communication with the larger system are converging to 600–700 ng g − 1 (1967 maxima of 70,000 + ng g − 1 ). However, to recover from Hg(0) of 700 ng g − 1 to a Hg(∞) of − 1 would require 3 or more half-times.

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.

Large amounts of oil containing mucous-like marine snow formed in surface waters adjacent to the Deepwater Horizon spill that was implicated in oil delivery to the seafloor. However, whether chemical dispersants that were used increased or decreased the oil incorporation and sedimentation efficiency, and how exopolymeric substances (EPS) are involved in this process remains unresolved. To investigate the microbial responses to oil and dispersants in different oceanic settings, indicated by EPS production, petro- and non-petro carbon sedimentation, four mesocosm (M) experiments were conducted: 1) nearshore seawater with a natural microbial consortia (M2); 2) offshore seawater with f/20 nutrients (M3); 3) coastal seawater with f/20 nutrients (M4); 4) nearshore seawater with a natural microbial consortia for a longer duration (M5). Four treatments were conducted in M2, M3 and M4 whereas only three in M5: 1) a water accommodated fraction of oil (WAF), 2) a chemically-enhanced WAF prepared with Corexit (CEWAF, not in M5), 3) a 10-fold diluted CEWAF (DCEWAF); and 4) controls. Overall, oil and dispersants input, nutrient and microbial biomass addition enhanced EPS production. Dispersant addition tended to induce the production of EPS with higher protein/carbohydrate (P/C) ratios, irrespective of oceanic regions. EPS produced in M4 was generally more hydrophobic than that produced in M3. The P/C ratio of EPS in both the aggregate and the colloidal fraction was a key factor that regulated oil contribution to sinking aggregates, based on the close correlation with %petro-carbon in these fractions. In the short term (4–5 days), both the petro and non-petro carbon sedimentation efficiencies showed decreasing trends when oil/dispersants were present. In comparison, in the longer-term (16 days), petro-carbon sedimentation efficiency was less influenced by dispersants, possibly due to biological and physicochemical changes of the components of the oil-EPS-mineral phase system, which cooperatively controlled the sinking velocities of the aggregates.

Silver (Ag)-based technologies are amongst the most common approaches to removing radioiodine from aqueous waste streams. As a result, a large worldwide inventory of radioactive AgI waste presently exits, which must be stabilized for final disposition. In this work, the efficacy of silver-impregnated granular activated carbon (Ag-GAC) to remove iodide (I−), iodate (IO3−) and organo-iodine (org-I) from cementitious leachate was examined. In addition, cementitious materials containing I−, IO3−, or org-I loaded Ag-GAC were characterized by iodine K-edge XANES and EXAFS to provide insight into iodine stability and speciation in these waste forms. The Ag-GAC was very effective at removing I− and org-I, but ineffective at removing IO3− from slag-free grout leachate under oxic conditions. I− or org-I removal was due to the formation of insoluble AgI(s) or Ag-org-I(s) on the Ag-GAC. When I−-loaded Ag-GAC material was cured with slag-free and slag grouts, I− was released from AgI(s) to form a hydrated I− species. Conversely, when org-I loaded Ag-GAC material was cured in the two grout formulations, no change was observed in the iodine speciation, indicating the org-I species remained bound to the Ag. Because little IO3− was bound to the Ag-GAC, it was not detectable in the grout. Thus, grout formulation and I speciation in the waste stream can significantly influence the effectiveness of the long-term disposal of radioiodine associated with Ag-GAC in grout waste forms.

Extracellular polymeric substances (EPS), produced by microorganisms , are implicated for greatly influencing the fate of environmental contaminants , including oil. Transparent exopolymeric particles (TEP) are gel-like acidic polysaccharide particles that can be stained with Alcian blue, whereas Coomassie stainable particles (CSP) contain proteins and are stained with Coomassie brilliant blue. Marine microgels are reversibly formed from EPS. These terms are often used interchangeably, but they have rarely been measured simultaneously. Mesocosm and bottle experiments provided an opportunity to compare EPS, TEP, CSP and microgels in a water-accommodated fraction (WAF) of oil and seawater (control). Our results reveal that the biopolymers making up EPS, TEP and CSP consisted primarily of polysaccharides and proteins, mostly likely as proteoglycans and glycoproteins . Significant correlations were found between concentrations of TEP-C vs particulate organic carbon (POC), TEP-C vs particulate organic nitrogen (PON), TEP vs EPS, TEP vs CSP, TEP vs carbohydrates, proteins, CSP and carbohydrates, CSP vs proteins, and carbohydrates vs proteins. Chemical analysis of whole particles and colloids yielded both protein and polysaccharides concentrations higher than those in EDTA extraction, thus providing an upper limit of actual EPS contents in the particulate phase. The EPS that was electrostatically held onto particle surfaces (extractable by 1% EDTA) accounted for a minor (~4%) yet relatively constant proportion of TEP. Overall, the concentrations of the three terms ranked in the order of [gels] > [TEP] > [particulate EPS] in the water. Lastly, spectrophotometric methods have limitations in identifying complex or refractory polysaccharides, as evidenced by the comparison between NMR-quantified EPS and the total EPS determined by spectrophotometric methods. This study is the first time these terms were compared in the same sample. They provide useful information when reviewing historical TEP, CSP, EPS data collected field- and laboratory-studies, and provide linkages between them. In addition, they also demonstrate that they could provide complementary information relevant to ecosystem and flux studies.

