Ezgi
Yalçıntaş
*,
Xavier
Gaona
*,
Marcus
Altmaier
,
Kathy
Dardenne
,
Robert
Polly
and
Horst
Geckeis
Institute for Nuclear Waste Disposal, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany. E-mail: ezgi.yalcintas@kit.edu; xavier.gaona@kit.edu
First published on 20th April 2016
We present the first systematic investigation of Tc(IV) solubility, hydrolysis and speciation in dilute to concentrated NaCl, MgCl2 and CaCl2 systems, and comprehensive thermodynamic and activity models for the system Tc4+–H+–Na+–Mg2+–Ca2+–OH−–Cl−–H2O using both SIT and Pitzer approaches. The results are advancing the fundamental scientific understanding of Tc(IV) solution chemistry and are highly relevant in the applied context of nuclear waste disposal. The solubility of Tc(IV) was investigated in carbonate-free NaCl–NaOH (0.1–5.0 M), MgCl2 (0.25–4.5 M) and CaCl2 (0.25–4.5 M) solutions within 2 ≤ pHm ≤ 14.5. Undersaturation solubility experiments were performed under an Ar atmosphere at T = 22 ± 2 °C. Strongly reducing conditions (pe + pHm ≤ 2) were imposed with Na2S2O4, SnCl2 and Fe powder to stabilize technetium in the +IV redox state. The predominance of Tc(IV) in the aqueous phase was confirmed by solvent extraction and XANES/EXAFS spectroscopy. Solid phase characterization was accomplished after attaining thermodynamic equilibrium using XRD, SEM–EDS, XANES/EXAFS, TG–DTA and quantitative chemical analysis, and indicated that TcO2·0.6H2O(s) exerts solubility-control in all evaluated systems. The definition of the polyatomic Tc3O52+ species instead of TcO2+ is favoured under acidic conditions, consistently with slope analysis (mTcvs. pHm) of the solubility data gained in this work and spectroscopic evidence previously reported in the literature. The additional formation of Tc(IV)–OH/O–Cl aqueous species in concentrated chloride media ([Cl−] = 9 M) and pHm ≤ 4 is suggested by solubility and EXAFS data. The pH-independent behaviour of the solubility observed under weakly acidic to weakly alkaline pHm conditions can be explained with the equilibrium reaction TcO2·0.6H2O(s) + 0.4H2O(l) ⇔ TcO(OH)2(aq). Solubility data determined in dilute NaCl systems with pHm ≥ 11 follow a well-defined slope of +1, consistent with the predominance of TcO(OH)3− previously selected by NEA–TDB. In concentrated MgCl2 and CaCl2 solutions with pHm ≥ 8, the formation of the ternary Mg3[TcO(OH)5]3+ and Ca3[TcO(OH)5]3+ species is proposed based on the slope analysis of the solubility data, model calculations and previous observations for analogous An(IV) and Zr(IV) systems. The formation and stability of these hitherto unknown Tc(IV) species are supported by DFT calculations. Based on the newly generated experimental data and previous spectroscopic observations, new comprehensive chemical, thermodynamic and activity models (SIT, Pitzer) for these systems are derived.
The geochemical conditions in underground repositories are mostly defined by the host-rock formation, composition of the groundwater, backfill material, waste inventories and waste form, among others. Although dilute conditions (I < 0.1 M) are normally expected for intruding waters in clay and crystalline host-rock formations, high saline (5 M < I < 15 M) systems are expected in certain sedimentary rocks and salt-rock formations. The latter systems are characterized by high concentrations of Na+, Mg2+, K+, Cl− and SO42− with lower contributions of Ca2+, HCO3−, F− and Br−.2 The use of cement-based materials for conditioning/stabilization of the waste or construction purposes in a repository potentially leads to an alteration of the geochemical media buffering the pH in the hyperalkaline range and inducing a significant increase in the Ca concentration (≈0.02 M at pH ≈ 12.5).3 In concentrated salt brine systems, the interaction of MgCl2 with cement can further lead to the formation of concentrated CaCl2 systems (up to 2.0 M) with pHm ≈ 12 (pHm = −logmH+).4 The solution chemistry of radionuclides in saline systems of high ionic strength cannot be predicted from data and model descriptions gained in dilute systems, mainly because of strong ion interaction processes taking place in the former, leading to a potential strong stabilisation or de-stabilisation of species in brine systems. Besides ion interaction processes which may significantly affect the chemical behaviour and thermodynamic equilibria, the presence of high concentrations of cations like Mg2+ or Ca2+ can further result in the formation of new aqueous species or solid compounds not observed in dilute systems. Apart from being an interesting research topic from the perspective of fundamental aquatic chemistry, this tendency can lead to completely different chemical properties and migration behaviour of radionuclides in salt brine systems, which therefore justifies dedicated research efforts.
