Accumulation mechanisms for contaminants on weak-base hybrid ion exchange resins.

Mechanism of hexavalent chromium removal (Cr(VI) as CrO42-) by the weak-base ion exchange (IX) resin ResinTech® SIR-700-HP (SIR-700) from simulated groundwater is assessed in the presence of radioactive contaminants iodine-129 (as IO3-), uranium (U as uranyl UO22+), and technetium-99 (as TcO4-), and common environmental anions sulfate (SO42-) and chloride (Cl-). Batch tests using the acid sulfate form of SIR-700 demonstrated Cr(VI) and U(VI) removal exceeded 97%, except in the presence of high SO42- concentrations (536 mg/L) where Cr(VI) and U(VI) removal decreased to ≥ 80%. However, Cr(VI) removal notably improved with co-mingled U(VI) that complexes with SO42- at the protonated amine sites. These U-SO42- complexes are integral to U(VI) removal, as confirmed by the decrease in U(VI) removal (<40%) when the acid chloride form of SIR-700 was used instead. Solid phase characterization revealed that CrO42- is removed by IX with SO42- complexes and/or reduced to amorphous Cr(III)(OH)3 at secondary alcohol sites. Tc(VII)O4- and I(V)O3- also undergo chemical reduction, following a similar removal mechanism. Oxyanion removal preference is determined by the anion reduction potential (CrO42->TcO4->IO3-), geometry, and charge density. For these reasons, 39% and 69% of TcO4- and 17% and 39% of IO3- are removed in the presence and absence of Cr(VI), respectively.

Reductive removal of pertechnetate and chromate by zero valent iron under variable ionic strength conditions.

Radioactive technetium-99 (Tc) present in waste streams and subsurface plumes at legacy nuclear reprocessing sites worldwide poses potential risks to human health and environment. This research comparatively evaluated efficiency of zero-valent iron (ZVI) toward reductive removal of Tc(VII) in presence of Cr(VI) from NaCl and Na2SO4 electrolyte solutions under ambient atmospheric conditions. In both electrolytes, anticorrosive Cr(VI) suppressed oxidation of ZVI at elevated concentrations resulting in the delay of initiation of Tc(VII) reduction to Tc(IV). In the absence of Cr(VI), no delay was observed in the analogous systems. At low ionic strength (IS), retarded ZVI oxidation inhibited Tc(VII) reduction. Higher IS favored reduction of both Tc(VII) and Cr(VI), which followed second-order reaction rates in both electrolytes attributed to the more efficient iron oxidation as evident from solids characterization studies. Magnetite was the primary iron oxide phase, and its higher fraction in the SO42- solutions facilitated reductive removal of Tc(VII) and Cr(VI). In the Cl- matrix, Cr(VI) promoted further oxidation of magnetite as well as formation of chromite diminishing overall reductive capacity of this system and resulting in less effective removal of Tc(VII) compared to the SO42- solutions.

Water Defect Stabilizes the Bi3+ Lone-Pair Electronic State Leading to an Unusual Aqueous Hydration Structure.

The aqueous hydration structure of the Bi3+ ion is probed using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) simulations of ion-water clusters and condensed-phase solutions. Anomalous features in the EXAFS spectra are found to be associated with a highly asymmetric first-solvent water shell. The aqueous chemistry and structure of the Bi3+ ion are dramatically controlled by the water stabilization of a lone-pair electronic state involving the mixed 6s and 6p orbitals. This leads to a distinct multimodal distribution of water molecules in the first shell that are separated by about 0.2 Å. The lone-pair structure is stabilized by a collective response of multiple waters that are localized near the lone-pair anti-bonding site. The findings indicate that the lone-pair stereochemistry of aqueous Bi3+ ions plays a major role in the binding of water and ligands in aqueous solutions.

Removable coatings: Thermal stability and decontamination of steel surfaces from 241Am.

