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MiR-26 has emerged as a key tumour suppressor in various cancers. Accumulating evidence supports that miR-26 regulates inflammation and tumourigenicity largely through down-regulating IL-6 production, but the underlying mechanism remains obscure. Here, combining a transcriptome-wide approach with manipulation of cellular miR-26 levels, we showed that instead of directly targeting IL-6 mRNA for gene silencing, miR-26 diminishes IL-6 transcription activated by TNF-α through silencing NF-κB signalling related factors HMGA1 and MALT1. We demonstrated that miR-26 extensively dampens the induction of many inflammation-related cytokine, chemokine and tissue-remodelling genes that are activated via NF-κB signalling pathway. Knocking down both HMGA1 and MALT1 by RNAi had a silencing effect on NF-κB-responsive genes similar to that caused by miR-26. Moreover, we discovered that poor patient prognosis in human lung adenocarcinoma is associated with low miR-26 and high HMGA1 or MALT1 levels and not with levels of any of them individually. These new findings not only unravel a novel mechanism by which miR-26 dampens IL-6 production transcriptionally but also demonstrate a direct role of miR-26 in down-regulating NF-κB signalling pathway, thereby revealing a more critical and broader role of miR-26 in inflammation and cancer than previously realized.

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.

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.

Lactobacillus kefiranofaciens M1 (M1) has been shown to possess many different beneficial health effects including anti-colitis activity. The purpose of this study was to develop a novel and easily scaled-up encapsulating technique that would improve the temperature tolerance of the bacterium and reduce the sensitivity of the organism to gastrointestinal fluid. A mixture of sodium alginate, gellan gum and skim milk powder was used as a coating material to entrap M1. The M1 gel was then directly freeze dried in order to dehydrate the covering and form microcapsules. The viable cell numbers of M1 present only dropped ten folds after the freeze-drying encapsulation process. The viable cell counts remained constant at 5 × 10(7) CFU/g after heating from 25 °C to 75 °C and holding at 75 °C for 1 min. The viable cell counts were reduced to 10(6) CFU/g and 10(5) CFU/g after 8-week storage at 4 °C and subsequent heat treatment with simulated gastrointestinal fluid test (SGFT) and bile salts, respectively. The effect of encapsulated M1 on the organism's anti-colitis activity was evaluated using the dextran sodium sulfate (DSS) induced colitis mouse model. An in vivo study indicated that administration of heat treated encapsulated M1 was able to ameliorate DSS-induced colitis producing a significant reduction in the bleeding score and an attenuation of inflammatory score. These findings clearly demonstrate that encapsulation of M1 using this novel technique is able to provide good protection from temperature changes and SGFT treatment and also does not affect the organism's anti-colitis activity.

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

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.

Laboratory studies were conducted to examine the sorption of selected radionuclides (234Th, 233Pa, 210Po, 210Pb, and 7Be) onto inorganic (pure silica and acid-cleaned diatom frustules) and organic (diatom cells with or without silica frustules) particles in natural seawater and the role of templating biomolecules and exopolymeric substances (EPS) extracted from the same species of diatom, Phaeodactylum tricornutum, in the sorption process. The range of partition coefficients (Kd, reported as logKd) of radionuclides between water and the different particle types was 4.78–6.69 for 234Th, 5.23–6.71 for 233Pa, 4.44–5.86 for 210Pb, 4.47–4.92 for 210Po, and 4.93–7.23 for 7Be, similar to values reported for lab and field determinations. The sorption of all radionuclides was significantly enhanced in the presence of organic matter associated with particles, resulting in Kd one to two orders of magnitude higher than for inorganic particles only, with highest values for 7 Be (logKd of 7.2). Results further indicate that EPS and frustule-embedded biomolecules in diatom cells are responsible for the sorption enhancement rather than the silica shell itself. By separating radiolabeled EPS via isoelectric focusing, we found that isoelectric points are radionuclide specific, suggesting that each radionuclide binds to specific biopolymeric functional groups, with the most efficient binding sites likely occurring in acid polysaccharides, iron hydroxides, and proteins. Further progress in evaluating the effects of diatom frustule–related biopolymers on binding, scavenging, and fractionation of radionuclides would require the application of molecular-level characterization techniques.