The solubility of Tc(IV) was previously investigated by a number of research groups, in most of the cases at low ionic strength. Meyer et al.5 studied the solubility of Tc(IV) in the pH range 1 to 10. Two different approaches were used for the preparation of the solid phase, namely electrodeposition of an oxide solid phase and the oxide precipitation onto sand particles from reduction of Tc(VII) by hydrazine. The authors determined the number of hydration waters in TcO2·xH2O(s) as (1.63 ± 0.28) by weighing the dried solid phases reduced under acidic and alkaline conditions. Based on their solubility data, Meyer and co-workers proposed a chemical model with TcO2+ and TcO(OH)+ species prevailing under acidic conditions. On the other hand, the chemical equilibrium TcO2·1.6H2O(s) ⇔ TcO(OH)2(aq) + 0.6H2O(l) was proposed to explain the very low and pH-independent solubility behaviour within 4 ≤ pH ≤ 10. Eriksen et al.6 performed solubility experiments with an electrodeposited Tc(IV) oxide as a function of pH and PCO2. Consistently with Meyer and co-workers, these authors observed a pH-independent solubility (≈7 × 10−9 M) within the pH range 6 to 9.5. The increase in solubility with slope +1 observed above pH = 9.5 was interpreted as the formation of the TcO(OH)3− species in accordance with the chemical reaction TcO2·xH2O(s) ⇔ TcO(OH)3− + H+ + (x − 2)H2O(l) and . Hess et al. (2004)7 conducted solubility experiments in dilute to concentrated saline systems (up to 5.0 M NaCl and 6.0 M HCl) under acidic to near-neutral pH conditions. Samples were equilibrated for up to 65 days. The solubility study was complemented with extensive solid and aqueous phase characterization, including XRD, UV-vis, XANES/EXAFS and liquid–liquid extraction. In spite of the high [Cl−] considered in the study, the authors only reported evidence on the formation of Tc(IV)–Cl species (TcCl4(aq) and TcCl62−) at pHm ≤ 1 and I ≥ 2.5 M. The transformation of TcO2·xH2O(s) to TcCl4(s) was also proposed to take place under these conditions. Above pHm ≈ 1, Hess and co-workers reported the predominance of Tc(IV) hydrolysis species and explained the significant increase in solubility observed in concentrated NaCl solutions exclusively by ion interaction processes. The authors derived comprehensive chemical, thermodynamic and activity models for Tc(IV) in acidic HCl–NaCl systems based on their solubility data at short equilibration times (t = 11 days) and the corresponding solid and aqueous phase characterization. The chemical model reported by Hess et al. is in agreement with previous publications available in the literature and with the current NEA–TDB data selection, although the authors reported greater for the TcO(OH)+ species, which accordingly becomes predominant in the acidic pH region. Later, Liu et al. (2007)8 performed Tc(IV) solubility experiments in simulated ground water within 1 ≤ pH ≤ 12 and 10−4 M ≤ [CO32−] ≤ 0.05 M. The authors found a good agreement with previous publications and did not observe any relevant increase in Tc(IV) solubility due to carbonate complexation. Warwick et al.9 investigated the solubility of Tc(IV) reduced by Sn(II) and Fe(II) within the pH range 11.8 to 14.4. In contrast to the solubility data by Eriksen and co-workers, the authors only observed a slight increase of Tc(IV) solubility above pH = 13.5. Unfortunately, no solid phase characterization was conducted by the authors, and thus it can only be speculated that a more crystalline solid or alteration phase was eventually responsible for the control of the solubility in this study. Kobayashi and co-workers (2013)10 investigated the reduction of Tc(VII) to Tc(IV) in 0.1 M NaCl and the presence of various reducing systems. The authors compared their experimental results with thermodynamic calculations of the Tc(VII)/Tc(IV) redox border, with the aim of assessing the kinetics of the reduction process and the reliability of Eh–pH measurements. Recently, Yalcintas et al.11 extended the redox experiments by Kobayashi et al. to dilute and concentrated NaCl and MgCl2 solutions in order to evaluate the effect of elevated ionic strength on the redox behaviour of Tc. Besides the impact of salt concentration on the measured Eh values, a systematic increase in the concentration of Tc(IV) under acidic conditions was observed with increasing ionic strength, thus reflecting a relevant impact of ion interaction processes on the aquatic chemistry of Tc(IV).
Besides these studies specifically targeting the determination of thermodynamic data, a number of spectroscopic investigations providing relevant insights into the speciation of Tc under acidic conditions have been published since 2000.12–16 Hence, Vichot et al. (2002) investigated the speciation of Tc(IV) in aqueous Cl− and SO42− media at pH ≈ 1.5 and I ≤ 3 M.12 Based on the evaluation of their EXAFS data, the authors proposed the formation of small sized polynuclear species independently of the composition of the background electrolyte. EXAFS data disregarded also the presence of Cl-backscatterers in the first coordination shell of Tc. In 2003, the same authors confirmed the formation and predominance of polymeric TcnOp(4n–2p)+ species up to pH = 3 using UV-vis spectroscopy, clearly contradicting the previously postulated predominance of the monomeric TcO2+ and TcO(OH)+ species. The authors interpreted their data with the formation of the trimer Tc3O44+, which shows clear analogies with the cluster M3O4·9H2O4+ previously described for Mo(IV).13 Poineau et al. (2006)16 investigated the aqueous speciation of Tc in 3.0 M HCl–NaCl solutions with 0 ≤ pH ≤ 1.5 using a combination of spectroscopic techniques (UV-vis/NIR and EXAFS). The authors confirmed the predominance of the Tc2OCl104− species at 0.1 ≤ pH ≤ 1.1, whereas TcCl62− and TcnOp(4n–2p)+ prevailed below and above this pH range, respectively.17
In spite of the abundant experimental studies focussing on the aquatic chemistry of Tc(IV), a number of open questions remain with regard to the chemical and thermodynamic models available for this system. Furthermore, the lack of systematic studies at elevated ionic strength hinders the development of accurate activity models able to predict the chemical behaviour of Tc(IV) at I ≠ 0 and directly impacts the possibilities to model Tc chemistry in salt media. In this context, the present study aims at a comprehensive and systematic investigation of Tc(IV) solubility and hydrolysis in dilute to concentrated NaCl, MgCl2 and CaCl2 systems relevant for different nuclear waste disposal concepts and scenarios. Solubility experiments are complemented with comprehensive solid and aqueous phase characterisation contributing to the development of an accurate chemical model for this system. The thermodynamic and activity models for the system Tc4+–H+–Na+–Mg2+–Ca2+–OH−–Cl−–H2O are derived based on the newly generated experimental data using SIT and Pitzer approaches.