This study presents a comparative analysis of several commercial removable materials for radioactive decontamination of steel surfaces using 241Am as representative radionuclide. The selection criteria of removable coatings for this study included a history of application, commercial availability, easy handling conditions and different composition and formulation. Carbon steel and stainless steel coupons were utilized as common industrial materials, and the experimental series were expanded to include the rusting treatment of these surfaces as it is common for decommissioned nuclear facilities. Radionuclide 241Am was deposited on the coupon surfaces and used to evaluate decontamination efficiency of the removable coatings, which were pre-screened for the ease of application and removal from the surface. Selected coatings were characterized with Fourier-transform infrared spectroscopy and thermogravimetric analysis, decontamination efficiencies for different types of steel surfaces, and potential enhancement of the removal efficiencies of the select removable coatings via amendment with EDTA. Across all the coatings, decontamination efficiencies for stainless steel (both pristine and with oxidizing treatment) were higher than for pristine carbon steel, which in turn were higher than for rusted carbon steel. Amendment with EDTA improved removal efficiency of a removable coating. CC Strip coating exhibited easy handling and high decontamination efficiency, (up to 97% when EDTA-amended), but its drying time was the longest, and thermal analysis indicated higher release of energy during thermal decomposition compared to the other coatings. Hydrogel-based DeconGel coating, even though not the easiest in handling among the rest of materials, exhibited high decontamination efficiency, efficient drying at the ambient temperature leading to the loss of about 80 wt% due to solvent evaporation, and extremely low heat released during thermal decomposition; therefore, it is considered a preferable choice for the considered factors.

Time dependent zero valent iron oxidation and the reductive removal of pertechnetate at variable pH.

Elemental iron Fe0 is a promising reductant for removal of radioactive technetium-99 (Tc) from complex aqueous waste streams that contain sulfate, halides, and other inorganic anions generated during processing of legacy radioactive waste. The impact of sulfate on the kinetics of oxidation and reduction capacity of Fe0 in the presence of Tc has not been examined. We investigated the oxidative transformation of Fe0 and reductive removal of TcO4- in 0.1 M Na2SO4 as a function of initial pH (i.e., pHi 4, 7, and 10) under aerobic conditions up to 30 days. Tc reduction was the fastest at pHi 7 and slowest at pHi 10 (Tc reduction rate pHi 7 > 4 > 10). Aqueous fraction of Tc was measured at 0.4% at pHi 7 within 6 h, whereas ≥ 97% of Tc was removed from solutions at pHi of 4 and 10 within 24 h. Solid phase characterization showed that magnetite was the only oxidized crystalline phase for the first 6 h regardless of initial pH. Lepidocrocite was the most abundant oxidized product for pHi 10 after 5 days, but was not observed at pH of 4 or 7.

Simultaneous immobilization of aqueous co-contaminants using a bismuth layered material.

The remediation of co-located contaminants in the vadose zone can be challenging due to accessibility and responses of different contaminants to remedial actions. At the Hanford Site (WA, USA), multiple radionuclides and other hazardous contaminants are present in the vadose zone and groundwater, including iodine-129 (I), technetium-99 (Tc), uranium-238 (U), chromium (Cr), and nitrate (NO3-). We evaluated a layered Bi oxyhydroxide material for its potential to remove individual and co-located contaminants with a series of batch experiments that investigated a range of plume conditions, followed by solid phase characterization of the reacted bismuth material. The results demonstrated successful removal of four contaminants (>98% removal of I, Tc, U, and Cr from the aqueous phase after 30 days) when tested individually. When contaminants were combined, a slight decrease in Tc removal occurred (-6%p). The addition of sediment decreased the removal for Tc and I, but U and Cr removal was unaffected. The results of these batch tests demonstrated that the bismuth based oxy-hydroxide material is a promising material for sequestering multiple contaminants in situ.

Identification and Quantification of Technetium Species in Hanford Waste Tank AN-102.

Technetium-99 (Tc), a high yield fission product generated in nuclear reactors, is one of the most difficult contaminants to address at the U.S. Department of Energy Hanford, Savannah River, and other sites. In strongly alkaline solutions typifying Hanford tank waste, Tc exists as pertechnetate (TcO4-) (oxidation state VII) as well as in reduced forms (oxidation state < VII), collectively known as non-pertechnetate (non-TcO4-) species. Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non-TcO4- species and their identification in actual tank waste samples. Identification of non-TcO4- species would facilitate the development of new treatment technologies effective for dissimilar Tc species. Toward this objective, a spectroscopic library of the Tc(I) [fac-Tc(CO)3]+ and Tc(II, IV, V, VII) compounds was generated and applied to the characterization of the actual Hanford AN-102 tank waste supernatant, which was processed to adjust Na concentration to ∼5.6 M and remove 137Cs by spherical resorcinol-formaldehyde (sRF) ion-exchange resin. Post 137Cs removal, the cesium-loaded sRF column was eluted with 0.45 M HNO3. As-received AN-102, Cs-depleted effluent, and sRF eluate fractions were comprehensively characterized for chemical composition and speciation of Tc using 99Tc nuclear magnetic resonance spectroscopy and X-ray absorption spectroscopy. It was demonstrated for the first time that non-TcO4- Tc present in the AN-102 tank waste is composed of several low-valent Tc species, including the Tc(I) [fac-Tc(CO)3]+ and Tc(IV) compounds. This is the first demonstration of multiple non-TcO4- species co-existing in the Hanford tank waste, highlighting their importance for the waste processing.

