Influence of Uranium Concentration and pH on U-Phosphate Biomineralization by Caulobacter OR37.

Uranium contamination of soils and groundwater in the United States represents a significant health risk and will require multiple remediation approaches. Microbial phosphatase activity coupled to the addition of an organic P source has recently been studied as a remediation strategy that provides an extended release of inorganic P (Pi) into U-contaminated sites, resulting in the precipitation of meta-autunite minerals. Previous laboratory- and field-based biomineralization studies have investigated environments with relatively high U concentrations (>20 µM). However, most contaminated sites have much lower U concentrations (<2 µM). The Environmental Protection Agency (EPA) limit for U in drinking water is 0.126 µM. Reaching this regulatory limit becomes challenging as U concentrations approach autunite solubility. We studied the precipitation of U(VI)-phosphate minerals by an environmental isolate of Caulobacter sp. (strain OR37) from an Oak Ridge, Tennessee, U-contaminated site. Abiotic U(VI) solubility experiments reveal that U(VI)-phosphate minerals do not form in the presence of excess Pi (500 µM) when U(VI) concentrations are <1 µM and pH is <5. When OR37 cells are reacted under the same conditions with Pi or glycerol-2-phosphate, U(VI)-phosphate mineral formation was observed, along with the formation of intracellular polyphosphate granules. These results show that bacteria provide supersaturated microenvironments needed for U(VI)-phosphate mineralization while hydrolyzing organic P sources. This provides a pathway to lower U concentrations to below EPA limits for drinking water.

Hydrothermal Alteration of Nuclear Melt Glass, Colloid Formation, and Plutonium Mobilization at the Nevada National Security Site, U.S.A.

Approximately 2.8 t of plutonium (Pu) has been deposited in the Nevada National Security Site (NNSS) subsurface as a result of underground nuclear testing. Most of this Pu is sequestered in nuclear melt glass. However, Pu migration has been observed and attributed to colloid facilitated transport. To identify the mechanisms controlling Pu mobilization, long-term (∼3 year) laboratory nuclear melt glass alteration experiments were performed at 25 to 200 °C to mimic hydrothermal conditions in the vicinity of underground nuclear tests. The clay and zeolite colloids produced in these experiments are similar to those identified in NNSS groundwater. At 200 °C, maximum Pu and colloid concentrations of 30 Bq/L and 150 mg/L, respectively, were observed. However, much lower Pu and colloid concentrations were observed at 25 and 80 °C. These data suggest that Pu concentrations above the drinking water Maximum Contaminant Levels (0.56 Bq/L) may exist during early hydrothermal conditions in the vicinity of underground nuclear tests. However, formation of colloid-associated Pu will tend to decrease with time as nuclear test cavity temperatures decrease. Furthermore, median colloid concentrations in NNSS groundwater (1.8 mg/L) suggest that the high colloid and Pu concentrations observed in our 140 and 200 °C experiments are unlikely to persist in downgradient NNSS groundwater. While our experiments did not span all groundwater and nuclear melt glass conditions that may be present at the NNSS, our results are consistent with the documented low Pu concentrations in NNSS groundwater.

Plutonium(IV) and (V) Sorption to Goethite at Sub-Femtomolar to Micromolar Concentrations: Redox Transformations and Surface Precipitation.

Pu(IV) and Pu(V) sorption to goethite was investigated over a concentration range of 10(-15)-10(-5) M at pH 8. Experiments with initial Pu concentrations of 10(-15) - 10(-8) M produced linear Pu sorption isotherms, demonstrating that Pu sorption to goethite is not concentration-dependent across this concentration range. Equivalent Pu(IV) and Pu(V) sorption Kd values obtained at 1 and 2-week sampling time points indicated that Pu(V) is rapidly reduced to Pu(IV) on the goethite surface. Further, it suggested that Pu surface redox transformations are sufficiently rapid to achieve an equilibrium state within 1 week, regardless of the initial Pu oxidation state. At initial concentrations >10(-8) M, both Pu oxidation states exhibited deviations from linear sorption behavior and less Pu was adsorbed than at lower concentrations. NanoSIMS and HRTEM analysis of samples with initial Pu concentrations of 10(-8) - 10(-6) M indicated that Pu surface and/or bulk precipitation was likely responsible for this deviation. In 10(-6) M Pu(IV) and Pu(V) samples, HRTEM analysis showed the formation of a body centered cubic (bcc) Pu4O7 structure on the goethite surface, confirming that reduction of Pu(V) had occurred on the mineral surface and that epitaxial distortion previously observed for Pu(IV) sorption occurs with Pu(V) as well.