The first definition of TcO2+ as Tc(IV) cation prevailing under very acidic conditions dates back to the electrophoretic study by Gorski and Koch (1969),19 who reported a Tc(IV) species with charge +2 dominating at pH < 1.3. This formulation was adopted by the NEA–TDB, although more recent spectroscopic studies strongly hint towards the predominance of positively charged Tc(IV) polyatomic species under acidic conditions.12–16 In spite of selecting the TcO(OH)3− species, Rard and co-workers1 acknowledged the need of additional experimental studies focussing on the alkaline pH region due to the limited number of data points in the study of Eriksen et al. (1992).6 The lack of experimental studies at I > 0.1 M hindered the development of an activity model for Tc(IV), which remains as one of the main limitations of the current Tc(IV) thermodynamic selection in the NEA–TDB.
Redox potentials were measured with Pt combination electrodes with the Ag/AgCl reference system (Metrohm) and converted to Ehvs. the standard hydrogen electrode (SHE) by correction for the potential of the Ag/AgCl reference electrode (+208 mV for 3 M KCl at T = 22 °C). The measurement of Eh values in highly saline systems was previously discussed elsewhere.11
The solubility of Tc(IV) was studied from undersaturation conditions in 0.1–5.0 M NaCl, 0.25–4.5 M MgCl2 and 0.25–4.5 M CaCl2 solutions. A total of 52 independent batch samples were prepared in these background electrolytes. The pH values were adjusted at 1.5 ≤ pHm ≤ 14.5 by using HCl–NaCl–NaOH, HCl–MgCl2 and HCl–CaCl2 of appropriate ionic strength, as well as Mg(OH)2(s) and Ca(OH)2(s). 0.5 M PIPES and 1.0 M TRIS stock solutions were used for buffering the solubility samples at pHm ≈ 7 and pHm ≈ 8, respectively. In both cases, the final buffer concentration was 12 mM. Based on a previous comprehensive study on the redox chemistry of Tc(VII)/Tc(IV) in dilute to concentrated saline systems,11 Na2S2O4, SnCl2 and Fe powders (depending upon target pH) were used to stabilize the +IV redox state of Tc in the solubility samples. Background electrolyte solutions with adjusted pHm and Eh conditions were equilibrated for two weeks. About 5 mg of the Tc(IV) solid phase were washed three times with 1 mL of the respective pre-equilibrated matrix solution and added to 20 mL of the same matrix solution in 50 mL screw cap centrifuge vials (Nalgene™, Thermo Scientific). Those samples with expectedly high solubility were prepared in smaller volumes (1 to 5 mL) to avoid the complete dissolution of the Tc(IV) solid phase. pHm and mTc in the solubility samples were repeatedly measured at regular time intervals, usually from 3 to 600 days. During this time, samples were agitated manually about once per week. After reaching equilibrium conditions (stable pHm and mTc readings), the pH of some unbuffered samples was slightly shifted by addition of acidic or basic solutions of the same ionic strength to obtain additional data points in the solubility curve. This approach was strictly followed from pH values with lower to higher solubility, in order to avoid oversaturation conditions and the potential formation of colloidal phases.22
Tc concentration in solution was quantified by Liquid Scintillation Counting (LSC, Quantulus, Perkin Elmer) after 10 kD ultrafiltration (2–3 nm, Pall Life Sciences). Samples for LSC analysis were mixed with 10 mL of LSC-cocktail Ultima Gold XR (Perkin-Elmer). The detection limit of LSC for this system was calculated as ≈4 × 10−10 M (signal of the blank +3 standard deviations). The error associated with the sorption of Tc on the ultrafiltration filters was found below the uncertainty of the measurement of mTc. The oxidation state of Tc in the aqueous phase was determined by solvent extraction as reported elsewhere.23,24 The supernatant of the sample was contacted with 50 mM TPPC in chloroform. After vigorous mixing for 1 minute and subsequent separation of the aqueous and organic phases by centrifugation, Tc concentration in the aqueous phase was determined by LSC. Since TcO4− is extracted to the organic solvent, the activity remaining in the aqueous phase is interpreted as Tc(IV).
Solid phase characterization was conducted for selected batch samples after attaining equilibrium conditions. A fraction of the solid phase (≈1 mg) was washed 3–5 times with ethanol under an Ar atmosphere to remove the salt-containing matrix solution. After the last cleaning step, the solid was re-suspended in approximately 20 μL ethanol, transferred to a capped silicon single crystal sample holder (Dome, Bruker), dried under an Ar atmosphere for a few minutes before sealing of the sample holder, and transferred outside the glovebox for the collection the XRD diffractogram. XRD measurements were performed on a Bruker AXS D8 Advance X-ray powder diffractometer at 10° ≤ 2θ ≤ 78° with incremental steps of 0.015° and a measurement time of 1.7 seconds per step. The spectra collected were compared with the JCPDS database (Joint Committee on Powder Diffraction Standards25). After XRD measurement, the solid phase was dissolved in 1 mL of 2–3% HNO3 and used for quantitative chemical analysis. The dissolved solid phase was analysed by LSC and inductively coupled plasma-optical emission spectroscopy (ICP-OES, Perkin-Elmer Optima 2000™) to determine the Tc and Na, Mg, or Ca contents, respectively. Analytical errors in the quantitative chemical analysis by LSC and ICP–OES can be safely considered to be below 10%. A second fraction of the washed solid was investigated in the selected samples by scanning electron microscope-energy disperse spectrometry (SEM–EDS) with the aim of characterizing the morphology and crystallinity of the solid phase, and to further assess its chemical composition. Measurements were performed with a FEI Quanta 650 FEG equipped with a Noran EDS unit.