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.

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 (O 2 − ). 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.

Most subsurface environmental radioactivity contamination is expected to eventually resurface in riparian zones, or wetlands. There are a number of extremely sharp biogeochemical interfaces in wetlands that could alter radionuclide speciation and promote accumulation. The objective of this study was to determine if a wetland concentrated (129)I emanating from a former waste disposal basin located on the Savannah River Site (SRS) in South Carolina, USA. Additionally, studies were conducted to evaluate the role of sediment organic matter in immobilizing the radioiodine. Groundwater samples were collected along a 0.7-km transect away from the seepage basin and in the downstream wetlands. The samples were analyzed for (129)I speciation (iodide (I(-)), iodate (IO3(-)), and organo-I). Groundwater (129)I concentrations in many locations in the wetlands (as high as 59.9 Bq L(-1)(129)I) were greatly elevated with respect to the source term (5.9 Bq L(-1)(129)I). (129)I concentration profiles in sediment cores were closely correlated to organic matter concentrations (r(2) = 0.992; n = 5). While the sediment organic matter promoted the uptake of (129)I to the wetland sediment, it also promoted the formation of a soluble organic fraction: 74% of the wetland groundwater (129)I could pass through a 1 kDa (1 nm) membrane and only 26% of the (129)I was colloidal. Of that fraction that could pass through a 1 kDa membrane, 39% of the (129)I was organo-I. Therefore, while wetlands may be highly effective at immobilizing aqueous (129)I, they may also promote the formation of a low-molecular-weight organic species that does not partition to sediments. This study provides a rare example of radioactivity concentrations increasing rather than decreasing as it migrates from a point source and brings into question assumptions in risk models regarding continuous dilution of released contaminants.

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.

The concentrations of potential organic (e.g., proteins, polysaccharides, uronic acids, hydroquinones, hydroxamate- and catechol-type siderophores) and inorganic (Fe, Mn, Si, and CaCO 3 ) carrier phases for radionuclides ( 234 Th, 233 Pa, 210 Po, 210 Pb and 7 Be) and their particle–water partition coefficients (K d ) were determined for particles collected by sediment traps deployed at the Oceanic Flux Program (OFP) site off Bermuda (500, 1500 and 3200 m). The purpose was to better understand the mechanisms that control the chemical composition of sinking particles as well as the scavenging and fractionation behavior of those five radionuclides. Different components contributed differently to the scavenging of different radionuclides at the three depths. Chemical considerations (e.g., ionic potential, ionization energy, multifunctional group structures), as well as factor analysis (FA) and correlations of logK d values with chemical parameters, indicate that hydroxamate siderophores are major classes of biopolymers that have a role in binding Po and Pa. MnO 2 and FeO 2 , whose presence is closely related to that of hydroxamate siderophores (HS), are also involved in binding of Pa and Po. The carbonate and biogenic silica phases are identified to be important in predicting removal and fractionation of Th and Be in the ocean.

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.

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.

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.

Lipase from Pseudomonas fluorescens efficiently catalyzed the alcoholysis of various TG in dry alcohols. For TG with short-chain FA, more MG were accumulated. The yields of MG were affected by the alcohols used. The maximum yields of MG were as follows: 85% for monoacetin in n-butanol, 96% for monobutyrin in ethanol or n-butanol, 50% for monocaprylin in n-butanol, 48% for monolaurin in isopropanol, and 45% for monopalmitin in isopropanol. The MG produced were judged to be 2-MG by TLC analysis. The presence of organic cosolvent affected the reaction rate of the lipase-catalyzed alcoholysis of TG. For the alcoholysis of various TG in ethanol and cosolvent (1∶1, vol/vol), the rates had the following orders: (i) for tributyrin, hexane > toluene > acetone > ethyl acetate > chloroform > acetonitrile > pyridine; (ii) for tricaprylin, hexane > acetone > toluene > acetonitrile > ethyl acetate > pyridine > chloroform; and (iii) for trialurin, hexane > acetonitrile=acetone > ethyl acetate > pyridine=chloroform > toluene.