Mechanisms of Plutonium Redox Reactions in Nitric Acid Solutions.

Plutonium (Pu) exhibits a complex redox behavior in aqueous solutions. This is due to the ability of the element to adapt a wide range of oxidation states typically from +3 to +6 and the tendency for dynamic interconversion between the oxidation states that primarily depend upon acid concentration and presence of coordinating ligands. This work interrogates the Pu redox behavior in aqueous nitric acid via a combination of voltammetry and in situ vis-NIR spectroelectrochemistry under controlled potentials to map the interconversion between the various Pu oxidation states. The NIR-spectroelectrochemistry studies used to complement the visible spectroscopy bring a new and more complete perspective into the plutonium redox transformations. This allows elucidation of the mechanisms of the involved redox reactions facilitating an in-depth understanding of the relative stability of the Pu oxidation states as a function of redox potentials and nitric acid concentrations. It is observed that oxidation of Pu(III) results in generation of Pu(IV) and Pu(VI) (the latter as PuO22+), bypassing the Pu(V) oxidation state. Further, with increasing acid concentrations, the formation of the Pu(VI) species progressively decreases so that the dynamic equilibrium between the Pu(III) and Pu(IV) oxidation states dominates. These findings have significant implications for developing separation processes for used nuclear fuel reprocessing and treatment.

Hybrid Sorbents for 129I Capture from Contaminated Groundwater.

Radioiodine (129I) poses a risk to the environment due to its long half-life, toxicity, and mobility. It is found at the U.S. Department of Energy Hanford Site due to legacy releases of nuclear wastes to the subsurface where 129I is predominantly present as iodate (IO3-). To date, a cost-effective and scalable cleanup technology for 129I has not been identified, with hydraulic containment implemented as the remedial approach. Here, novel high-performing sorbents for 129I remediation with the capacity to reduce 129I concentrations to or below the US Environmental Protection Agency (EPA) drinking water standard and procedures to deploy them in an ex-situ pump and treat (P&T) system are introduced. This includes implementation of hybridized polyacrylonitrile (PAN) beads for ex-situ remediation of IO3--contaminated groundwater for the first time. Iron (Fe) oxyhydroxide and bismuth (Bi) oxyhydroxide sorbents were deployed on silica substrates or encapsulated in porous PAN beads. In addition, Fe-, cerium (Ce)-, and Bi-oxyhydroxides were encapsulated with anion-exchange resins. The PAN-bismuth oxyhydroxide and PAN-ferrihydrite composites along with Fe- and Ce-based hybrid anion-exchange resins performed well in batch sorption experiments with distribution coefficients for IO3- of >1000 mL/g and rapid removal kinetics. Of the tested materials, the Ce-based hybrid anion-exchange resin was the most efficient for removal of IO3- from Hanford groundwater in a column system, with 50% breakthrough occurring at 324 pore volumes. The functional amine groups on the parent resin and amount of active sorbent in the resin can be customized to improve the iodine loading capacity. These results highlight the potential for IO3- remediation by hybrid sorbents and represent a benchmark for the implementation of commercially available materials to meet EPA standards for cleanup of 129I in a large-scale P&T system.

Evolution of Acid-Dependent Am3+ and Eu3+ Organic Coordination Environment: Effects on the Extraction Efficiency.