The number of hydration waters in the TcO2·xH2O(s) solid phase used in the present work before and after solubility experiments was quantified by thermogravimetric analysis (TG–DTA) using a Netzsch STA 449C equipment. Three samples were prepared for thermogravimetric analysis: (i) 6.6 mg of the original Tc(IV) solid phase prepared by electrolysis and consecutive precipitation in alkaline media (presence of Na2S2O4, pHm ≈ 12), (ii) 6.1 mg of the Tc(IV) solid phase equilibrated in 5.0 M NaCl (presence of Na2S2O4, pHm = 12, 13 and 14) and (iii) 1.4 mg of the Tc(IV) solid phase equilibrated in 4.5 M MgCl2 (presence of Sn(II), pHm = 4). All investigated samples were washed 3–5 times with ethanol under an Ar atmosphere to remove the salt-containing matrix solution. After the last cleaning step, the solid was left to dry under an Ar atmosphere for 2–3 days and transferred to a glovebox specifically dedicated to DTA analyses. Measurements were performed under an Ar atmosphere up to T = 200 °C at a rate of 5 K min−1.
Tc-K edge (21044 eV) XAFS spectra (3–4 replicates per sample) were recorded at room temperature under a continuous flow of Ar. Ge(422) crystals were used in the double crystal monochromator, Lemonnier-type operating in fixed-exit mode. The monochromatic beam is focused by a toroidal mirror, delivering a beam spot-size of ∼500 × 300 μm2 at the sample position at a photon energy of 18 keV. The parallel alignment of the crystal faces was detuned to ≈70% of the maximum beam intensity at the beginning of each scan. The incident intensity was held constant by means of a piezo-driven feedback system to the second crystal. The intensity of the incoming beam (I0) was monitored using an Ar filled ionization chamber at ambient pressure. Spectra were recorded in fluorescence mode using a five pixel LEGe solid state detector (Canberra, Belgium). Tc spectra were energy-calibrated with respect to the first inflection point in the XANES spectra of a Mo metal foil (20000 eV), which was measured simultaneously in transmission geometry.
XANES/EXAFS data reduction and analysis were performed with the ATHENA/ARTEMIS package following standard procedures.27 Structural information was obtained following a multi-shell step-wise approach for the EXAFS data fitting. The fit included the neighbouring atomic distances (R), EXAFS Debye–Waller factors (σ2), coordination numbers (CN) and relative shift in ionization energy E0 (ΔE0). EXAFS spectra were Fourier transformed (FT) in the k-range between 2.6–10.4 Å−1 and 2.0–8.5 Å−1 using Hanning windows for solid and aqueous phases, respectively. The fit was performed in R-space (1.2–2.5 Å) using paths files calculated with Feff8.4 based on the TcO2 crystal structure reported in the ICSD database with record number 17–3151. The coordination number of O-shells was allowed to vary in the fit, whereas Tc- and Cl-shells were constrained to 1 and 1.4, respectively. The value of 1.4 for Cl in the fit of aqueous phases was obtained in a preliminary fit where CN(Cl) was defined such that the total CN(O) + CN(Cl) for the first coordination shell was equal to 6. The overall amplitude factor S02 was set to 0.75 to obtain a good match with the coordination number of ∼6 in the solid and reference samples.
All investigated NaCl systems follow a well-defined slope of −2 (logmTc(IV)vs. pHm, dashed lines in Fig. 1) within the pHm-range 1.5 to 4, which indicates that 2 H+ are consumed in the chemical reaction controlling the solubility of Tc(IV) in this pH region. This observation agrees very well with the slope analysis in the study of Meyer et al.,5 whereas it is in disagreement with the slope of −1 proposed by Hess et al.7 Note that Hess and co-workers disregarded their solubility data at longer equilibration times for the slope analysis (and thus for the definition of their chemical model), which was mostly based on solubility data gained after 11 days of equilibration time. Provided the strong kinetics observed (both in the present work and in Hess et al.) for the solubility equilibria under acidic conditions, we consider that the interpretation by the latter authors is not representing the thermodynamic equilibrium under these conditions (see Fig. A1 in the ESI†).
At 4 ≤ pHm ≤ 9, a pH-independent solubility behaviour is observed in dilute to concentrated NaCl solutions, indicating that no H+ are exchanged in the chemical reaction controlling the solubility of Tc(IV) in this pH-region. The concentration of Tc is not affected by ionic strength either, and thus data in 0.1 M and 5.0 M NaCl show similar solubility. A very large scattering in mTc (1–1.5 log-units) is observed in this pH region. This behaviour is likely related with the very low solubility (close to the detection limit of LSC) and the expected predominance of neutral species in solution, which are prone to form oligomeric species and strongly sorb on surfaces (filters, vessel walls, solid phases, etc.). A similar behaviour was previously reported for An(III)/Ln(III) and An(IV).22,34 Meyer and co-workers reported very similar observations, i.e. pH- and ionic strength independent behaviour and large scattering of the solubility data. Although not discussed in the original publication, we hypothesize that the very stable Tc concentrations measured by Eriksen et al. (1992)6 within 6 ≤ pH ≤ 10 (logmTc = –8.2) likely correspond to the detection limit of their quantification method.
