Impact of the Fe(III)-reducing bacteria <Emphasis Type="Italic">Geobacter sulfurreducens</Emphasis> and <Emphasis Type="Italic">Shewanella oneidensis</Emphasis> on the speciation of plutonium

Microbial bioreduction of radionuclides has been the subject of much recent interest, in particular as a method for the in situ bioremediation of uranium contaminated sites. However, there have been very few studies investigating the microbially mediated redox transformations of plutonium. The redox chemistry of Pu is complicated, but the dominant environmental oxidation state is insoluble Pu(IV). However, microbial reduction of Pu(IV) to more soluble Pu(III) may enhance migration of Pu in the environment. In this study we investigated the effect of two model metal-reducing bacteria, Geobacter sulfurreducens and Shewanella oneidensis, on the redox speciation of Pu. Our results show that in all cases, the presence of bacterial cells enhanced removal of Pu from solution. UV/Visible spectra of cells and precipitates formed (dissolved in 1 M HCl), showed that the sorbed and precipitated Pu was mainly Pu(IV), but Pu(III) was also present. The results suggest that the mechanism of interaction between Pu(IV) and the two microorganisms is initial sorption to the cell surface, followed by slow reduction. Although both bacteria could reduce Pu(IV) to Pu(III), there was no increase in the solution concentrations of Pu. This suggests that the potential reduction of sorbed Pu(IV) in sediments that have been stimulated to bioremediate U(VI) may not result in problematic mobilization of Pu(III).     

Plutonium(IV) Reduction by the Metal-Reducing Bacteria Geobacter metallireducens GS15 and Shewanella oneidensis MR1

The bacterial reduction of actinides has been suggested as a possible remedial strategy for actinide-contaminated environments, and the bacterial reduction of Pu(VI/V) has the potential to produce highly insoluble Pu(IV) solid phases. However, the behavior of plutonium with regard to bacterial reduction is more complex than for other actinides because it is possible for Pu(IV) to be further reduced to Pu(III), which is relatively more soluble than Pu(IV). This work investigates the ability of the metal-reducing bacteria Geobacter metallireducens GS15 and Shewanella oneidensis MR1 to enzymatically reduce freshly precipitated amorphous Pu(IV) (OH)₄ [Pu(IV)(OH)_4(am)] and soluble Pu(IV)(EDTA). In cell suspensions without added complexing ligands, minor Pu(III) production was observed in cultures containing S. oneidensis, but little or no Pu(III) production was observed in cultures containing G. metallireducens. In the presence of EDTA, most of the Pu(IV)(OH)_4(am) present was reduced to Pu(III) and remained soluble in cell suspensions of both S. oneidensis and G. metallireducens. When soluble Pu(IV)(EDTA) was provided as the terminal electron acceptor, cell suspensions of both S. oneidensis and G. metallireducens rapidly reduced Pu(IV)(EDTA) to Pu(III)(EDTA) with nearly complete reduction within 20 to 40 min, depending on the initial concentration. Neither bacterium was able to use Pu(IV) (in any of the forms used) as a terminal electron acceptor to support growth. These results have significant implications for the potential remediation of plutonium and suggest that strongly reducing environments where complexing ligands are present may produce soluble forms of reduced Pu species.     

Speciation and Bioavailability Measurements of Environmental Plutonium Using Diffusion in Thin Films

The biological uptake of plutonium (Pu) in aquatic ecosystems is of particular concern since it is an alpha-particle emitter with long half-life which can potentially contribute to the exposure of biota and humans. The diffusive gradients in thin films technique is introduced here for in-situ measurements of Pu bioavailability and speciation. A diffusion cell constructed for laboratory experiments with Pu and the newly developed protocol make it possible to simulate the environmental behavior of Pu in model solutions of various chemical compositions. Adjustment of the oxidation states to Pu(IV) and Pu(V) described in this protocol is essential in order to investigate the complex redox chemistry of plutonium in the environment. The calibration of this technique and the results obtained in the laboratory experiments enable to develop a specific DGT device for in-situ Pu measurements in freshwaters. Accelerator-based mass-spectrometry measurements of Pu accumulated by DGTs in a karst spring allowed determining the bioavailability of Pu in a mineral freshwater environment. Application of this protocol for Pu measurements using DGT devices has a large potential to improve our understanding of the speciation and the biological transfer of Pu in aquatic ecosystems.     