In order to assess how environmental factors are affecting the distribution and migration of radioiodine and plutonium that were emitted from the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident, we quantified iodine and (239,240)Pu concentration changes in soil samples with different land uses (urban, paddy, deciduous forest and coniferous forest), as well as iodine speciation in surface water and rainwater. Sampling locations were 53-63 km northwest of the FDNPP within a 75-km radius, in close proximity of each other. A ranking of the land uses by their surface soil (4 cm) stable (127)I concentrations was coniferous forestdeciduous foresturbanpaddy, and (239,240)Pu concentrations ranked as deciduous forestconiferous forestpaddy ≥ urban. Both were quite distinct from that of (134)Cs and (137)Cs: urbanconiferous forestdeciduous forestpaddy, indicating differences in their sources, deposition phases, and biogeochemical behavior in these soil systems. Although stable (127)I might not have fully equilibrated with Fukushima-derived (129)I, it likely still works as a proxy for the long-term fate of (129)I. Surficial soil (127)I content was well correlated to soil organic matter (SOM) content, regardless of land use type, suggesting that SOM might be an important factor affecting iodine biogeochemistry. Other soil chemical properties, such as Eh and pH, had strong correlations to soil (127)I content, but only within a given land use (e.g., within urban soils). Organic carbon (OC) concentrations and Eh were positively, and pH was negatively correlated to (127)I concentrations in surface water and rain samples. It is also noticeable that (127)I in the wet deposition was concentrated in both the deciduous and coniferous forest throughfall and stemfall water, respectively, comparing to the bulk rainwater. Further, both forest throughfall and stemflow water consisted exclusively of organo-iodine, suggesting all inorganic iodine in the original bulk deposition (∼ 28.6% of total iodine) have been completely converted to organo-iodine. Fukushima-derived (239,240)Pu was detectable at a distance ∼ 61 km away, NW of FDNPP. However, it is confined to the litter layer, even three years after the FDNPP accident-derived emissions. Plutonium-239,240 activities were significantly correlated with soil OC and nitrogen contents, indicating Pu may be associated with nitrogen-containing SOM, similar to what has been observed at other locations in the United States. Together, these finding suggest that natural organic matter (NOM) plays a key role in affecting the fate and transport of I and Pu and may warrant greater consideration for predicting long-term stewardship of contaminated areas and evaluating various remediation options in Japan.

Iron (Fe), a micronutrient for algal growth, and plutonium (Pu), an anthropogenic radionuclide , share some common features. This includes similar oceanic distributions when different input modes are taken into account, as well as their chemical behavior, such as a high affinity to natural organic matter (NOM). The NOM produced by various phytoplankton communities can potentially influence Fe cycling in the ocean, and likely also influence the transport behavior of Pu. We conducted laboratory incubation experiments using the coccolithophore Emiliania huxleyi and the diatom Skeletonema costatum, in the presence of 59Fe and 238 Pu as radiotracers, in order to differentiate Fe and Pu uptake by extracellular exopolymeric substances (EPS) and intracellular biopolymers . The Fe and Pu distributions in select organic compound classes produced by these two types of phytoplankton, including proteins, total carbohydrates (TCHO) and uronic acids (URA), were compared. Our results indicated that most of the Fe and Pu (>95%) were found concentrated in E. huxleyi-derived non-attached EPS, while much less ( intracellular biopolymers > outer cell covering (i.e., frustule). In fact, over 50% of the Fe was concentrated in S. costatum -derived attached EPS and intracellular biopolymers. The diatom derived Fe-EPS complexes were more hydrophobic, with stronger tendency to aggregate in seawater . Fe binding to biopolymers in both E. huxleyi and S. costatum cultures was related to URA concentrations, but the overall distribution of URA between these two phytoplankton species was different (e.g., high intracellular abundance of URA in S. costatum but low intracellular URA abundance in E. huxleyi). Our findings suggest that the presence of URA on cellular surfaces of S. costatum (i.e., attached EPS) and its high intracellular fraction could be an indicator for Fe transport from the surrounding seawater to the diatom cells. However, for the coccolithophore E. huxleyi, Fe was not efficiently taken up during its growth. Instead, the more hydrophilic non-attached EPS (i.e., low protein/TCHO ratio) produced by E. huxleyi could have stabilized Fe in the colloidal form as Fe-EPS complexes. Similar partitioning behavior of Fe and Pu suggests that Pu isotopes can potentially serve as a tracer for Fe biogeochemistry in the ocean.