The solubility of Tc(IV) increases with a well-defined slope of +1 (logmTc(IV)vs. pHm) at pHm ≥ 11. Although the same slope is retained, the solubility decreases almost one order of magnitude when increasing the ionic strength from 0.1 to 5.0 M NaCl. Note that a similar trend with increasing ionic strength was reported for the solubility of Zr(IV) under alkaline to hyperalkaline pH conditions,21 where anionic hydrolysis species are dominant in solution. The solubility data and slope determined in this work in 0.1 M NaCl are consistent with the results reported by Eriksen et al. (1992).6 Significantly lower Tc(IV) solubility was observed by Warwick et al. (2007)9 within 12 ≤ pH ≤ 14. Unfortunately, the authors did not properly characterize the solid phase controlling the solubility. Although a solubility-control by a more crystalline Tc(IV) solid phase can be hypothesized, a direct comparison with the solubility data gained in this work is not feasible.
The solubility of Tc(IV) shows a pH-independent behaviour at 4 ≤ pHm ≤ 9 in 0.25 M MgCl2, in analogy with the NaCl systems. The pH-independent region is significantly smaller in 4.5 M MgCl2 (7 ≤ pHm ≤ 8), mainly due to the very relevant increase in the solubility under acidic pH conditions, but also because of a likely change in the aqueous speciation above pHm ≈ 8. As in the case of NaCl systems, the solubility of Tc(IV) in this pH region scatters within −8.2 ≥ logmTc ≥ −9.4.
A steep increase in the Tc(IV) solubility is observed in 4.5 M MgCl2 solutions with pHm ≈ 8. This behaviour differs from the findings gained in the NaCl systems, where the formation of anionic Tc(IV) hydrolysis species (and consequent increase of the solubility) takes only place at pHm ≈ 11. Similar observations were previously reported for Zr(IV) and An(IV) in concentrated alkaline CaCl2 solutions.21,35,36 Based on the collected spectroscopic evidence (EXAFS) and model calculations, the solubility behaviour of Zr(IV) and An(IV) under these conditions was explained with the formation of ternary Ca–Zr(IV)/An(IV)–OH aqueous species. The predominance of analogous Mg–Tc(IV)–OH aqueous species is accordingly suspected in concentrated alkaline MgCl2 solutions, in spite of the limitations in pHm posed by the precipitation of Mg–OH–Cl(s) (pHmax ≈ 9). In order to gain more conclusive insights into the aqueous chemistry of Tc(IV) in concentrated alkaline MCl2 (M = Mg2+, Ca2+) systems, the solubility of Tc(IV) was further investigated in dilute to concentrated alkaline CaCl2 solutions and is discussed in the following section.
Background electrolyte | Reducing system | pHma | E hb (mV) | %Tc(IV)c |
---|---|---|---|---|
a ± 0.05. b ± 50 mV. c ± 10%; n.m. = not measured. d Same sample also investigated by XAFS. | ||||
0.5 M NaCl | Na2S2O4 | 12.4 | −670 | 99 |
5.0 M NaCl | Sn(II) | 2.5 | 80 | 99 |
5.0 M NaCl | Na2S2O4 | 13.0 | −540 | 98 |
5.0 M NaCl | Na2S2O4 | 14.0 | −580 | 98 |
4.5 M MgCl2 | Sn(II) | 2.0 | n.m. | 13d |
4.5 M MgCl2 | Sn(II) | 4.0 | −50 | 52 |
4.5 M MgCl2 | Fe Powder | 8.9 | −170 | 91 |
4.5 M MgCl2 | Sn(II) | 9.0 | −175 | 94 |
Fig. 4 XRD patterns collected for Tc solid phases equilibrated in dilute to concentrated NaCl and MgCl2 solutions (left), and concentrated CaCl2 solutions (right). |
Background electrolyte | Reducing system | pHma | XRD | Chemical analysis |
---|---|---|---|---|
Na:Tc | ||||
a ± 0.05, n.m. = not measured. b pH = pHmax, presence of Mg–OH–Cl(s) expected. c pH = pHmax, presence of Ca–OH–Cl(s) expected. | ||||
0.5 M NaCl | Na2S2O4 | 12.4 | am | <0.01 |
5.0 M NaCl | Sn(II) | 2.5 | am | <0.01 |
5.0 M NaCl | Na2S2O4 | 13.0 | n.m. | <0.01 |
5.0 M NaCl | Na2S2O4 | 14.0 | am | <0.01 |
Mg:Tc | ||||
0.25 M MgCl2 | Sn(II) | 2.0 | am | <0.01 |
4.5 M MgCl2 | Sn(II) | 4.0 | am | <0.01 |
4.5 M MgCl2 | Fe Powder | 8.9 | n.m. | 25.0b |
4.5 M MgCl2 | Sn(II) | 9.0 | n.m. | 0.3b |
Ca:Tc | ||||
2.0 M CaCl2 | Na2S2O4 | 11.8 | am | n.m. |
4.5 M CaCl2 | Sn(II) | 10.9 | am, (11.6, 23, 33) | 2.7c |
4.5 M CaCl2 | Na2S2O4 | 11.7 | am | 1.6c |
4.5 M CaCl2 | Sn(II) | 11.4 | am, (11.6, 23, 33) | n.m. |
4.5 M CaCl2 | Sn(II) | 10.7 | am, (11.6, 23, 33) | n.m. |
