Metal-organic framework-based materials: superior adsorbents for the capture of toxic and radioactive metal ions.

Highly efficient removal of metal ion pollutants, such as toxic and nuclear waste-related metal ions, remains a serious task from the biological and environmental standpoint because of their harmful effects on human health and the environment. Recently, highly porous metal-organic frameworks (MOFs), with excellent chemical stability and abundant functional groups, have represented a new addition to the area of capturing various types of hazardous metal ion pollutants. This review focuses on recent progress in reported MOFs and MOF-based composites as superior adsorbents for the efficient removal of toxic and nuclear waste-related metal ions. Aspects related to the interaction mechanisms between metal ions and MOF-based materials are systematically summarized, including macroscopic batch experiments, microscopic spectroscopy analysis, and theoretical calculations. The adsorption properties of various MOF-based materials are assessed and compared with those of other widely used adsorbents. Finally, we propose our personal insights into future research opportunities and challenges in the hope of stimulating more researchers to engage in this new field of MOF-based materials for environmental pollution management.

Effect of U(VI) aqueous speciation on the binding of uranium by the cell surface of Rhodotorula mucilaginosa, a natural yeast isolate from bentonites.

This study presents the effect of aqueous uranium speciation (U-hydroxides and U-hydroxo-carbonates) on the interaction of this radionuclide with the cells of the yeast Rhodotorula mucigilanosa BII-R8. This strain was isolated from Spanish bentonites considered as reference materials for the engineered barrier components of the future deep geological repository of radioactive waste. X-ray absorption and infrared spectroscopy showed that the aqueous uranium speciation has no effect on the uranium binding process by this yeast strain. The cells bind mobile uranium species (U-hydroxides and U-hydroxo-carbonates) from solution via a time-dependent process initiated by the adsorption of uranium species to carboxyl groups. This leads to the subsequent involvement of organic phosphate groups forming uranium complexes with a local coordination similar to that of the uranyl mineral phase meta-autunite. Scanning transmission electron microscopy with high angle annular dark field analysis showed uranium accumulations at the cell surface associated with phosphorus containing ligands. Moreover, the effect of uranium mobile species on the cell viability and metabolic activity was examined by means of flow cytometry techniques, revealing that the cell metabolism is more affected by higher concentrations of uranium than the cell viability. The results obtained in this work provide new insights on the interaction of uranium with bentonite natural yeast from genus Rhodotorula under deep geological repository relevant conditions.

On the sequential separation and quantification of 237Np, 241Am, thorium, plutonium, and uranium isotopes in environmental and urine samples.

The implementation of the one-pass-through separation technique using two stacked chromatography columns of TEVA - TRU resins for the separation of 237Np, 241Am, thorium, plutonium and uranium from environmental and urine samples was investigated. The sequential separation technique proved to be successful and gave similar results to those obtained when using individual separations. The analysis time was considerably improved. The amount of chemical waste was also reduced by 50% and the use of HClO4 was avoided. The technique of ICP-MS was also investigated as a complementary technique to alpha-spectrometry.

Evaluation of Chlorella as a Decorporation Agent to Enhance the Elimination of Radioactive Strontium from Body.

BACKGROUND: Release of radionuclides, such as 137Cs and 90Sr, into the atmosphere and the ocean presents an important problem because internal exposure to 137Cs and 90Sr could be very harmful to humans. Chlorella has been reported to be effective in enhancing the excretion of heavy metals; thus, we hypothesized that Chlorella could also enhance the elimination of 137Cs or 90Sr from the body. We evaluated the potential of Chlorella as a decorporation agent in vitro and in vivo, using 85Sr instead of 90Sr. METHODS: In vitro experiments of adsorption of 137Cs and 85Sr to Chlorella were performed under wide pH conditions. The maximum sorption capacity of Chlorella to strontium was estimated using the Langmuir model. A 85Sr solution was orally administrated to mice pretreated with Chlorella. At 48 h after 85Sr administration, the biodistribution of radioactivity was determined. RESULTS: In the in vitro experiments, although 85Sr barely adsorbed to Chlorella at low pH, the 85Sr adsorption ratio to Chlorella increased with increasing pH. The maximum sorption capacity of Chlorella to strontium was 9.06 mg / g. 137Cs barely adsorbed to Chlorella under any pH conditions. In the biodistribution experiments, bone accumulation of radioactivity after 85Sr administration was significantly decreased in the Chlorella pretreatment group compared with the non-treatment control group. CONCLUSIONS: In conclusion, these results indicated that Chlorella could inhibit the absorption of 90Sr into the blood and enhance the elimination of 90Sr from the body through adsorption in intestine. Further studies are required to elucidate the mechanism and the components of Chlorella needed for adsorption to strontium and could promote the development of more effective decorporation agents.