Effect of fulvic acid surface coatings on plutonium sorption and desorption kinetics on goethite.

The rates and extent of plutonium (Pu) sorption and desorption onto mineral surfaces are important parameters for predicting Pu mobility in subsurface environments. The presence of natural organic matter, such as fulvic acid (FA), may influence these parameters. We investigated the effects of FA on Pu(IV) sorption/desorption onto goethite in two scenarios: when FA was (1) initially present in solution or (2) found as organic coatings on the mineral surface. A low pH was used to maximize FA coatings on goethite. Experiments were combined with kinetic modeling and speciation calculations to interpret variations in Pu sorption rates in the presence of FA. Our results indicate that FA can change the rates and extent of Pu sorption onto goethite at pH 4. Differences in the kinetics of Pu sorption were observed as a function of the concentration and initial form of FA. The fraction of desorbed Pu decreased in the presence of FA, indicating that organic matter can stabilize sorbed Pu on goethite. These results suggest that ternary Pu-FA-mineral complexes could enhance colloid-facilitated Pu transport. However, more representative natural conditions need to be investigated to quantify the relevance of these findings.

Plutonium desorption from mineral surfaces at environmental concentrations of hydrogen peroxide.

Knowledge of Pu adsorption and desorption behavior on mineral surfaces is crucial for understanding its environmental mobility. Here we demonstrate that environmental concentrations of H2O2 can affect the stability of Pu adsorbed to goethite, montmorillonite, and quartz across a wide range of pH values. In batch experiments where Pu(IV) was adsorbed to goethite for 21 days at pH 4, 6, and 8, the addition of 5-500 µM H2O2 resulted in significant Pu desorption. At pH 6 and 8 this desorption was transient with readsorption of the Pu to goethite within 30 days. At pH 4, no Pu readsorption was observed. Experiments with both quartz and montmorillonite at 5 µM H2O2 desorbed far less Pu than in the goethite experiments highlighting the contribution of Fe redox couples in controlling Pu desorption at low H2O2 concentrations. Plutonium(IV) adsorbed to quartz and subsequently spiked with 500 µM H2O2 resulted in significant desorption of Pu, demonstrating the complexity of the desorption process. Our results provide the first evidence of H2O2-driven desorption of Pu(IV) from mineral surfaces. We suggest that this reaction pathway coupled with environmental levels of hydrogen peroxide may contribute to Pu mobility in the environment.

Pu(V) and Pu(IV) sorption to montmorillonite.

Plutonium (Pu) adsorption to and desorption from mineral phases plays a key role in controlling the environmental mobility of Pu. Here we assess whether the adsorption behavior of Pu at concentrations used in typical laboratory studies (≥10(-10) [Pu] ≤ 10(-6) M) are representative of adsorption behavior at concentrations measured in natural subsurface waters (generally <10(-12) M). Pu(V) sorption to Na-montmorillonite was examined over a wide range of initial Pu concentrations (10(-6)-10(-16) M). Pu(V) adsorption after 30 days was linear over the wide range of concentrations studied, indicating that Pu sorption behavior from laboratory studies at higher concentrations can be extrapolated to sorption behavior at low, environmentally relevant concentrations. Pu(IV) sorption to montmorillonite was studied at initial concentrations of 10(-6)-10(-11) M and was much faster than Pu(V) sorption over the 30 day equilibration period. However, after one year of equilibration, the extent of Pu(V) adsorption was similar to that observed for Pu(IV) after 30 days. The continued uptake of Pu(V) is attributed to a slow, surface-mediated reduction of Pu(V) to Pu(IV). Comparison between rates of adsorption of Pu(V) to montmorillonite and a range of other minerals (hematite, goethite, magnetite, groutite, corundum, diaspore, and quartz) found that minerals containing significant Fe and Mn (hematite, goethite, magnetite, and groutite) adsorbed Pu(V) faster than those which did not, highlighting the potential importance of minerals with redox couples in increasing the rate of Pu(V) removal from solution.