Microbially secreted exopolymeric substances (EPS), rich in polysaccharides and proteins, make up an important part of natural organic matter in the ocean, especially marine snow. While the attention in the oceanographic literature is focused more on the role of polysaccharides and less of proteins in EPS functions, the role of proteins, especially the role of the protein/carbohydrate (P/C) ratio of particles and colloids (macromolecular fraction) remains to be explored. EPS associated with particles forms a biofilm, where proteins are not only involved in cell surface attachment, but also in the stabilization of the biofilm matrix, and the development of a three-dimensional biofilm architecture. Here, we provide a perspective based on the most recent literature on EPS, marine oil spills and waste water treatment to describe the relationship between the P/C ratio of EPS and a number of biophysical properties related to biopolymer aggregation propensity, e.g., relative hydrophobicity, surface activity and surface tension, attachment efficiency, light-induced chemical crosslinking, and sedimentation efficiency of marine snow in marine environments.

Organic matter export from the euphotic zone is a key component of oceanic carbon (C) and nitrogen (N) cycles. Although interactions between these two cycles are important, studies on geochemical processes to directly connect them are limited. Here we show that sunlight can induce chemical aggregation of dissolved organic matter (DOM) into high N containing photo-aggregates. The size of microgels in natural coastal seawaters increased by18~25% compared to corresponding dark controls. Within a relatively short time (1 h), the C and N sequestered into the photo-aggregates accounted for 10% and 13% of the bulk particulate C and N, respectively. The N/C ratio of the photo-aggregates was two times higher after sunlight irradiation. Furthermore, we show that the aggregation process was dependent on reactive oxygen species (ROS). To accommodate for the different organic material in the marine environment, we monitored the particle size in various extracellular polymeric substances (EPS) and model biopolymers using flow cytometry, dynamic laser scattering, and scanning electron microscopy. We found that proteins play important roles in light-induced aggregation, which is in contrast to previous views that sunlight can break down DOM and interrupt aggregation. The photo-flocculation process involving organic N provides new insights into DOM assembly, bioavailability, and sedimentation, and thus potentially link the C and N cycles.

To study the binding mechanisms of radionuclides to organic moieties in colloidal organic matter (COM), marine colloids (1 kDa–0.2 μm) were isolated by cross-flow ultrafiltration from seawater of the west Pacific Ocean and the northern Gulf of Mexico. For the same purpose, exopolymeric substances (EPS) produced by laboratory-cultured diatoms were collected as well. In our study areas, colloidal organic carbon (COC) concentrations ranged from 6.5 to 202 μg-C/L in the Pacific Ocean, and were 808 μg-C/L in the Gulf of Mexico. The COM compositions (organic carbon, organic nitrogen, proteins, total hydrolysable amino acids, total polysaccharides, uronic acids, hydroxamate siderophores, hydroquinone) were quantified to examine the relationships between partition coefficients (Kc) of five different radionuclides, 234Th, 233Pa, 210Pb, 210Po and 7Be, and concentration ratios to COC of individual chelating biomolecules that could potentially act as a chelating moiety. The range of partition coefficients (Kc, reported as logKc) of radionuclides between water and the different colloidal materials was 5.12 to 5.85 for 234Th, 5.19 to 6.01 for 233Pa, 4.21 to 4.85 for 210Pb, 4.87 to 5.68 for 210Po, and 4.49 to 4.92 for 7Be, similar to values previously reported for lab and field determinations under different particle concentrations. While any relationship obtained between Kc and abundance of specific moieties could not be taken as proving the existence of colloidal organic binding ligands for the different radionuclides, it could suggest possible organic moieties involved in the scavenging of these natural radionuclides. Together with results from isoelectric focusing of radiolabeled COM, we conclude that binding to different biomolecules is nuclide-specific, with colloidal hydroxamate siderophoric moieties being important for the binding of Th and Pa radionuclides. Hydroquinones/quinone (HQ/Q) facilitated redox and chelation reactions seem to be involved in the binding of Pa and Be. However, the actual mechanisms are not clear. Individual amino acids, proteins, total polysaccharides and uronic acids did not yield significant relationships with logKc values of the different radionuclides. Nonetheless, our results provide new insights into the relative importance of different potential ligand moieties in COM in the binding and possible scavenging of specific radionuclides in the ocean.