The SEM images (Fig. 5 and 6) of all investigated samples show the predominance of amorphous Tc aggregates, in good agreement with the observed absence of well-defined XRD patterns. The particle size of these aggregates varies between 50 and 80 nm. Quantitative chemical analyses (Table 3) show the absence of Na in the Tc solid phases controlling the solubility in NaCl systems, even for those phases equilibrated in 5.0 M NaCl solutions. Similarly, no Mg is detected in solid phases controlling the solubility under acidic conditions in 4.5 M MgCl2, whereas very high Mg content is quantified in alkaline samples with pHm ≈ pHmax. SEM images of the later samples confirm the presence of needle-like precipitates of Mg–OH–Cl(s) (Fig. 5, right). Similar observations are gained for Tc solid phases equilibrated in CaCl2 solutions with pHm ≈ pHmax, for which SEM pictures indicate the presence of Ca(OH)2(s) and/or Ca–OH–Cl(s) phases (Fig. 6). The absence of Na, Mg, or Ca in the Tc solid phases (except those at pHm ≈ pHmax) controlling the solubility in NaCl, MgCl2 and CaCl2 systems, in combination with the amorphous character of the solid confirmed by XRD and SEM, strongly points towards a solubility-control exerted by TcO2·xH2O(s).
TG–DTA analyses indicate a mass loss of 5–11% in the investigated solid phases, corresponding to x = 0.4–0.8 in TcO2·xH2O(s). These results highlight the similar hydration degree of the Tc(IV) solid phase in the different background electrolytes and salt concentrations considered in this study. The unweighted mean value of the number of hydration waters x = 0.6 ± 0.3 is considered in the following in the definition of the Tc(IV) solid phase used in this study: TcO2·0.6H2O(s). Note that a very discrepant number of hydration waters was previously reported by Meyer and co-workers,5 who measured x = 0.44–4.22 and 1.38–1.81 for solid phases obtained from acidic and alkaline deposition, respectively. Although the number of hydration waters has a minor influence on solubility phenomena and calculations in dilute systems, it becomes relevant in concentrated brines where water activities significantly lower than 1 arise (e.g. aw = 0.5083 in 4.0 M MgCl2).18
k 2-weighted Tc K-edge EXAFS spectra and corresponding Fourier transforms are shown in Fig. 8. Structural parameters of all investigated samples resulting from the fit of the EXAFS spectra are summarized in Table 4. The EXAFS fit of the original TcO2·0.6H2O(s) material shows an O-shell at 2.07 Å with a coordination number (CN) of 6.7, and a Tc-shell at 2.59 Å with CN = 1. These results are in excellent agreement with structural parameters reported in the literature for TcO2·xH2O(s).7 Similar structural parameters are obtained from the fit to EXAFS data of the Tc(IV) solid phase equilibrated in 4.5 M CaCl2 at pHm = 11.4. This observation indicates that no solid phase transformation occurred within the 325 days of equilibration time, and that TcO2·0.6H2O(s) remains as the solubility-controlling phase under these conditions. Hence, Tc(IV) solubility data obtained in [CaCl2] ≥ 2.0 M at pHm ≈ pHmax are not representative of a thermodynamic equilibrium and can only be explained by the very slow kinetics in the presence of Ca(OH)2(s) or Ca–OH–Cl(s) phases or eventually a solubility control by an unidentified surface “coating”.
Sample | Path | CN | R (Å) | σ 2 (Å2) | ΔE0 (eV) | R-factor |
---|---|---|---|---|---|---|
Fit errors: CN: ± 20%, R: 0.01 Å, σ2: 0.001 Å2.a Held constant during the fit. | ||||||
Original TcO2·0.6H2O(s) material | Tc–O | 6.7 | 2.07 | 0.010 | −5.146 | 0.002 |
R-Space [1.2–2.5 Å] | Tc–Tc | 1.0a | 2.59 | 0.002 | ||
k-Range [2.6–10.4 Å−1] | ||||||
Tc(IV) solid phase in 4.5 M CaCl2 at pHm = 11.4 | Tc–O | 6.4 | 2.07 | 0.009 | −5.635 | 0.015 |
R-Space [1.2–2.5 Å] | Tc–Tc | 1.0a | 2.59 | 0.003 | ||
k-Range [2.6–10.4 Å−1] | ||||||
Tc(IV)(aq) in 4.5 M MgCl2 at pHm = 2 | Tc–O | 3.5 | 2.21 | 0.002 | 0.842 | 0.010 |
R-Space [1.0–2.5 Å] | Tc–Cl | 1.4a | 2.53 | 0.007 | ||
k-Range [2.0–8.5 Å−1] |
The EXAFS fit of the supernatant solution in the solubility sample equilibrated in 4.5 M MgCl2 at pHm = 2 unequivocally shows the co-existence of O- (CN = 3.5, R = 2.21 Å) and Cl- (CN = 1.4, R = 2.53 Å) backscatterers in the first coordination sphere of Tc. The substitution of Tc–Cl by Tc–O interactions significantly worsens the fit. The addition of a Tc–Tc contribution at R = 2.77 Å decreased the residual of the fit (%R), although this farther shell was disregarded in the final model due to the limited k-range considered in the fit (2.0 ≤ k [Å−1] ≤ 8.5). These observations hint towards the possible formation of Tc(IV)–O/OH–Cl oligomers in acidic concentrated MgCl2 solutions. Note that Poineau and co-workers16 reported the predominance of the Tc2OCl104− species at pH = 0.3 and [Cl−] = 3.0 M. The structural parameters determined for this species by EXAFS for Tc–O (CN = 1.2, R = 1.79 Å) and Tc–Cl (CN = 4.7, R = 2.36 Å) interactions are significantly different compared to those determined in the present study, suggesting the predominance of a different aqueous species at pHm = 2.0 and [Cl−] = 9.0 M (present work). The formation of Tc(IV) – chloride species in acidic concentrated MgCl2 solutions is in line with the results obtained by liquid–liquid extraction. Hence, the solvent extraction method used in the present work has been reported to extract into the organic phase not only MO4− species, but also anionic chloride complexes.39