Plutonium(V/VI) Reduction by the Metal-Reducing Bacteria Geobacter metallireducens GS-15 and Shewanella oneidensis MR-1

We examined the ability of the metal-reducing bacteria Geobacter metallireducens GS-15 and Shewanella oneidensis MR-1 to reduce Pu(VI) and Pu(V). Cell suspensions of both bacteria reduced oxidized Pu [a mixture of Pu(VI) and Pu(V)] to Pu(IV). The rate of plutonium reduction was similar to the rate of U(VI) reduction obtained under similar conditions for each bacteria. The rates of Pu(VI) and U(VI) reduction by cell suspensions of S. oneidensis were slightly higher than the rates observed with G. metallireducens. The reduced form of Pu was characterized as aggregates of nanoparticulates of Pu(IV). Transmission electron microscopy images of the solids obtained from the cultures after the reduction of Pu(VI) and Pu(V) by S. oneidensis show that the Pu precipitates have a crystalline structure. The nanoparticulates of Pu(IV) were precipitated on the surface of or within the cell walls of the bacteria. The production of Pu(III) was not observed, which indicates that Pu(IV) was the stable form of reduced Pu under these experimental conditions. Experiments examining the ability of these bacteria to use Pu(VI) as a terminal electron acceptor for growth were inconclusive. A slight increase in cell density was observed for both G. metallireducens and S. oneidensis when Pu(VI) was provided as the sole electron acceptor; however, Pu(VI) concentrations decreased similarly in both the experimental and control cultures.Effective bioremediation and waste management strategies at nuclear sites require an understanding of the fundamental biogeochemical processes that control the mobility of actinides. Microorganisms can influence the chemical speciation, valence state, and distribution of actinides in subsurface environments (2, 8, 12, 14). Dissimilatory metal-reducing bacteria (DMRB), which derive energy by respiring oxidized metals (Fe and Mn in nature), may play a particularly important role in the mobility of actinides, since the oxidized forms of many radionuclides are more mobile than their reduced forms. Remedial strategies have been proposed to biomineralize radionuclides via direct reduction by DMRB or indirectly by DMRB by-products (9-11). Several DMRB have been shown to conserve energy for anaerobic growth via the reduction of U(VI) (9-11, 14).Plutonium redox chemistry is more complex than that of most other actinides. Under environmental conditions, plutonium can exist in the III, IV, V, and VI oxidation states, and multiple oxidation states can coexist simultaneously (4, 5). The oxidized species of plutonium [Pu(V) and Pu(VI)] generally are much more soluble than the reduced species (4). Predicting the influence DMRB have on plutonium biogeochemistry is complicated by the fact that both Pu(III) and Pu(IV) are possible products of biological reduction. Also, the presence of chelating ligands can greatly influence the oxidation state formed during reduction as well as the reduction rate. The reduction of oxidized Pu species to Pu(IV) is desired, because it is highly insoluble and not very mobile. However, in the presence of complexing ligands and under reducing conditions the production of Pu(III) is favored, and Pu(III) complexes can be quite soluble (2). The conditions leading to the reduction of Pu(V) and Pu(VI) need to be understood and controlled so that they do not lead to the production of Pu(III), if the biological reduction of Pu(V) or Pu(VI) is to be used as an effective remediation strategy.There is little information available concerning the influence DMRB have on plutonium biogeochemistry. Few previous studies have reported the biological reduction of Pu(IV) to Pu(III) (2, 7, 16). During the earlier experiments (16), the solubilization of PuO₂ increased approximately ∼40% in solutions with DMRB. In solutions with DMRB and nitrilotriacetic acid (NTA), approximately 90% of the available Pu was solubilized, but the production of Pu(III) was not observed in any of the cultures, either with or without NTA added (16). The enhanced solubility of Pu was attributed to Pu(IV) reduction, the solubilization of resultant Pu(III), and the reoxidation of Pu(III) to Pu(IV) with the NTA complexation of Pu(III). Since Pu(III) was not observed, the biological reduction of Pu(IV) was inferred from the data (16). The biological reduction of Pu(IV) to Pu(III) was first conclusively documented with the production of Pu(III) in monocultures of G. metallireducens GS-15 and S. oneidensis MR-1 both with and without the addition of a chelating agent (EDTA) (2). In experiments without EDTA, the aqueous concentration of Pu(III) in DMRB cultures was very low (<0.05 mM Pu) (2). The aqueous concentration of Pu(III) increased to approximately 60 to 80% (0.3 to 0.4 mM Pu) of the total Pu(IV) when EDTA was added to the cultures (2). To our knowledge, there are no published studies documenting the biological reduction of Pu(V) or Pu(VI) to either Pu(IV) or Pu(III). However, based on thermodynamics calculations, the reduction of Pu(V) and Pu(VI) by DMRB should be possible and yield greater energy for the bacteria than Pu(IV) reduction (2).The study presented here was designed first to assess the ability of G. metallireducens GS-15 and S. oneidensis MR-1 to reduce Pu(V) and Pu(VI) in monocultures under cell resting and growth conditions. Second, the aqueous and solid phases produced during the experiments were analyzed to determine the extent of biological reduction [i.e., to Pu(IV) or Pu(III)].     