(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 and5-133 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.

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

A quantitative method using artificial antibody to detect creatine kinases was developed. Linear epitope sequences were selected based on an artificial-epitope mapping strategy. Nine different MIPs corresponding to the selected peptides were then fabricated on QCM chips. The subtle conformational changes were also recognized by these chips.

Protein phosphorylation was studied in Xanthomonas campestris pv. oryzae in vivo and in vitro. In vitro labelling showed that the protein kinases in this bacterium used both ATP and GTP as nucleotide substrates at nearly the same efficiency. At least 6 proteins were phosphorylated in vitro, including abundant species of p81, p44, and p32 with Mr of 81000, 44000, and 32000, respectively. Three types of phosphate-protein linkage were found in this bacterium: O-phosphate, N-phosphate and probably acyl phosphate. The p81 and p32 were phosphorylated at histidine. The p44 had mainly phosphoserine and a small part of phosphohistidine. The phosphorylation profile was variable depending on the growth conditions. Furthermore, by a virulent phage Xp10 infection the quantity of phosphorylation increased: for phosphohistinine more than 10-fold, and for phosphoserine about 3-fold. Thus, in this bacterium phosphorylation may be linked with a physiological regulation system and with Xp10 phage development.

Several crystal structures of AFL, a novel lipase from the archaeon Archaeoglobus fulgidus, complexed with various ligands, have been determined at about 1.8 A resolution. This enzyme has optimal activity in the temperature range of 70-90 degrees C and pH 10-11. AFL consists of an N-terminal alpha/beta-hydrolase fold domain, a small lid domain, and a C-terminal beta-barrel domain. The N-terminal catalytic domain consists of a 6-stranded beta-sheet flanked by seven alpha-helices, four on one side and three on the other side. The C-terminal lipid binding domain consists of a beta-sheet of 14 strands and a substrate covering motif on top of the highly hydrophobic substrate binding site. The catalytic triad residues (Ser136, Asp163, and His210) and the residues forming the oxyanion hole (Leu31 and Met137) are in positions similar to those of other lipases. Long-chain lipid is located across the two domains in the AFL-substrate complex. Structural comparison of the catalytic domain of AFL with a homologous lipase from Bacillus subtilis reveals an opposite substrate binding orientation in the two enzymes. AFL has a higher preference toward long-chain substrates whose binding site is provided by a hydrophobic tunnel in the C-terminal domain. The unusually large interacting surface area between the two domains may contribute to thermostability of the enzyme. Two amino acids, Asp61 and Lys101, are identified as hinge residues regulating movement of the lid domain. The hydrogen-bonding pattern associated with these two residues is pH dependent, which may account for the optimal enzyme activity at high pH. Further engineering of this novel lipase with high temperature and alkaline stability will find its use in industrial applications.

In his comment on our paper “Iodine-129 and Iodine-127 Speciation in Groundwater at Hanford Site, U.S.: Iodate Incorporation into Calcite”, Lu specified three concerns for Zhang et al’s study,1 including (1) precipitation mechanism (degassing vs freezing), (2) analytical methods, and (3) mass balance control. In response, comparative and comprehensive discussions on the precipitation mechanisms and iodine incorporation can be found in the paper, as well as below. This includes additional experiments of iodine distribution and speciation in calcite precipitates. In addition, the measurements of total iodine in soils/sediment were clarified below as well. The calculations on mass balance in this comment were clarified by using correct data sets. Lu proposed that freezing samples