Tc(IV) solubility data obtained in concentrated CaCl2 solutions hint towards the formation of the previously unreported [TcO(OH)5]3− moiety in the aqueous phase, considering the slope of +3 (logmTcvs. pHm) and the solubility control by TcO2·0.6H2O(s). In the absence of Ca in the background electrolyte (e.g. NaCl or KCl systems), TcO(OH)3− is the only anionic hydrolysis species forming under hyperalkaline pH conditions (see section 3.1 and references therein). As previously described for Zr(IV) and An(IV) (An = Th, Np, Pu), the formation of highly charged anionic hydrolysis species in concentrated alkaline CaCl2 solutions is stabilized by the contribution of Ca2+ in the second coordination sphere of the tetravalent cation.21,35,36 The number of Ca2+ ions participating in the complex formation was inferred from model calculations and EXAFS spectroscopy for Zr(IV) and Th(IV), and was based on the analogy with Th(IV) in the case of Np(IV) and Pu(IV). In this work, the stability of the Can[TcO(OH)5]2n−3 species (n = 1–3) was evaluated by large-scale DFT calculations. In order to understand the role of Ca2+ in the stabilization of the highly charged [TcO(OH)5]3− moiety, the stability of the latter in the absence of Ca2+ ions was also investigated.
DFT calculations show that only the Ca3[TcO(OH)5]3+ species is stable both in the gas phase and enwrapped by one hundred water molecules (Fig. 9). In contrast, the Ca[TcO(OH)5]−, Ca2[TcO(OH)5]+ and [TcO(OH)5]3− species break apart both in the gas and aqueous phases, mostly due to the insufficient or inexistent charge compensation of the [TcO(OH)5]3− moiety. Tc(IV)–Ca distances optimized by DFT for the Ca3[TcO(OH)5]3+ species enwrapped by one hundred water molecules (RTc–Ca1 = 3.01 Å, RTc–Ca2 = 3.11 Å, RTc–Ca3 = 3.33 Å; average RTc–Ca = 3.15 Å) are in line with distances determined by EXAFS for Zr(IV)–Ca (R = 3.38 ± 0.02 Å) and Th(IV)–Ca (R = 3.98 ± 0.02 Å) in Ca3[Zr(OH)6]4+ and Ca4[Th(OH)8]4+, respectively.‡,40 The outcome of these theoretical calculations supports the predominance of the Ca3[TcO(OH)5]3+ species in concentrated CaCl2 systems, which otherwise cannot be assessed by spectroscopic means. The quantum chemical and DFT studies performed will be presented in more detail in a separate manuscript by R. Polly et al. currently under preparation.
Provided the solubility-control exerted by TcO2·0.6H2O(s) (see sections 3.4.2 and 3.4.3), the slope of −2 defined by solubility data in acidic dilute to concentrated NaCl and MgCl2 solutions is consistent with the predominance of the TcnOm(OH)2+(2–4n+2m) species in the aqueous phase. Although NEA–TDB (consistently with previous publications) defined the formation of the TcO2+ species in this pH region, more recent spectroscopic studies strongly hint towards the predominance of cationic polynuclear Tc(IV) species.12–16 Based on the analogy with Mo(IV) and the proven formation of the cluster Mo3O4·9H2O4+, Vichot and co-workers13 proposed the formation of the trimeric Tc3O44+ species at pH ≤ 3. The predominance of trimeric Zr(IV) species was also favoured by Altmaier et al. (2008) to explain the solubility behaviour of Zr(OH)4(s) under acidic pH conditions.21 In view of the available experimental evidence and in analogy with Mo(IV) and Zr(IV), the predominance of the trimeric Tc3O52+ species in the acidic pH region is proposed in the present work. Note that the formation/predominance of other polyatomic species such as Tc2O32+ or Tc4O72+ is also consistent with the available solubility data and spectroscopic evidence, but has been disregarded in the chemical model derived in this work. The formation of the TcO(OH)+ species is not needed to properly explain the experimentally determined solubility data, and has been also disregarded in the chemical model considered in this work. The predominance of the latter species under acidic conditions was claimed by Hess and co-workers,7 but the large stability field proposed by the authors for TcO(OH)+ is ruled out in the present work due to the relevant experimental shortcomings discussed in section 3.1.