Coordination of trivalent lanthanide and actinide metal ions by lipophilic diglycolamides and phosphonic acids has been proposed for their separation through extraction from aqueous nitric acid solutions. However, the nature of M3+ coordination complexes in these combined solvent systems is not well understood, resulting in low predictability of their behavior. This work demonstrates that a combination of N,N,N',N'-tetrakis(2-ethylhexyl)diglycolamide (T2EHDGA) and weakly acidic 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) in n-dodecane exhibits a complicated extraction mechanism for Eu3+ and Am3+, which continuously evolves as a function of the aqueous phase acidity. At low aqueous phase nitric acid concentrations, M3+ ions are primarily extracted via exchange of the phosphonic acid proton and coordination with HEH[EHP]. At high aqueous phase nitric acid concentrations, HEH[EHP] remains protonated, and M3+ ions are transported to the organic phase by the coextraction of nitrate anions from the aqueous phase, thus forming complex species with T2EHDGA. At moderate acid regimes, both ligands participate in the coordination of M3+ ions and show a synergistic relationship resulting in considerable enhancement of M3+ transport into the combined solvent system over the simple sum of the individual extractants. The observed synergism is caused by differences in organic phase M3+ speciation and has a significant impact on the performance of the organic solvent. Distribution studies with Eu3+ indicate that nominally two or three T2EHDGA ligands participate in metal extraction in the presence of phosphonic acid, while nominally three diglycolamide ligands participate in the presence or absence of phosphonic acid. While synergistic behavior has been observed in many solvent-extraction processes, this system demonstrates a clear correlation between the continuously changing organic speciation of M3+ and its transport into the organic solvent. This paper reports the spectroscopic characterization of the organic phase M3+ species by IR, X-ray absorption, and visible spectroscopies. Spectroscopic evidence indicates a mixed-ligand complex, i.e., a ternary complex at the moderate acid regime, where the greatest degree of synergism is observed. Differences in synergistic extraction of Am3+ and Eu3+ at the low acid regime were observed, indicating their dissimilar extraction behavior.

Technetium immobilization by materials through sorption and redox-driven processes: A literature review.

The objective of this review is to evaluate materials for use as a barrier or other deployed technology to treat technetium-99 (Tc) in the subsurface. To achieve this, Tc interactions with different materials are considered within the context of remediation strategies. Several naturally occurring materials are considered for Tc immobilization, including iron oxides and low solubility sulfide phases. Synthetic materials are also considered, and include tin-based materials, sorbents (resins, activated carbon, modified clays), layered double hydroxides, metal organic frameworks, cationic polymeric networks and aerogels. All of the materials were evaluated for their potential in-situ and ex-situ performance with respect to long-term Tc uptake and immobilization, environmental impacts and deployability. Other factors such as the technology maturity, cost and availability were also considered. Given the difficulty of evaluating materials under different experimental conditions (e.g., solution chemistry, redox conditions, solution to solid ratio, Tc concentration etc.), a subset of these materials will be selected, on the basis of this review, for subsequent standardized batch loading tests.

Evaluation of materials for iodine and technetium immobilization through sorption and redox-driven processes.

Radioactive iodine-129 (129I) and technetium-99 (99Tc) pose a risk to groundwater due to their long half-lives, toxicity, and high environmental mobility. Based on literature reviewed in Moore et al. (2019) and Pearce et al. (2019), natural and engineered materials, including iron oxides, low-solubility sulfides, tin-based materials, bismuth-based materials, organoclays, and metal organic frameworks, were tested for potential use as a deployed technology for the treatment of 129I and 99Tc to reduce environmental mobility. Materials were evaluated with metrics including capacity for IO3- and TcO4- uptake, selectivity and long-term immobilization potential. Batch testing was used to determine IO3- and TcO4- sorption under aerobic conditions for each material in synthetic groundwater at different solution to solid ratios. Material association with IO3- and TcO4- was spatially resolved using scanning electron microscopy and X-ray microprobe mapping. The potential for redox reactions was assessed using X-ray absorption near edge structure spectroscopy. Of the materials tested, bismuth oxy(hydroxide) and ferrihydrite performed the best for IO3-. The commercial Purolite A530E anion-exchange resin outperformed all materials in its sorption capacity for TcO4-. Tin-based materials had high capacity for TcO4-, but immobilized TcO4- via reductive precipitation. Bismuth-based materials had high capacity for TcO4-, though slightly lower than the tin-based materials, but did not immobilize TcO4- by a redox-drive process, mitigating potential negative re-oxidation effects over longer time periods under oxic conditions. Cationic metal organic frameworks and polymer networks had high Tc removal capacity, with TcO4- trapped within the framework of the sorbent material. Although organoclays did not have the highest capacity for IO3- and TcO4- removal in batch experiments, they are available commercially in large quantities, are relatively low cost and have low environmental impact, so were investigated in column experiments, demonstrating scale-up and removal of IO3- and TcO4- via sorption, and reductive immobilization with iron- and sulfur-based species.