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

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) 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 bindin...

A primary obstacle in understanding the fate and transport of the toxic radionuclide (129)I (a thyroid seeker) is an accurate method to distinguish it from the stable isotope, (127)I, and to quantify the various species at environmentally relevant concentrations (~10(-8) M). A pH-dependent solvent extraction and combustion method was paired with accelerator mass spectrometry (AMS) to measure ambient levels of (129)I/(127)I isotope ratios and iodine speciation (iodide (I(-)), iodate (IO3(-)), and organo-I (OI)) in aquatic systems. The method exhibited an overall uncertainty of 10% or less for I(-) and IO3(-), and less than 30% for OI species concentrations and enabled (129)I measurements as low as 0.001 Bq/L (1 Bq/L=10(-13) M). The method was used to analyze groundwater from the Savannah River Site (SRS), South Carolina, USA, along a pH, redox potential (Eh), and organic carbon gradient (8-60 μM DOC). The data confirmed that the (129)I/(127)I ratios and species distribution were strongly pH dependent and varied in a systematic manner from the strongly acidic source. While (129)I speciation in plume samples containing total I concentrations >1.7 Bq/L was similar whether measured by AMS or GC-MS ([I(-)]≫[IO3(-)]=[OI]), AMS enabled (129)I speciation measurements at much lower concentrations than what was possible with GC-MS. AMS analyses demonstrated that groundwater samples minimally impacted by the plume were still orders of magnitude higher than ambient (129)I concentrations typically found elsewhere in the USA groundwaters and rivers. This is likely due to past atmospheric releases of volatile (129)I species by SRS nuclear reprocessing facilities near the study site. Furthermore, the results confirmed the existence of (129)I not only as I(-), but also as OI and IO3(-) species.

Because iodine-129 has a half-life of nearly 16 million years, poses major health threats, and can be mobile in the environment, it is important to use the best estimates for kinetics of sorption in risk assessment models. Previous work estimating the iodine sorption has not allowed for samples to reach full equilibrium and field studies have reported significant fractions of up to three major species of iodine; therefore, further research into the kinetics of iodine sorption to sediments is warranted. The objective of this study is to investigate the kinetics of iodine sorption in the presence of subsurface upland sediments and wetland sediments from an area within an 129 I plume at the Savannah River Site in Aiken, SC. Batch sorption studies for these systems took longer than 8 weeks to reach equilibrium, which is significant as previous studies did not reach such timescales. In addition, experiments were conducted under oxic and anoxic conditions. Results confirm that there are three species present in these systems (iodide, iodate, and organo-iodine) with a majority as organo-iodine species at equilibrium for systems with high organic matter content. It is notable that the anoxic conditions exhibited reduced sorption for the iodate species to wetland sediment with high organic matter.

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.

Sunlight can inhibit or disrupt the aggregation process of marine colloids via cleavage of high molecular weight compounds into smaller, less stable fragments. In contrast, some biomolecules, such as proteins excreted from bacteria can form aggregates via cross-linking due to photo-oxidation. To examine whether light-induced aggregation can occur in the marine environment, we conducted irradiation experiments on a well-characterized protein-containing exopolymeric substance (EPS) from the marine bacterium Sagitulla stellata. Our results show that after 1 h sunlight irradiation, the turbidity level of soluble EPS was 60% higher than in the dark control. Flow cytometry also confirmed that more particles of larger sized were formed by sunlight. In addition, we determined a higher mass of aggregates collected on filter in the irradiated samples. This suggests light can induce aggregation of this bacterial EPS. Reactive oxygen species hydroxyl radical and peroxide played critical roles in the photo-oxidation process, and salts assisted the aggregation process. The observation that Sagitulla stellata EPS with relatively high protein content promoted aggregation, was in contrast to the case where no significant differences were found in the aggregation of a non-protein containing phytoplankton EPS between the dark and light conditions. This, together with the evidence that protein-to-carbohydrate ratio of aggregates formed under light condition is significantly higher than that formed under dark condition suggest that proteins are likely the important component for aggregate formation. Light-induced aggregation provides new insights into polymer assembly, marine snow formation, and the fate/transport of organic carbon and nitrogen in the ocean.