Effects of plutonium on soil microorganisms

As a first phase in an investigation of the role of the soil microflora in Pu complex formation and solubilization in soil, the effects of Pu concentration, form, and specific activity on microbial types, colony-forming units, and CO(2) evolution rate were determined in soils amended with C and N sources to optimize microbial activity. The effects of Pu differed with organism type and incubation time. After 30 days of incubation, aerobic sporeforming and anaerobic bacteria were significantly affected by soil Pu levels as low as 1 mug/g when Pu was added as the hydrolyzable Pu(NO(3))(4) (solubility, <0.1% in soil). Other classes of organisms, except the fungi, were significantly affected at soil Pu levels of 10 mug/g. Fungi were affected only at soil Pu levels of 180 mug/g. Soil CO(2) evolution rate and total accumulated CO(2) were affected by Pu only at the 180 mug/g level. Because of the possible role of resistant organisms in complex formation, the mechanisms of effects of Pu on the soil fungi were further evaluated. The effect of Pu on soil fungal colony-forming units was a function of Pu solubility in soil and Pu specific activity. When Pu was added in a soluble, complexed form [Pu(2)(diethylenetriaminepentaacetate)(3)], effects occurred at Pu levels of 1 mug/g and persisted for at least 95 days. Toxicity was due primarily to radiation effects rather than to chemical effects, suggesting that, at least in the case of the fungi, formation of Pu complexes would result primarily from ligands associated with normal (in contrast to chemically-induced) biochemical pathways.     

A biogeochemical framework for bioremediation of plutonium(V) in the subsurface environment

Accidental release of plutonium (Pu) from storage facilities in the subsurface environment is a concern for the safety of human beings and the environment. Given the complexity of the subsurface environment and multivalent state of Pu, we developed a quantitative biogeochemical framework for bioremediation of Pu(V)O(2) (+) in the subsurface environment. We implemented the framework in the biogeochemical model CCBATCH by expanding its chemical equilibrium for aqueous complexation of Pu and its biological sub-models for including Pu's toxicity and reduction reactions. The quantified framework reveals that most of the Pu(V) is speciated as free Pu(V)O(2) (+) ((aq)), which is a problem if the concentration of free Pu(V)O(2) (+) is ≥28?μM (the half-maximum toxicity value for bacteria able to reduce Pu(V) to Pu(III)PO(4(am))) or ≥250?μM (the full-toxicity value that takes the bioreduction rate to zero). The framework includes bioreduction of Fe(3+) to Fe(2+), which abiotically reduces Pu(V)O(2) (+) to Pu(IV) and then to Pu(III). Biotic (enzymatic) reduction of Pu(V)O(2) (+) directly to Pu(III) by Shewanella alga (S. alga) is also included in the framework. Modeling results also reveal that for formation of Pu(III)PO(4(am)), the desired immobile product, the concentration of coexisting model strong ligand-nitrilotriacetic acid (NTA)-should be less than or equal to the concentration of total Pu(III).     