Iodine immobilization by materials through sorption and redox-driven processes: A literature review.

Radioiodine-129 (129I) in the subsurface is mobile and limited information is available on treatment technologies. Scientific literature was reviewed to compile information on materials that could potentially be used to immobilize 129I through sorption and redox-driven processes, with an emphasis on ex-situ processes. Candidate materials to immobilize 129I include iron minerals, sulfur-based materials, silver-based materials, bismuth-based materials, ion exchange resins, activated carbon, modified clays, and tailored materials (metal organic frameworks (MOFS), layered double hydroxides (LDHs) and aerogels). Where available, compiled information includes material performance in terms of (i) capacity for 129I uptake; (ii) long-term performance (i.e., solubility of a precipitated phase); (iii) technology maturity; (iv) cost; (v) available quantity; (vi) environmental impact; (vii) ability to emplace the technology for in situ use at the field-scale; and (viii) ex situ treatment (for media extracted from the subsurface or secondary waste streams). Because it can be difficult to compare materials due to differences in experimental conditions applied in the literature, materials will be selected for subsequent standardized batch loading tests.

Author Correction: Closing the Nuclear Fuel Cycle with a Simplified Minor Actinide Lanthanide Separation Process (ALSEP) and Additive Manufacturing.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Spontaneous redox continuum reveals sequestered technetium clusters and retarded mineral transformation of iron.

The sequestration of metal ions into the crystal structure of minerals is common in nature. To date, the incorporation of technetium(IV) into iron minerals has been studied predominantly for systems under carefully controlled anaerobic conditions. Mechanisms of the transformation of iron phases leading to incorporation of technetium(IV) under aerobic conditions remain poorly understood. Here we investigate granular metallic iron for reductive sequestration of technetium(VII) at elevated concentrations under ambient conditions. We report the retarded transformation of ferrihydrite to magnetite in the presence of technetium. We observe that quantitative reduction of pertechnetate with a fraction of technetium(IV) structurally incorporated into non-stoichiometric magnetite benefits from concomitant zero valent iron oxidative transformation. An in-depth profile of iron oxide reveals clusters of the incorporated technetium(IV), which account for 32% of the total retained technetium estimated via X-ray absorption and X-ray photoelectron spectroscopies. This corresponds to 1.86 wt.% technetium in magnetite, providing the experimental evidence to theoretical postulations on thermodynamically stable technetium(IV) being incorporated into magnetite under spontaneous aerobic redox conditions.

Closing the Nuclear Fuel Cycle with a Simplified Minor Actinide Lanthanide Separation Process (ALSEP) and Additive Manufacturing.

Expanded low-carbon baseload power production through the use of nuclear fission can be enabled by recycling long-lived actinide isotopes within the nuclear fuel cycle. This approach provides the benefits of (a) more completely utilizing the energy potential of mined uranium, (b) reducing the footprint of nuclear geological repositories, and (c) reducing the time required for the radiotoxicity of the disposed waste to decrease to the level of uranium ore from one hundred thousand years to a few hundred years. A key step in achieving this goal is the separation of long-lived isotopes of americium (Am) and curium (Cm) for recycle into fast reactors. To achieve this goal, a novel process was successfully demonstrated on a laboratory scale using a bank of 1.25-cm centrifugal contactors, fabricated by additive manufacturing, and a simulant containing the major fission product elements. Americium and Cm were separated from the lanthanides with over 99.9% completion. The sum of the impurities of the Am/Cm product stream using the simulated raffinate was found to be 3.2 × 10-3 g/L. The process performance was validated using a genuine high burnup used nuclear fuel raffinate in a batch regime. Separation factors of nearly 100 for 154Eu over 241Am were achieved. All these results indicate the process scalability to an engineering scale.

Comparative analysis of ZVI materials for reductive separation of 99Tc(VII) from aqueous waste streams.