Sinking marine oil snow was found to be a major mechanism in the transport of spilled oil from the surface to the deep sea following the Deepwater Horizon (DwH) oil spill. Marine snow formation is primarily facilitated by extracellular polymeric substances (EPS), which are mainly composed of proteins and carbohydrates secreted by microorganisms. While numerous bacteria have been identified to degrade oil, there is a paucity of knowledge on bacteria that produce EPS in response to oil and Corexit exposure in the northern Gulf of Mexico (nGoM). In this study, we isolated bacteria from surface water of the nGoM that grow on oil or Corexit dispersant. Among the 100 strains isolated, nine were identified to produce remarkable amounts of EPS. 16S rRNA gene analysis revealed that six isolates (strains C1, C5, W10, W11, W14, W20) belong to the genus Alteromonas; the others were related to Thalassospira (C8), Aestuariibacter (C12), and Escherichia (W13a). The isolates preferably degraded alkanes (17-77%), over polycyclic aromatic hydrocarbons (0.90-23%). The EPS production was determined in the presence of a water accommodated fraction (WAF) of oil, a chemical enhanced WAF (CEWAF), Corexit, and control. The highest production of visible aggregates was found in Corexit followed by CEWAF, WAF, and control; indicating that Corexit generally enhanced EPS production. The addition of WAF and Corexit did not affect the carbohydrate content, but significantly increased the protein content of the EPS. On the average, WAF and CEWAF treatments had nine to ten times more proteins, and Corexit had five times higher than the control. Our results reveal that Alteromonas and Thalassospira, among the commonly reported bacteria following the DwH spill, produce protein rich EPS that could have crucial roles in oil degradation and marine snow formation. This study highlights the link between EPS production and bacterial oil-degrading capacity that should not be overlooked during spilled oil clearance.

In order to assess the overall risk posed by engineered nanoparticles (ENPs), the biological effects of this emergent pollutant to aquatic ecosystems must be evaluated. We present findings from studies conducted with a diversity of ENPs (metallic, quantum dots) on a variety of freshwater and marine algae (phytoplankton) illustrating both their direct and indirect effects. We show that in general, while the surface properties of ENPs govern their aggregation behavior and ionic strength controls their dissolution, exopolymeric substances (EPS) produced by algae determine their potential to be toxic and thereby movement through the water column and food web. The production of EPS reduces the impact of ENPs (bioavailability and toxicity) and/or their ions on cellular activities of algae. It does not however directly reduce the aggregation and/or solubility of ENPs but rather affects their stability. Complicating understanding of these interactions is the great assortment of surface coatings for ENPs. This per...

Major fractions of radioiodine ((129)I) are associated with natural organic matter (NOM) in the groundwater and surface soils of the Savannah River Site (SRS). Electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) was applied to elucidate the interactions between inorganic iodine species (iodide and iodate) and a fulvic acid (FA) extracted from a SRS surface soil. Iodate is likely reduced to reactive iodine species by the lignin- and tannin-like compounds or the carboxylic-rich alicyclic molecules (CRAM), during which condensed aromatics and lignin-like compounds were generated. Iodide is catalytically oxidized into reactive iodine species by peroxides, while FA is oxidized by peroxides into more aliphatic and less aromatic compounds. Only 9% of the total identified organo-iodine compounds derived from molecules originally present in the FA, whereas most were iodine binding to newly-produced compounds. The resulting iodinated molecules were distributed in three regions in the van Krevelen diagrams, denoting unsaturated hydrocarbons, lignin and protein. Moreover, characteristics of these organo-iodine compounds, such as their relatively low O/C ratios (0.2 or0.4) and yet some degree of un-saturation close to that of lignin, have multiple important environmental implications concerning possibly less sterically-hindered aromatic ring system for iodine to get access to and a lower hydrophilicity of the molecules thus to retard their migration in the natural aquatic systems. Lastly, ~69% of the identified organo-iodine species contains nitrogen, which is presumably present as NH2 or HNCOR groups and a ring-activating functionality to favor the electrophilic substitution. The ESI-FTICR-MS technique provides novel evidence to better understand the reactivity and scavenging properties of NOM towards radioiodine and possible influence of NOM on (129)I migration.

a b s t r a c t Quantum dots (QDs) are engineered nanoparticles (ENs) that have found increasing applications and shown great potential in drug delivery, biological imaging and industrial products. Knowledge of their stability, fate and transport in the aquatic environment is still lacking, including details of how these nanomaterials interact with marine phytoplankton. Here, we examined the toxicity of functional- ized CdSe/ZnS QDs (amine- and carboxyl-) by exposing them for five days to Thalassiosira pseudonana (marine diatom) grown under different nutrient-conditions (enriched versus nitrogen-limited media). The released polysaccharides and proteins, the major components of extracellular polymeric substances (EPS), were measured to assess their potential effects on the interactions between QDs and T. pseudonana. The partitioning of QDs was analyzed by monitoring the concentration of Cd in different size fractions of the cultures (i.e., filtrate