Importance of humidity for characterization and communication of dangerous heatwave conditions.

Heatwaves are one of the leading causes of climate-induced mortality. Using the examples of recent heatwaves in Europe, the United States and Asia, we illustrate how the communication of dangerous conditions based on temperature maps alone can lead to insufficient societal perception of health risks. Comparison of maximum daily values of temperature with physiological heat stress indices accounting for impacts of both temperature and humidity, illustrates substantial differences in geographical extent and timing of their respective peak values during these recent events. This signals the need to revisit how meteorological heatwaves and their expected impacts are communicated. Close collaboration between climate and medical communities is needed to select the best heat stress indicators, establish them operationally, and introduce them to the public. npj Climate and Atmospheric Science (2023) 6:33.

Plutonium mobilization from contaminated estuarine sediments, Esk Estuary (UK).

Since 1952, liquid radioactive effluent containing238-242Pu, 241Am, 237Np, 137Cs, and 99Tc has been released with authorization from the Sellafield nuclear complex (UK) into the Irish Sea. This represents the largest source of plutonium (Pu) discharged in all western Europe, with 276 kg having been released. In the Eastern Irish Sea, the majority of the transuranic activity has settled into an area of sediments (Mudpatch) located off the Cumbrian coast. Radionuclides from the Mudpatch have been re-dispersed via particulate transport in fine-grained estuarine and intertidal sediments to the North-East Irish Sea, including the intertidal saltmarsh located at the mouth of the Esk Estuary. Saltmarshes are highly dynamic systems which are vulnerable to external agents (sea level change, erosion, sediment supply, and freshwater inputs), and their stability remains uncertain under current sea level rise projections and possible increases in storm activity. In this work, we examined factors affecting Pu mobility in contaminated sediments collected from the Esk Estuary by conducting leaching experiments under both anoxic and oxic conditions. Leaching experiments were conducted over a 9-month period and were periodically sampled to determine solution phase Pu via multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS), and to measure redox indicators (Eh, pH and extractable Fe(II)). Microbial community composition was also characterized in the sediments, and at the beginning and end of the anoxic/oxic experiments. Results show that: 1) Pu leaching is about three times greater in solutions leached under anoxic conditions compared to oxic conditions, 2) the sediment slurry microbial communities shift as conditions change from anoxic to oxic, 3) Pu leaching is enhanced in the shallow sediments (0-10 cm depth), and 4) the magnitude of Pu leached from sediments is not correlated with total Pu, indicating that the biogeochemistry of sediment-associated Pu is spatially heterogeneous. These findings provide constraints on the stability of redox sensitive Pu in biogeochemically dynamic/transient environments on a timescale of months and suggests that anoxic conditions can enhance Pu mobility in estuarine systems.

Geomicrobiological redox cycling of the transuranic element neptunium.

Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management.

Cesium sorption reversibility and kinetics on illite, montmorillonite, and kaolinite.