Technetium-99 (Tc) is a long-lived radioactive contaminant present in legacy nuclear waste streams and contaminated plumes of the nuclear waste storage sites worldwide that poses risks for human health and the environment. Pertechnetate (TcO4-), the most common chemical form of Tc under oxidative conditions, is of particular concern due to its high aqueous solubility and mobility in the subsurface. One approach to treatment and remediation of TcO4- is reduction of Tc7+ to less soluble and mobile Tc4+ and its removal from the contaminated streams such as liquid secondary waste generated during vitrification of the Hanford low activity tank waste. Zero valent iron (ZVI) is a common reactive agent for reductive treatment of environmental contaminants, including reducible heavy metal ions, which can offer a potential solution to this challenge. Here, we present a comparative study of eleven commercial ZVI materials manufactured by different methods that were evaluated for the reductive removal of TcO4- from an aqueous 80 mM NaCl solution at near neutral pH representing low activity waste off-gas condensate. Performance of ZVI materials was analyzed in relation to time-dependent Fe2+ dissolution as well as pH and ORP profiles of the contact solution. Large variability in the efficiency and kinetics of Tc7+ reduction by different ZVI materials was contingent on their origin. ZVI materials manufactured by electrolytic method exhibited superior performance, and the kinetics of the Tc7+ reduction correlated to particle size. ZVI materials manufactured by iron pentacarbonyl reduction with hydrogen were ineffective for Tc7+ reduction. In general, our results highlight the need for thorough performance analysis of commercial ZVI materials for any contaminant of interest.

Combinations of NIR, Raman spectroscopy and physicochemical measurements for improved monitoring of solvent extraction processes using hierarchical multivariate analysis models.

The reliability of chemical processes can be greatly improved by implementing inline monitoring systems. Combining multivariate analysis with non-destructive sensors can enhance the process without interfering with the operation. We present here hierarchical models using both principal component analysis and partial least square analysis developed for different chemical components representative of solvent extraction process streams. A training set of 380 samples and an external validation set of 95 samples were prepared and Near infrared and Raman spectral data as well as conductivity under variable temperature conditions were collected. The results from the models indicate that careful selection of the spectral range is important. By compressing the data through Principal Component Analysis (PCA), we lower the rank of the data set to its most dominant features while maintaining the key principal components to be used in the regression analysis. Within the studied data set, concentration of five chemical components were modeled; total nitrate (NO3-), total acid (H+), neodymium (Nd3+), sodium (Na+), and ionic strength (I.S.). The best overall model prediction for each of the species studied used a combined data set comprised of complementary techniques including NIR, Raman, and conductivity. Our study shows that chemometric models are powerful but requires significant amount of carefully analyzed data to capture variations in the chemistry.

Spectroscopic Characterization of Aqua [ fac-Tc(CO)3]+ Complexes at High Ionic Strength.

Understanding fundamental Tc chemistry is important to both the remediation of nuclear waste and the reprocessing of nuclear fuel; however, current knowledge of the electronic structure and spectral signatures of low-valent Tc compounds significantly lags behind the remainder of the d-block elements. In particular, identification and treatment of Tc speciation in legacy nuclear waste is challenging due to the lack of reference data especially for Tc compounds in the less common oxidation states (I-VI). In an effort to establish a spectroscopic library corresponding to the relevant conditions of extremely high ionic strength typical for the legacy nuclear waste, compounds with the general formula of [ fac-Tc(CO)3(OH2)3- n(OH) n]1- n (where n = 0-3) were examined by a range of spectroscopic techniques including 99Tc/13C NMR, IR, XPS, and XAS. In the series of monomeric aqua species, stepwise hydrolysis results in the increase of the Tc metal center electron density and corresponding progressive decrease of the Tc-C bond distances, Tc electron binding energies, and carbonyl stretching frequencies in the order [ fac-Tc(CO)3(OH2)3]+ > [ fac-Tc(CO)3(OH2)2(OH)] > [ fac-Tc(CO)3(OH2)(OH)2]-. These results correlate with established trends of the 99Tc upfield chemical shift and carbonyl 13C downfield chemical shift. The lone exception is [ fac-Tc(CO)3(OH)]4 which exhibits a comparatively low electron density at the metal center attributed to the µ3-bridging nature of the -OH ligands causing less σ-donation and no π-donation. This work also reports the first observations of these compounds by XPS and [ fac-Tc(CO)3Cl3]2- by XAS. The unique and distinguishable spectral features of the aqua [ fac-Tc(CO)3]+ complexes lay the foundation for their identification in the complex aqueous matrixes.