Extraction of Np(IV), Pu(IV) and Am(III) by bidentate organophosphorus extractant

This paper summarizes the extraction of Np(IV), Pu(IV) and Am(III) with dihexyl-N,Ndiethyl carbamyl methylene phosphonate (DHDECMP)-diethyl benzene (DEB) in nitric acid.The distribution ratio of Np(IV), Pu(IV) and Am(III) was studied as a function of a number of parameters such as concentration of nitric acid, salting-out reagent in the aqueous phase, contact time and temperature. Stripping and separation of Np(IV), Pu(IV) and Am(III) from the pregnant organic phase were also studied. The suitable stripping and separation conditions were obtained. The enthalpy changes ΔH_Np, ΔH_Pu, ΔH_Am associated with their extraction process were estimated individually. The composition of extracted complex of Np(IV), Pu(IV) and Am(III) was determined.     

Plutonium(IV) reduction by the metal-reducing bacteria Geobacter metallireducens GS15 and Shewanella oneidensis MR1

The bacterial reduction of actinides has been suggested as a possible remedial strategy for actinide-contaminated environments, and the bacterial reduction of Pu(VI/V) has the potential to produce highly insoluble Pu(IV) solid phases. However, the behavior of plutonium with regard to bacterial reduction is more complex than for other actinides because it is possible for Pu(IV) to be further reduced to Pu(III), which is relatively more soluble than Pu(IV). This work investigates the ability of the metal-reducing bacteria Geobacter metallireducens GS15 and Shewanella oneidensis MR1 to enzymatically reduce freshly precipitated amorphous Pu(IV) (OH)(4) [Pu(IV)(OH)(4(am))] and soluble Pu(IV)(EDTA). In cell suspensions without added complexing ligands, minor Pu(III) production was observed in cultures containing S. oneidensis, but little or no Pu(III) production was observed in cultures containing G. metallireducens. In the presence of EDTA, most of the Pu(IV)(OH)(4(am)) present was reduced to Pu(III) and remained soluble in cell suspensions of both S. oneidensis and G. metallireducens. When soluble Pu(IV)(EDTA) was provided as the terminal electron acceptor, cell suspensions of both S. oneidensis and G. metallireducens rapidly reduced Pu(IV)(EDTA) to Pu(III)(EDTA) with nearly complete reduction within 20 to 40 min, depending on the initial concentration. Neither bacterium was able to use Pu(IV) (in any of the forms used) as a terminal electron acceptor to support growth. These results have significant implications for the potential remediation of plutonium and suggest that strongly reducing environments where complexing ligands are present may produce soluble forms of reduced Pu species.     

Chelation therapy of incorporated plutonium-238 and americium-241: comparison of LICAM(C), DTPA and DFOA in rats, hamsters and mice

The carboxylated catechoylamide 3,4,3-LICAM(C) was tested for removal of 238Pu and 241Am from small laboratory rodents. The effectiveness of treatment was compared with that of two ligand preparations approved for clinical use: calcium-trisodium diethylenetriaminepentaacetate (DTPA) and desferrioxamine (DFOA). With early treatment and at the dosage used clinically for the decorporation of actinides with DTPA (30 mumol/kg body weight) LICAM(C) was superior to DFOA but when compared with DTPA, the effect of LICAM(C) on 238Pu was greater only in bone; as little as 1 mumol LICAM(C)/kg was as effective as 30 mumol DTPA/kg. However, in all animals treated with LICAM(C) there was a large increase in the 238Pu content of the kidney. With 241Am the effect of DTPA was always superior to that of LICAM(C). The best overall results early (1 day) after injection of 238Pu and 241Am were achieved by a combination of a single injection of LICAM(C) and DTPA with subsequent continuous administration of DTPA in drinking water. LICAM(C) affected the retention of 238Pu even if given orally; the data suggested that about 3 per cent of ingested LICAM(C) was absorbed. When the beginning of treatment was delayed, LICAM(C) became equally effective or less effective than DTPA even as far as 238Pu retention in bone was concerned, but it still increased the accumulation of 238Pu in the kidneys.     