The human and environmental risks associated with Pu disposal, remediation, and nuclear accidents scenarios stems mainly from the very long half-lives of several of its isotopes. The SRS, holding one-third of the nation’s Pu inventory, has a long-term stewardship commitment to investigation of Pu behavior in the groundwater and downgradient vast wetlands. Pu is believed to be essentially immobile due to its low solubility and high particle reactivity to mineral phase or natural organic matter (NOM). For example, in sediments collected from a region of SRS, close to a wetland and a groundwater plume, 239,240Pu concentrations suggest immobilization by NOM compounds, as Pu correlate with NOM contents. Micro-SXRF data indicate, however, that Pu does not correlate with Fe. However, previous studies reported Pu can be transported several kilometers in surface water systems, in the form of a colloidal organic matter carrier, through wind/water interactions. The role of NOM in both immobilizing or re-mobilizing Pu thus has been demonstrated. Our results indicate that more Pu (IV) than (V) was bound to soil colloidal organic matter (COM), amended at far-field concentrations. Contrary to expectations, the presence of NOM in the F-Area soil did not enhance Pu fixation to the organic-rich soil, whenmore » 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 at elevated pH, 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. Sediment Pu concentrations in the SRS F-Area wetland 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 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 isoelectric focusing experiment (IEF). An 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.« less

129 I is a major by-product of nuclear fission and had become one of the major radiation risk drivers at Department of Energy (DOE) sites. 129 I is present at elevated levels in the surface soils of the Savannah River Site (SRS) F-Area and was found to be bound predominantly to soil organic matter (SOM). Naturally bound 127 I and 129 I to sequentially extracted humic acids (HAs), fulvic acids (FAs) and a water extractable colloid (WEC) were measured in a 129 I-contaminated wetland surface soil located on the SRS. WEC is a predominantly colloidal organic fraction obtained from soil re-suspension experiments to mimic the fraction that may be released during groundwater exfiltration, storm water or surface runoff events. For the first time, NMR techniques were applied to infer the molecular environment of naturally occurring stable iodine and radioiodine binding to SOM. Iodine uptake partitioning coefficients ( K d ) by these SOM samples at ambient iodine concentrations were also measured and related to quantitative structural analyses by 13 C DPMAS NMR and solution state 1 H NMR on the eight humic acid fractions. By assessing the molecular environment of iodine, it was found that it was closely associated with the aromatic regions containing esterified products of phenolic and formic acids or other aliphatic carboxylic acids, amide functionalities, quinone-like structures activated by electron-donating groups (e.g., NH 2 ), or a hemicellulose–lignin-like complex with phenyl-glycosidic linkages. However, FAs and WEC contained much greater concentrations of 127 I or 129 I than HAs. The contrasting radioiodine contents among the three different types of SOM (HAs, FAs and WEC) suggest that the iodine binding environment cannot be explained solely by the difference in the amount of their reactive binding sites. Instead, indirect evidence indicates that the macro-molecular conformation, such as the hydrophobic aliphatic periphery hindering the active aromatic cores and the hydrophilic polysaccharides favoring the access by hydrophilic iodine species, also influences iodine–SOM interactions.

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.

In order to investigate the distributions and speciation of (129)I (and (127)I) in a contaminated F-Area groundwater plume of the Savannah River Site that cannot be explained by simple transport models, soil resuspension experiments simulating surface runoff or stormflow and erosion events were conducted. Results showed that 72-77% of the newly introduced I(-) or IO(3)(-) were irreversibly sequestered into the organic-rich riparian soil, while the rest was transformed by the soil into colloidal and truly dissolved organo-iodine, resulting in (129)I remobilization from the soil greatly exceeding the 1 pCi/L drinking water permit. This contradicts the conventional view that only considers I(-) or IO(3)(-) as the mobile forms. Laboratory iodination experiments indicate that iodine likely covalently binds to aromatic structures of the soil organic matter (SOM). Under very acidic conditions, abiotic iodination of SOM was predominant, whereas under less acidic conditions (pH ≥5), microbial enzymatically assisted iodination of SOM was predominant. The organic-rich soil in the vadose zone of F-Area thus acts primarily as a "sink," but may also behave as a potentially important vector for mobile radioiodine in an on-off carrying mechanism. Generally the riparian zone provides as a natural attenuation zone that greatly reduces radioiodine release.