Automation of 99Tc extraction by LOV prior ICP-MS detection: application to environmental samples.

A new, fast, automated and inexpensive sample pre-treatment method for (99)Tc determination by inductively coupled plasma-mass spectrometry (ICP-MS) detection is presented. The miniaturized approach is based on a lab-on-valve (LOV) system, allowing automatic separation and preconcentration of (99)Tc. Selectivity is provided by the solid phase extraction system used (TEVA resin) which retains selectively pertechnetate ion in diluted nitric acid solution. The proposed system has some advantages such as minimization of sample handling, reduction of reagents volume, improvement of intermediate precision and sample throughput, offering a significant decrease of both time and cost per analysis in comparison to other flow techniques and batch methods. The proposed LOV system has been successfully applied to different samples of environmental interest (water and soil) with satisfactory recoveries, between 94% and 98%. The detection limit (LOD) of the developed method is 0.005 ng. The high durability of the resin and its low amount (32 mg), its good intermediate precision (RSD 3.8%) and repeatability (RSD 2%) and its high extraction frequency (up to 5 h(-1)) makes this method an inexpensive, high precision and fast tool for monitoring (99)Tc in environmental samples.

Highly luminescent and stable hydroxypyridinonate complexes: a step towards new curium decontamination strategies.

The photophysical properties, solution thermodynamics, and in vivo complex stabilities of Cm(III) complexes formed with multidentate hydroxypyridinonate ligands, 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO), are reported. Both chelators were investigated for their ability to act as antenna chromophores for Cm(III), leading to highly sensitized luminescence emission of the metal upon complexation, with long lifetimes (383 and 196 µs for 3,4,3-LI(1,2-HOPO) and 5-LIO(Me-3,2-HOPO), respectively) and remarkable quantum yields (45 % and 16 %, respectively) in aqueous solution. The bright emission peaks were used to probe the electronic structure of the 5f complexes and gain insight into ligand field effects; they were also exploited to determine the high (and proton-independent) stabilities of the corresponding Cm(III) complexes (log ß110 = 21.8(4) for 3,4,3-LI(1,2-HOPO) and log ß120 = 24.5(5) for 5-LIO(Me-3,2-HOPO)). The in vivo complex stability for both ligands was assessed by using (248) Cm as a tracer in a rodent model, which provided a direct comparison with the in vitro thermodynamic results and demonstrated the great potential of 3,4,3-LI(1,2-HOPO) as a therapeutic Cm(III) decontamination agent.

Evaluation of vegetables in Tsukuba for contamination with radioactive materials from the accident at Fukushima Daiichi nuclear power plant.

A large amount of radioactive material was released into the atmosphere after the accident of the Fukushima Daiichi Nuclear Power Plant following the Tohoku earthquake on 11 March 2011, and traces of these materials were detected in Tsukuba. Because radioactive materials can adhere to vegetables, the authors made a qualitative evaluation of vegetables in Tsukuba, estimated internal exposure dose based on quantitative measurement results, and investigated several decontamination methods. Qualitative analysis of vegetable contamination was done by autoradiography. Quantitative analysis was done using a high-purity germanium detector. To assess decontamination, two methods were tested: one with running water and the other with boiling water. In addition, boiled soup stock was measured. In the qualitative evaluation by autoradiography, radioactive materials were not uniformly distributed but adhered to vegetables in clumps and hot spots. In the quantitative evaluation to measure contamination of outer and inner leaves of sanchu lettuce, it was observed that the concentration of I was 8,031.35 ± 764.79 Bq kg in the outer leaves and 115.28 ± 20.63 Bq kg in the inner leaves. In addition, the concentration of Cs was 1,371.93 ± 366.45 Bq kg in the outer leaves and 9.68 ± 15.03 Bq kg in the inner leaves. This suggests that one can greatly reduce internal exposure dose by removing the outer leaves if one has to eat vegetables just after a nuclear accident. In the decontamination assessment, a decontamination efficiency of up to 70% was achieved by boiling vegetables for 20 min.

Decontamination of radionuclides from skin: an overview.