Localization of Purothionins and Genome Expression in Wheat Plants

The leaves, steins and ears of tetraploidal wheat, Triticumdurum (genomes AABB) harvested two weeks after heading wereanalyzed for purothionins. There were considerable amounts oftwo iso-purothionins (Pu-1 and Pu-2) in the young kernels ofthe ears, but not in the leaves and stems. The amino acid compositionsof Pu-1 and Pu-2 were in good agreement with those of Pu I andPu II from hexaploidal wheat. As diploidal wheat, T. monococcum(genome AA) is known to produce only Pu I [Fernandez de Caleyaet al. (1976) Genetics 83: 687], we conclude that the threeiso-purothionins, Pu I, Pu II and Pu III in hexaploidal wheat,T. aestivum (genomes AABBDD), are encoded by the genes of genomesA, B and D, respectively. (Received June 28, 1982; Accepted September 24, 1982)     

Removal of Pu and am from beagles and mice by 3,4,3-LICAM(C) or 3,4,3-LICAM(S)

Decorporation of Pu and Am by tetrameric catechoylamide (CAM) ligands has been investigated in beagles and mice. Eight dogs were injected intravenously (iv) with 237 + 239Pu(IV) + 241Am(III) citrate, and 30 min later, pairs of dogs were injected iv with 30 mumole/kg of 3,4,3-LICAM(C) [N1,N5,N10,N14-tetrakis(2,3-dihydroxy-5-sulfobenzoyl)tetr aazatetradecane, tetrasodium salt], 3,4,3-LICAM(S) [N1,N5,N10,N14-tetrakis(2,3-dihydroxy-4-carboxybenzoyl)te traazatetradecane, tetrasodium salt], CaNa3-DTPA, or each of the latter two ligands. Blood was sampled, and excreta were collected for 7 days, at which time the dogs were sacrificed and nuclide retention in liver and nonliver tissue was measured. Groups of five mice were each given 238Pu(IV) or 241Am(III) citrate iv; 3 min later 30 mumole/kg of a CAM ligand was injected intraperitoneally, mice were killed at 24 hr, and separated excreta and tissues were analyzed. In the dogs, average retention at 7 days of the injected Pu and Am, respectively, was as follows: 12 and 70% after treatment with a CAM ligand alone; 30 and 20% after DTPA; 12 and 20% after LICAM(S) plus DTPA; 90 and 89% without a ligand. In the mice, mean retention of the injected Pu and Am, respectively, was as follows: 14 and 66% after treatment with LICAM(C); 21 and 54% after LICAM(S); 91 and 87% without a ligand. In both species, about 99% of net Pu excretion (excretion with ligand - excretion without ligand) promoted in 24 hr by DTPA or LICAM(S) was in the urine, whereas about 10% of net Pu excretion promoted by the less hydrophilic LICAM(C) was in feces. Delayed excretion of both Am and Pu was significant in all ligand-treated dogs. Comparison of the nuclide content of tissues of ligand-treated mice with those of mice killed 3 min after nuclide injection indicated that the CAM ligands chelated circulating Pu and Am and prevented further deposition. In addition, the CAM ligands removed much of the presumably loosely bound Pu present in liver and skeleton at the time of ligand injection. LICAM(C) was more effective in removing Pu from liver and LICAM(S) was more effective in the skeleton. Moderate to severe uremia and histological evidence of cell killing in the distal tubules of the kidney were observed in the four dogs injected once with 30 mumole/kg of LICAM(S).(ABSTRACT TRUNCATED AT 400 WORDS)     

GABA from putrescine is bound in macromolecular form in keratinocytes

We report for the first time that the neurotransmitter γ-aminobutyric acid (GABA) exists in macromolecular form in keratinocytes. GABA derived from putrescine (Pu) has been identified as a component of acid-precipitable material of cultured human keratinocytes. Confluent, stratified cultures of human foreskin keratinocytes exposed to [³H]-Pu for 4 hours took up about 14% of the radioactivity from the medium and 1% of the total cell-associated radioactivity was precipitable by trichloroacetic acid (TCA). Both attached and shed cells were examined by HPLC for Pu and its radioactive metabolites in TCA-insoluble and TCA-soluble fractions. GABA accounted for the major portion (54%) of the radioactivity derived from Pu in the TCA-precipitable material of attached keratinocytes. Pu and spermidine represented lesser amounts, 35% and 9% respectively, of the total TCA-precipitable radioactivity. In addition, a large portion of acid soluble radioactivity derived from Pu (63%) was GABA, whereas Pu and spermidine represented 29% and 6% respectively of the total TCA-soluble radioactivity. The exact origin of GABA in acid-precipitable material, as well as its form of attachment, is currently under investigation.     