Understanding sorption and desorption processes is essential to predicting the mobility of radionuclides in the environment. We investigate adsorption/desorption of cesium in both binary (Cs+one mineral) and ternary (Cs+two minerals) experiments to study component additivity and sorption reversibility over long time periods (500days). Binary Cs sorption experiments were performed with illite, montmorillonite, and kaolinite in a 5mM NaCl/0.7mM NaHCO3 solution (pH8) and Cs concentration range of 10-3 to 10-11M. The binary sorption experiments were followed by batch desorption experiments. The sorption behavior was modeled with the FIT4FD code and the results used to predict desorption behavior. Sorption to montmorillonite and kaolinite was linear over the entire concentration range but sorption to illite was non-linear, indicating the presence of multiple sorption sites. Based on the 14day batch desorption data, cesium sorption appeared irreversible at high surface loadings in the case of illite but reversible at all concentrations for montmorillonite and kaolinite. A novel experimental approach, using a dialysis membrane, was adopted in the ternary experiments, allowing investigation of the effect of a second mineral on Cs desorption from the original mineral. Cs was first sorbed to illite, montmorillonite or kaolinite, then a 3.5-5kDalton Float-A-Lyzer® dialysis bag with 0.3g of illite was introduced to each experiment inducing desorption. Nearly complete Cs desorption from kaolinite and montmorillonite was observed over the experiment, consistent with our equilibrium model, indicating complete Cs desorption from these minerals. Results from the long-term ternary experiments show significantly greater Cs desorption compared to the binary desorption experiments. Approximately ~45% of Cs desorbed from illite. However, our equilibrium model predicted ~65% desorption. Importantly, the data imply that in some cases, slow desorption kinetics rather than permanent fixation may play an important role in apparent irreversible Cs sorption.

The behaviour of technetium during microbial reduction in amended soils from Dounreay, UK.

Radioactive technetium-99 forms during nuclear fission and has been found as a contaminant at sites where nuclear wastes have been processed or stored. Here we describe results from microcosm experiments containing soil samples representative of the UKAEA site at Dounreay to examine the effect of varying solution chemistry on the fate of technetium during microbial reduction. Analysis of a suite of stable element redox indicators demonstrated that microbial activity occurred in a range of microcosm experiments including unamended Dounreay sediments, carbonate buffered sediments, and microcosms amended with ethylenediaminetetraacetic acid (EDTA) a complexing ligand used in nuclear fuel cycle operations. During the development of anoxia mediated by indigenous microbial populations, TcO4- was removed from solution in experiments. In all cases, the removal of TcO4- from solution occurred during active microbial Fe(III)-reduction when Fe(II) was growing into the microcosms. Tc removal was most likely via reduction of TcO4- to poorly soluble Tc(IV) which is retained on the sediments. The potential stability of Tc associated with the soil to remobilisation via complexation with EDTA was examined as reduced Tc-labelled sediments were contacted with a de-oxygenated EDTA solution. No remobilisation of Tc(IV) in the presence of EDTA was observed.

Plutonium sorption and desorption behavior on bentonite.

Understanding plutonium (Pu) sorption to, and desorption from, mineral phases is key to understanding its subsurface transport. In this work we study Pu(IV) sorption to industrial grade FEBEX bentonite over the concentration range 10(-7)-10(-16) M to determine if sorption at typical environmental concentrations (≤10(-12) M) is the same as sorption at Pu concentrations used in most laboratory experiments (10(-7)-10(-11) M). Pu(IV) sorption was broadly linear over the 10(-7)-10(-16) M concentration range during the 120 d experimental period; however, it took up to 100 d to reach sorption equilibrium. At concentrations ≥10(-8) M, sorption was likely affected by additional Pu(IV) precipitation/polymerization reactions. The extent of sorption was similar to that previously reported for Pu(IV) sorption to SWy-1 Na-montmorillonite over a narrower range of Pu concentrations (10(-11)-10(-7) M). Sorption experiments with FEBEX bentonite and Pu(V) were also performed across a concentration range of 10(-11)-10(-7) M and over a 10 month period which allowed us to estimate the slow apparent rates of Pu(V) reduction on a smectite-rich clay. Finally, a flow cell experiment with Pu(IV) loaded on FEBEX bentonite demonstrated continued desorption of Pu over a 12 day flow period. Comparison with a desorption experiment performed with SWy-1 montmorillonite showed a strong similarity and suggested the importance of montorillonite phases in controlling Pu sorption/desorption reactions on FEBEX bentonite.