The accident in Fukushima has emphasized the need to increase the capacity of health protection for exposed workers, first responders, and the general public in a major accident situation with release of radioactivity. Skin contamination is one of the most probable risks following major nuclear or radiological incidents, but this risk also exists and incidents can happen in industry, research laboratories, or in nuclear medicine departments. The aim of this paper is to provide an overview of the products currently used after skin contamination in order to highlight the needs and ways to improve the medical management of victims. From this review, it can be observed that the current use of these radiological decontamination products is essentially based on empiricism. In addition, some of these products are harsh and irritating, even toxic, possibly damaging the skin barrier. In some emergency situations in which clean water is in short supply, most of the current products cannot be used. Research on the mechanisms of action of decontaminating products is needed to develop a decontamination strategy.

Dealing with the aftermath of Fukushima Daiichi nuclear accident: decontamination of radioactive cesium enriched ash.

Environmental radioactivity, mainly in the Tohoku and Kanto areas, due to the long living radioisotopes of cesium is an obstacle to speedy recovery from the impacts of the Fukushima Daiichi Nuclear Power Plant accident. Although incineration of the contaminated wastes is encouraged, safe disposal of the Cs enriched ash is the big challenge. To address this issue, safe incineration of contaminated wastes while restricting the release of volatile Cs to the atmosphere was studied. Detailed study on effective removal of Cs from ash samples generated from wood bark, household garbage, and municipal sewage sludge was performed. For wood ash and garbage ash, washing only with water at ambient conditions removed radioactivity due to (134)Cs and (137)Cs, retaining most of the components other than the alkali metals with the residue. However, removing Cs from sludge ash needed acid treatment at high temperature. This difference in Cs solubility is due to the presence of soil particle originated clay minerals in the sludge ash. Because only removing the contaminated vegetation is found to sharply decrease the environmental radioactivity, volume reduction of contaminated biomass by incineration makes great sense. In addition, need for a long-term leachate monitoring system in the landfill can be avoided by washing the ash with water. Once the Cs in solids is extracted to the solution, it can be loaded to Cs selective adsorbents such as Prussian blue and safely stored in a small volume.

Accident at the Fukushima Dai-ichi nuclear power stations of TEPCO--outline & lessons learned.

The severe accident that broke out at Fukushima Dai-ichi nuclear power stations on March 11, 2011, caused seemingly infinite damage to the daily life of residents. Serious and wide-spread contamination of the environment occurred due to radioactive materials discharged from nuclear power stations (NPSs). At the same time, many issues were highlighted concerning countermeasures to severe nuclear accidents. The accident is outlined, and lessons learned are extracted with respect to the safety of NPSs, as well as radiation protection of residents under the emergency involving the accident. The materials of the current paper are those released by governmental agencies, academic societies, interim reports of committees under the government, and others.

Redox behavior of uranium at the nanoporous aluminum oxide-water interface: implications for uranium remediation.

Sorption-desorption experiments show that the majority (ca. 80-90%) of U(VI) presorbed to mesoporous and nanoporous alumina could not be released by extended (2 week) extraction with 50 mM NaHCO(3) in contrast with non-nanoporous α alumina. The extent of reduction of U(VI) presorbed to aluminum oxides was semiquantitatively estimated by comparing the percentages of uranium desorbed by anoxic sodium bicarbonate between AH(2)DS-reacted and unreacted control samples. X-ray absorption spectroscopy confirmed that U(VI) presorbed to non-nanoporous alumina was rapidly and completely reduced to nanoparticulate uraninite by AH(2)DS, whereas reduction of U(VI) presorbed to nanoporous alumina was slow and incomplete (<5% reduction after 1 week). The observed nanopore size-dependent redox behavior of U has important implications in developing efficient remediation techniques for the subsurface uranium contamination because the efficiency of in situ bioremediation depends on how effectively and rapidly U(VI) bound to sediment or soil can be converted to an immobile phase.

Rapid determination of 226Ra in urine samples.

A new radiochemical separation method has been developed for rapid analysis of (226)Ra in urine samples. In this method, radium is separated from urine matrix using cation and anion exchange column chromatography. A (224)Ra tracer is added, together with its parent in the (228)Th standard, for chemical recovery correction. After separation, the sample is precipitated with hydrous titanium oxide and then prepared for counting by creating a thin-layer counting source using BaSO(4) micro-precipitation. The radium isotopes are then counted by alpha spectrometry. Replicate spike and blank samples were analysed for validation of the procedure. The detection limit was determined to be 0.22 Bq l(-1) with 4 h of counting for 20 ml of urine sample. Using this method, the results can be reported within an 8 h turn-around time. This method is suitable for quick dose assessment of (226)Ra exposure following a radiation emergency.

Investigation of strontium sorption onto Kula volcanics using Central Composite Design.