Enhanced decorporation of plutonium by DTPA encapsulated in small PEG-coated liposomes

The aim of the study was to demonstrate that decorporation of 238Pu is achieved more efficiently by an optimized liposomal formulation of diethylene triamine pentaacetic acid (DTPA) than by the usual free DTPA treatment. The optimized formulation consisted of polyethylene glycol-coated stealth liposomes with a mean diameter of 100 nm (SL-100 nm). Rats were intravenously injected with various Pu-phytate salt solutions in order to test different contamination conditions (activity and salt concentration) impacting liver kinetics and skeletal uptake of Pu. All treatments were given intravenously 1 h after contamination. Efficiency was evaluated 24 h, 7, 16 or 30 days later through their ability to promote Pu elimination and to reduce Pu burden in the skeleton and liver, the main organs of Pu deposition and radiotoxicological effects. Whatever the conditions of contaminations, a single injection of SL-100 nm (3.2 micromol kg(-1) DTPA) boosted urinary elimination of Pu to above 90% of the injected dose. In addition, liposomes strongly and significantly reduced the Pu burden of the liver and skeleton even 30 days after a single treatment: a dose of 0.3 micromol kg(-1) induced the same skeletal Pu reduction as four injections of free DTPA (30 micromol kg(-1)). A log dose-effect relation was found with SL-100 nm DTPA and Pu excretion in urine or Pu burden in the studied organs (liver, femurs, spleen and kidneys). This efficacy was attributed to an optimized targeting of DTPA to the main Pu retention organs and especially the liver.     

Structural genomic damage in plutonium workers

The research objective is assessment of structural genomic damages in plutonium workers. The study group included workers of the Mayak Production Association subject to chronic occupational internal exposure to incorporated ²³⁹Pu and/or external γ-rays. A lymphocyte culture of peripheral blood was chosen as an object of study. The yield of intrachromosomal exchange aberrations of chromosomal type on stained slides was analyzed using fluorescent in situ hybridization, mBAND. Linear relationships were revealed between (a) the total yield of chromosome-type aberrations (intra- and inter-chromosomal ones) and the absorbed dose from external exposure of the red bone marrow (RBM) to γ rays, the absorbed dose from internal exposure of the RBM to α-radiation from incorporated ²³⁹Pu, and ²³⁹Pu body burden, and (b) the yield of intrachromosomal aberrations and an absorbed dose from internal exposure of the RBM to ²³⁹Pu and ²³⁹Pu body burden.     

Effects of some factors on the susceptibility of Peromyscus leucopus to infestation by larvae of cuterebra fontinella (Diptera: Cuterebridae).

Two levels of 3 factors, (1) host age, (2) host dietary state in regard to vitamin A, and (3) previous infestation history, were tested individually and in combinations for their effects on the susceptibility of Peromyscus leucopus to infestation by larvae of the rodent bot fly, Cuterebra fontinella. Previous infestation was the only significant single factor. Previously uninfested (Pu) mice usually were more susceptible to infestation than previously infested (Pi) mice. Interactions of age and state of vitamin A had the following effects: 1) Young Pu mice that had been denied vitamin A were much less susceptible to infestation than equivalent mice that had been fed diets containing the vitamin; and 2) when Pu mice were deficient in vitamin A, old mice were more susceptible than young mice but when Pu mice were not deficient in the vitamin, young mice were more susceptible. These findings may have significance for natural infestations of P. leucopus.     

Structural genomic damages in workers of plutonium production

The research objective is assessment of structural genomic damages in plutonium workers. The study group included the Mayak nuclear workers subject to chronic occupational exposure to incorporated 239Pu and/or external gamma-rays. The analysis was performed based on the culture of lymphocytes in peripheral blood. The yield of intra-chromosomal exchange aberrations of chromosomal type on stained slides was analyzed using in situ fluorescent hybridization, mBAND. Linear relationships were revealed between (a) the total yield of chromosomal type aberrations (e.g. intra- and inter-chromosomal ones) and an absorbed dose from external exposure of the red bone marrow to gamma-rays, an absorbed dose from internal exposure to a-radiation from incorporated 239Pu; and (b) the yield of intra-chromosomal exchange aberrations of chromosomal type and an absorbed dose from exposure of the red bone marrow to 239Pu and 239Pu body burden.     