129 I is one of the three major radiation risk contributors to the public as a consequence of past nuclear processing activities at Department of Energy (DOE) facilities. Elevated levels of 129 I are present in the surface soils of F-Area of Savannah River Site, which used to be an isotope separation facility for the production of nuclear weapons components. The 129 I in soils is thought to be bound predominantly to soil organic matter (SOM). Measurements of stable 127 I and radioactive 129 I in humic acids (HAs) and fulvic acids (FAs) obtained by five successive alkaline, two glycerol and one citric acid–alkaline extraction, demonstrated that these extractable humic substances (HS) together account for 54–56% and 46% of the total 127 I and 129 I in the soil, respectively. The remainder was likely bound to residual SOM. The iodine content (μg-I/g-C) generally decreased with each subsequent extract, while 129 I/ 127 I increased concurrently. The coincident variations in chemical compositions, aromaticity (estimated by UV spectroscopy), functional groups (e.g., aliphatic), degree of humification, relative migration in the hydrophobic interaction column, and molecular weight indicated that: (1) iodine in different HAs was bound to a small-size aromatic subunit (∼10 kDa); (2) the large-size subunit (∼90 kDa), which likely linked the small-size unit through some weak chemical forces (hydrogen bonds, hydrophobic or electrostatic interactions), determined the relative mobility of iodine bound to organic matter; (3) from the strong correlation between iodine content and aromaticity in the HAs, we suggested that iodine incorporation into the SOM via covalent aromatic C–I bond is the key mechanism controlling iodine behavior in this system. However, this relationship is not universal for all fractions of organic matter as evidenced from the different slopes of this relationship at the two sampling sites, as well as from the different relationships for HAs and FAs, respectively. These differences in iodination are due to different SOM molecular sizes, compositions, and availability of preferred iodination sites. 129 I in the soil downstream from the contaminated site and near a wetland abruptly dropped below our detection limit (0.5 pCi- 129 I/g-soil), which suggests that the high SOM in the plume soil around the 129 I-contaminated F-Area might be a natural barrier to scavenge radioiodine released from the nuclear waste repository by forming organo-iodine compounds. Soil resuspension experiments showed that mobile 129 I was mostly associated with a low average molecular weight amphiphilic organic carrier (13.5–15 kDa). SOM clearly behaves as a sink for iodine at the Savannah River Site F-Area. However, this work demonstrates that a small fraction of the SOM can also behave as a source, namely that a small fraction that may be readily dispersible under some environmental conditions and presumably release iodine in the organic-colloidal form. This radioiodinated organo-colloid likely can get into the groundwater through infiltration or surface runoff where it might migrate further into the wetlands. Results from this study provide the geochemical basis for future 129 I migration controls, remediation, and/or land–groundwater management strategies.

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 Energy's 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.

Understanding the chemical and physical properties of microbially produced, actinide-carrying biopolymers is essential for the prediction of their relative binding affinities and particle-interaction propensities that are affecting the transport of actinide elements. In addition, they form the basis for their oceanographic applications, such as using POC/ 234 Th ratios to determine organic carbon fluxes and for tracing upper ocean particle dynamics. Furthermore, environmental applications of bioflocculation and bioremediation can benefit from such improved understanding. Exopolymeric substances (EPS) in “attached” and “non-attached” forms, produced by two bacteria and one alga, were extracted and purified using improved procedures. These biopolymers produced by the two bacteria, which were previously shown to contain strong 234 Th complexing ligands, were further fractionated by semi-preparative HPLC-anion exchange chromatography in order to relate Th(IV)-binding ability to chemical composition. Eluted fractions were further characterized at both semi-molecular and molecular levels. It was found that the EPS consisted of more than one biopolymer, with distinct monosaccharide and amino acid compositions, but very similar molecular weight (~ 25 kDa). 234 Th binding strength was correlated to their uronic acid to organic carbon ratios, suggesting that uronic acids are the actual binding agents of 234 Th, or more likely, proxy compounds for the actual macromolecular 234 Th binding ligands. These compounds were, however, not pure uronic acids, but rather amphiphilic glycoproteins or proteoglycans. Hydrophobic contact areas (HCA) of “attached” EPS, as measures of their relative hydrophobicity and amphiphilicity, were higher than those of “non-attached” EPS, and all were highly correlated to the ratios of the FTIR areas of amide-I bands from proteins to those of C O C bands from carbohydrates. This suggests that the relative hydrophobicity of the carrier biopolymers, which can be responsible for gel formation, particle aggregation and bioflocculation, was mainly regulated by their relative protein to polysaccharide contents.