In performance assessment studies, the uptake of the radioactive elements by rock formations play an important role in retarding their aqueous phase migration. Sorption studies of radionuclides have been conducted to obtain data on the distribution coefficient (K(d)) that is as an input parameter in the performance assessment of the geological disposal of radioactive wastes. In this work, sorption experiments were studied in a batch sorption system using Sr(NO(3))(2) solution on non-treated and HCl-treated Kula volcanics. The distribution coefficient (K(d)) values of Sr(2+) derived from batch experiments were used to evaluate the migration behavior of Sr(2+). Central Composite Design was used in the experiments. Sr sorption was studied as a function of pH, temperature, initial concentration of adsorbate and contact time. The results show that the K(d) values are higher at pH 7-9 which is the pH range of the natural waters. The kinetic data conformed better to the pseudo-second-order equation. Thermodynamic parameters ΔH°, ΔS° and ΔG° were estimated and these parameters show that adsorption is endothermic. The correlation coefficients indicate that the Langmuir model fits better for the strontium sorption onto non-treated and HCl-treated Kula volcanics with monolayer capacities as 2.04 and 1.72 mg/g, respectively.

An emergency radiobioassay method for 226Ra in human urine samples.

A new radioanalytical method was developed for rapid determination of (226)Ra in human urine samples. The method is based on organic removal and decolourisation of a urine sample by a polymeric (acrylic ester) solid phase sorbent material followed by extraction and preconcentration of (226)Ra in an organic solvent using a dispersive liquid-liquid microextraction technique. Radiometric measurement of (226)Ra was carried out using a liquid scintillation counting instrument. The minimum detectable activity for the method (0.15 Bq l(-1)) is lower than the required sensitivity of 0.2 Bq l(-1) for (226)Ra in human urine samples as defined in the requirements for radiation emergency bioassay techniques for the public and first responders based on the dose threshold for possible medical attention recommended by the International Commission on Radiological Protection (ICRP). The accuracy (expressed as relative bias, B(r)) and repeatability of the method (expressed as relative precision, S(B)) evaluated at the reference level (2 Bq l(-1)) were found to be -4.5 and 2.6 %, respectively. The sample turnaround time was <5 h for a single urine sample and <20 h for a batch of six urine samples. With the fast sample turnaround time combined with the potential to carry out the analysis in a field deployable mobile laboratory, the newly developed method can be used for emergency radiobioassay of (226)Ra in human urine samples following a radiological or nuclear accident.

Distribution of naturally occurring radioactive materials in sediments from the Ebro river reservoir in Flix (Southern Catalonia, Spain).

Industrial waste containing radioactive isotopes (from U-decay series) was released into Ebro river basin due to the activity of a dicalcium phosphate (DCP) plant for a period of more than two decades. Gross alpha, gross beta, (40)K, (226)Ra and (210)Pb activities were determined in several sludge samples taken at different depths from different points in the area of influence of the DCP plant located in Flix. Samples were collected from two different zones: one in front of the DCP plant and the second in front of a wastewater treatment plant installed several years after the DCP plant. The data obtained verify the influence of industrial DCP production on radioactivity levels present in the area.

Long-term leaching of uranium from different waste matrices.

A semi-dynamic leaching test was carried out for metallurgical wastes and ore samples from the uranium and copper mining industry over a 142 day period using distilled water and 0.1N NaNO(3) as solvents. Laser fluorimetry was used as the analytical technique to determine the total uranium content in the leachates. The cumulative leach fraction (CLF) of uranium release from the samples was calculated to be 0.22, 0.22, 0.07 and 0.39% for rock, uranium tailings, copper kinker ash samples and copper tailings respectively using distilled water as solvent and 0.31, 0.27, 0.05 and 0.59% for the same matrices using 0.1N NaNO(3). The release of mobile uranium fraction was very slow, being faster in the initial stage and then attained a near steady state condition. The diffusion coefficient and bulk release of uranium from the samples have been calculated. The processes governing the release of uranium from these matrices have been identified to be surface wash-off and diffusion. Hence the use of weak solvents (leach out the mobile/exchangeable fraction of uranium) under semi-dynamic conditions aids the determination of leaching parameters and identification of the leaching mechanism for mobile uranium fraction from different matrices by slow leaching processes.

The effectiveness of decontamination products in the nuclear medicine department.