Efficacy of polymeric 239Pu removal by liposome-encapsulated pentacin

Liposome-incapsulated pentacine (DTPA) removes intracellular polimeric 239Pu and colloidal hydroxide of polymeric 239Pu from a rat body in the amounts 2- and 4 times, respectively, exceeding those eliminated by free DTPA. However the amount of 239Pu removed decreases sharply with increasing 239Pu hydrolysation and polymerization. It is concluded that the effectiveness of 239Pu removal depends on the physico-chemical status of the radionuclide and its interaction with the biosubstrate rather than on the amount of DTPA entering the cells.     

Distribution of plutonium in the body of rats after its intratracheal administration in the form of a Pu(IV)-TBP complex

Tributyl phosphate intratracheally administered to rat body with a Pu(IV)-TBP complex does not increase the accumulation of plutonium in the skeleton and liver. Plutonium is excreted from the lungs more readily than Pu(IV) nitrate and its large amounts are resorbed in the blood early after the administration; its excretion in feces is approximately 100 times more intense than in urine.     

Influence of clay mineral type and organic matter content on the uptake of239Pu and241Am by plants

Summary The uptake of²³⁹Pu and²⁴¹Am from different clay mineral-organic matter-sand mixtures simulating contrasting soil types was examined in growth chamber experiments. The mixtures represented various combinations of organic matter (0, 5 and 10%), kaolinite (11 type) and montomorillonite (21 type) clay minerals, each at the levels of 5, 10 and 25%, and purified quartz sand (as filler).Results indicated a marked reduction in uptake of both²³⁹Pu and²⁴¹Am with increase in organic matter as well as clay content of the mixtures. The Pu Concentration Ratios (CRs) ranged from (2.5–7.0)×10^–3 in the case of kaolinite-organic matter mixtures, and from (0.9–5.5)×10^–3 in the case of montmorillonite-organic matter mixtures. The corresponding values of Am Concentration Ratios (CRs) obtained were (1.9–725.4)×10^–3 in the case of kaolinite-organic matter mixtures, and between (0.7–3.5)×10^–3 for the montmorillonite-organic matter mixtures.Reduction in the uptake of²⁴¹Am with increasing clay content was more pronounced in the montmorillonite clay-organic matter mixtures as compared to that in the case of kaolinite-organic matter mixtures. While similar qualitative reduction in²³⁹Pu CRs with increasing clay content was observed, the reduction was less marked than in the case of²⁴¹Am. The values for Am CRs were higher than the corresponding Pu CRs in kaolinite based mixtures whereas in the case of montmorillonite-organic matter mixtures Pu CRs exceeded the Am CRs.Increasing organic matter content and its interaction with both kaolinite and montmorillonite clay minerals were found to be equally effective in reducing the uptake of²³⁹Pu as well as²⁴¹Am by plants.     

Bacterial Pu(V) reduction in the absence and presence of Fe(III)–NTA: modeling and experimental approach

Plutonium (Pu), a key contaminant at sites associated with the manufacture of nuclear weapons and with nuclear-energy wastes, can be precipitated to “immobilized” plutonium phases in systems that promote bioreduction. Ferric iron (Fe³⁺) is often present in contaminated sites, and its bioreduction to ferrous iron (Fe²⁺) may be involved in the reduction of Pu to forms that precipitate. Alternately, Pu can be reduced directly by the bacteria. Besides Fe, contaminated sites often contain strong complexing ligands, such as nitrilotriacetic acid (NTA). We used biogeochemical modeling to interpret the experimental fate of Pu in the absence and presence of ferric iron (Fe³⁺) and NTA under anaerobic conditions. In all cases, Shewanella alga BrY (S. alga) reduced Pu(V)(PuO₂ ⁺) to Pu(III), and experimental evidence indicates that Pu(III) precipitated as PuPO_4(am). In the absence of Fe³⁺ and NTA, reduction of PuO₂ ⁺ was directly biotic, but modeling simulations support that PuO₂ ⁺ reduction in the presence of Fe³⁺ and NTA was due to an abiotic stepwise reduction of PuO₂ ⁺ to Pu⁴⁺, followed by reduction of Pu⁴⁺ to Pu³⁺, both through biogenically produced Fe²⁺. This means that PuO₂ ⁺ reduction was slowed by first having Fe³⁺ reduced to Fe²⁺. Modeling results also show that the degree of PuPO_4(am) precipitation depends on the NTA concentration. While precipitation out-competes complexation when NTA is present at the same or lower concentration than Pu, excess NTA can prevent precipitation of PuPO_4(am).