To gain new insights into the variability of particulate organic carbon (POC) fluxes and to better understand the factors controlling the POC/234Th ratios in suspended and sinking particulate matter, we investigated the relationships between POC/234Th ratios and biochemical composition (uronic acids, URA; total carbohydrates, TCHO; acid polysaccharides, APS; and POC) of suspended and sinking matter from the Gulf of Mexico in 2005 and 2006. Our data show that URA/POC in sediment traps (STs), APS/POC in the suspended particles, and turnover times of particulate 234Th in the water column and those of bacteria in STs inside eddies usually increased with depth, whereas particulate POC/234Th (10–50 μm) and the sediment-trap parameters (POC flux, POC/234Th ratio, bacterial biomass, and bacterial production) decreased with depth. However, this trend was not the case for most biological parameters (e.g., phytoplankton and bacterial biomass) or for the other parameters at the edges of eddies or at coastal-upwelling sites. In general, the following relationships were observed: 1) 234Th/POC ratios in STs were correlated with APS flux, and these ratios in the 10–50 μm suspended particles also correlated with URA/POC ratios; 2) neither URA fluxes nor URA/POC ratios were significantly related to bacterial biomass; 3) the sum of two uronic acids (G2, glucuronic, and galacturonic acid, which composed most of the URA pool) was positively related to bacterial biomass; and 4) the POC/234Th ratios in intermediate-sized particles (10–50 μm) were close to those in sinking particles but much lower than those in > 50 μm particles. The results indicate that acid polysaccharides, though a minor fraction (~ 1%) of the organic carbon, act more likely as proxy compound classes that might contain the more refractory 234Th-binding biopolymer, rather than acting as the original 234Th “scavenger” compound. Moreover, these acid polysaccharides, which might first be produced by phytoplankton and then modified by bacteria, also influence the on-and-off “piggy-back” processes of organic matter and 234Th, thus causing additional variability of the POC/234Th in particles of different sizes.

To better understand the inter-relationships between particulate organic carbon (POC) fluxes and phytoplankton and bacteria biomass and production, we compared POC fluxes determined in sediment traps and approaches based on size-fractionated (1–10, 10–50, 50–150 and > 150 μm) suspended particulate 234 Th and POC concentrations in oligotrophic sections of the Gulf of Mexico during August 2005 and May 2006 and in the oligotrophic northwestern Pacific Ocean during 2009. In 2005, the sediment trap POC flux near the bottom of the euphotic zone (120 m) ranged from 71 to 94 mg C m − 2 day − 1 , while 234 Th-derived POC fluxes using POC/ 234 Th ratios in the 10–50 µm and 50–150 µm varied from 71 to 150 mg C m − 2 day − 1 . In 2006, the sediment trap POC flux at 120 m ranged from 24 to 67 mg C m − 2 day − 1 , while the 234 Th-derived POC fluxes in the 10–50 µm fraction were comparable or somewhat higher, ranging from 71 to 119 mg C m − 2 day − 1 . The POC fluxes in 2006, calculated by using POC/ 234 Th ratios in the 1–10 µm and the 50–150 µm fractions were much higher, ranging from 847 to 1369 mg C m − 2 day − 1 . Correlations with biological and chemical parameters support a likely mechanism of sinking aggregates of haptophytes (0.2–20 µm) of higher density held together by Th-complexing and uronic acid containing exopolymeric substances. The observations that 234 Th (and POC) is mainly associated with medium-sized (10–15 µm) suspended particles rather than larger (50–150 µm) ones may be caused by the use of a one-filter method and standard filtration and processing procedures that were applied here for collecting suspended particles. This then raises the question of what constitutes representative material from the ocean that settles on the characteristic time scale of 234 Th. As a comparison, size-fractionated trap-collected particles in the oligotrophic northwestern Pacific Ocean showed that the 10–50 μm fraction contained the largest proportion of POC (22–41%), followed by the 50–150 μm (22–37%), the > 150 μm (15–27%), and the 1–10 μm (17–23%) fraction. The partitioning of 234 Th in trap-collected particles was slightly different from that of POC, with the 1–10 μm fraction representing the largest proportion (27–48%) of 234 Th flux. Together, the 234 Th ratios traditionally derived from large (> 50 µm) pump-collected particles may not accurately reflect the majority of sinking particles. Therefore, estimated POC fluxes may be significantly biased using a conventional 234 Th based approach, i.e., using POC/ 234 Th ratios from a single filter obtained from large (> 50 µm) pump-collected particles.

Different chemical extractants (NaCl, EDTA, HCl and NaOH) and physical methods (ultrasonication and heating) were examined by their efficacies of extracting “attached” exopolymeric substances (EPS) secreted by marine bacterium Sagittula stellata (SS) and terrestrial bacterium Pseudomonas fluorescens Biovar II (PF). Extraction by 0.5 N HCl for 3 h was best for SS while extraction by 0.05 N NaCl for 3–5 h was regarded as optimal for PF. Improvements in EPS purification included a pre-diafiltration step to remove the broth material and reduce the solution volume, thus the usage of ethanol, and time. The EPS harvested at the optimal time and purified by the improved method were enriched in polysaccharides, with smaller amounts of proteins, thus having amphiphilic properties. Isoelectric focusing of 234 Th or 240 Pu labeled EPS showed both actinides were strongly bound to macromolecules with low pI, similar to reported marine or soil colloidal natural organic matter (NOM).

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.