UNLABELLED: This study assesses the effectiveness of using everyday cleaning agents for the radioactive decontamination of wet (99m)Tc-pertechnetate spills in the nuclear medicine department. METHODS: Six cleaning agents (water, water and soap, alcohol, bleach, a commercial glass cleaner, and a commercial decontaminating agent) were analyzed for decontamination effectiveness for a wide range of surfaces (Formica, vinyl, vinyl-polyester, plastic, rubber, and polyester). RESULTS: Within the experiment, the contamination was removed to radioactivity levels of less than 1% of the original contamination level. CONCLUSION: The results indicate that for a range of surfaces, the investigated commercially available cleaning agents had little or no benefit over plain tap water when used to decontaminate (99m)Tc-pertechnetate spills.

New experimental approach for studying diffusion through an intact and unsaturated medium: a case study with Callovo-Oxfordian argillite.

The diffusion of tritiated water and anionic species was studied in an unsaturated core of Callovo-Oxfordian claystone, which is a potential host-rock for disposal of high-level radioactive wastes. The diffusion parameters in such conditions were determined using modified through-diffusion cells in which the suction is generated by the osmosis process. This specific device leads to values of saturation degree ranging from 81% to 100%. The results show that the diffusion through unsaturated samples is clearly slower than that in fully saturated samples, with steady-state fluxes decreasing by a factor up to 7 for tritium and up to 50 for anionic species. While tritium porosity values follow volumetric water contents (from 21 to 16%), the porosity accessible to anionic species significantly decreases (from 7.5 to 0.7%). Such diffusive behaviors have been modeled by means of a modified Archie's law, taking into account a critical water saturation below which no tracer can percolate. These results indicate that the largest pores, which are initially affected by dehydration, would play an important role on the connectivity of the porous medium. This would especially affect anionic species diffusion behavior because they are constrained to diffuse into the largest pores first.

Sorption profile and chromatographic separation of uranium (VI) ions from aqueous solutions onto date pits solid sorbent.

The retention profile of uranium (VI) as uranyl ions (UO(2)(2+)) from the aqueous media onto the solid sorbent date pits has been investigated. The sorption of UO(2)(2+) ions onto the date pits was achieved quantitatively (98+/-3.4%, n=5) after 15 min of shaking at pH 6-7. The sorption of UO(2)(2+) onto the used sorbent was found fast, followed by a first order rate equation with an overall rate constant, k of 4.8+/-0.05 s(-1). The sorption data were explained in a manner consistent with a "solvent extraction" mechanism. The sorption data were also subjected to Freundlich isotherm model over a wide range of equilibrium concentration (1-20 microgmL(-1)) of UO(2)(2+). The results revealed that, a "dual-mode" of sorption mechanism involving absorption related to "solvent extraction" and an added component for "surface adsorption" is most likely operated simultaneously for uranyl ions uptaking the solid sorbent. The thermodynamic parameters (-DeltaH, DeltaS and DeltaG) of the uranyl ions uptake onto the date pits indicated that, the process is endothermic and proceeds spontaneously. The interference of some diverse ions on the sorption UO(2)(2+) from the aqueous media onto the date pits packed column was critically investigated and the data revealed quantitative collection of UO(2)(2+) at 5 mLmin(-1) flow rate. The retained UO(2)(2+) was recovered quantitatively with HCl (3.0 molL(-1)) from the column at 5 mLmin(-1) flow rate. The mode of binding of the date pits with UO(2)(2+) was determined from the IR spectral date bits before and after extraction of uranium (VI). The height equivalent (HETP) and the number (N) of theoretical plates of the date pits packed column were determined from the chromatograms. Complete retention and recovery of UO(2)(2+) spiked to wastewater samples by the date pits packed column was successfully achieved. The capacity of the used sorbent towards retention of uranium (VI) from aqueous solutions was much better than the most common sorbents.

Sorption of uranyl ions on titanium oxide studied by ATR-IR spectroscopy.

ATR-IR spectroscopy was used to study the sorption of uranyl ions (10(-4) M) onto titanium oxide (mixture of rutile and anatase). A circulation setup, filled with a solution in D(2)O, allowed recording of the evolution of the antisymmetric O=U=O stretching of uranyl species onto titanium oxide particles deposited on the ATR crystal. The band centered at 915 cm(-1) has been decomposed in two Gaussian peaks at 920 and 905 cm(-1). From these values, and the observation that the ratio of the areas of the two peaks vs pH was constant, we have proposed that uranyl sorption on titanium oxide in the pH range 4-7 leads to the formation of one surface complex where uranium atoms have two different chemical environments. A trimer surface complex linked by two uranium atoms to the titanium oxide surface would be consistent with this interpretation.