Besides the formation of Tc3O52+, the very large increase in solubility (>5 orders of magnitude!) between solubility data in dilute and concentrated chloride media may hint towards the formation of Tc(IV)–O/OH–Cl aqueous complexes in concentrated chloride solutions also beyond pHm > 4. Previous spectroscopic studies16 confirmed the predominance of the TcCl5(H2O)− and Tc2OCl104− species in 3.0 M NaCl solutions with pH < 1.1. Above this pH, the authors proposed the predominance of a polyatomic oxo-cation TcnO4n−2yy. In the present work, the formation of Tc(IV)–O/OH–Cl aqueous complexes in 4.5 M MgCl2 solutions with pHm ≤ 4 is also hinted by EXAFS. Besides this spectroscopic evidence, Tc(IV) solubility data follows a well-defined slope of −2 both in dilute and concentrated chloride solutions, thus indicating that the number of H+ involved in the solubility reaction is the same in both cases. Provided the proposed predominance of the Tc3O52+ species under acidic conditions with low mCl−, the possible formation of Tc(IV) chloro-complexes of the type Tc3O5Cl(2−m)m with 1 ≤ m ≤ 4 was also considered in the development of the chemical model. Thus, chemical reactions (1) and (2) are taken into account for the assessment of Tc(IV) solubility under acidic conditions:
TcO2·0.6H2O(s) + 2/3 H+ ⇔ 1/3 Tc3O52+ + 0.93H2O(l) | (1) |
TcO2·0.6H2O(s) + 2/3 H+ + m/3Cl− ⇔ 1/3 Tc3O5Cl(2−m)m + 0.93H2O(l) | (2) |
with
(3) |
(4) |
(5) |
(6) |
In the first step, different chemical models involving the formation of Tc3O52+ and Tc3O5Cl(2−m)m complexes were evaluated using the SIT approach. Then, the chemical model chosen was used to fit the corresponding conditional equilibrium constants with the Pitzer approach to derive and ion interaction parameters.
1. only the formation of Tc3O52+ was considered to explain Tc(IV) solubility data in dilute to concentrated NaCl and MgCl2 solutions.
2. Formation of both Tc3O52+ and Tc3O5Cl(2−m)m with 1 ≤ m ≤ 4 was considered to explain Tc(IV) solubility data in dilute to concentrated NaCl and MgCl2 solutions:
a. Use of Tc(IV) solubility data at low ionic strength (0.1 M NaCl) and ε(Tc3O52+, Cl−) = (0.15 ± 0.1) kg mol−1 estimated according to charge analogies42 to determine . Solubility data not explained by the contribution of this species are then fitted assuming the formation of Tc3O5Cl(2−m)m. Four independent models (including the formation of Tc(IV) chloro-complexes with 1 ≤ m ≤ 4) are evaluated.
b. Use of Tc(IV) solubility data at [Cl−] ≤ 3.0 M to determine and ε(Tc3O52+, Cl−), and data at [Cl−] > 3.0 M to determine and ε(Tc3O5Cl(2−m)m,Na+/Cl−).
Approach 2a properly explains Tc(IV) solubility data in dilute to concentrated NaCl and MgCl2 solutions (data not shown). However, this approach suggests the predominance of Tc3O5Cl(2−m)m complexes at [Cl−] ≥ 0.5 M. This is in strong contradiction with previous spectroscopic observations, which confirmed the predominance of TcnO4n−2yy in NaCl systems with [Cl−] ≤ 3.0 M and pH > 1.1.
Approach 2b clearly overestimates the solubility of Tc(IV) (data not shown). Hence, and ε(Tc3O52+, Cl−) derived from solubility data at [Cl−] ≤ 3.0 M are able to perfectly explain experimental observations gained up to [Cl−] = 9.0 M. Any additional contribution to the solubility provided by the definition of Tc3O5Cl(2−m)m species results in the overestimation of mTc(IV) in equilibrium with TcO2·0.6H2O(s). The outcome of approach 2b further indicates that the chemical model in approach 1 is the only one consistent with both solubility in dilute to concentrated NaCl and MgCl2 systems and spectroscopic observations available in the literature.12,17Fig. 10 shows the perfect agreement between the SIT-plots derived for NaCl and MgCl2 systems considering the only formation of Tc3O52+. This observation supports again that the same chemical model applies to dilute and concentrated chloride systems, and further that the formation of Tc(IV)–O/OH–Cl complexes can be disregarded under these pHm and mCl− conditions.
Fig. 10 SIT-plot for the solubility reaction TcO2·0.6H2O(s) + 2/3 H+ ⇔ 1/3 Tc3O52+ + 0.93H2O(l) considering experimental determined in dilute to concentrated NaCl and MgCl2 solutions. |
The y-intercept and slope determined by linear regression of the SIT-plots in Fig. 10 correspond to and −Δε (with −Δε = −1/3 ε(Tc3O52+, Cl−) + 2/3 ε(H+, Cl−)), respectively. The combination of −Δε and ε(H+, Cl−) reported in the NEA–TDB further allows the calculation of ε(Tc3O52+, Cl−). Excellent agreement is found between and ε(Tc3O52+, Cl−) derived from NaCl and MgCl2 systems. The final selection gained in this work is:
The SIT ion interaction coefficient determined for Tc3O52+ is much lower than that expected for a typical divalent cation according with charge-based correlations (ε(M2+, Cl−) = 0.15 ± 0.10 kg mol−1).42 However, the use of charge analogies for very large or oligomeric species must be considered with caution. The effect of size and the distribution of the formal charge throughout the voluminous species can lead to large deviations with respect to monomeric/simple species. Similar effects are observed for ternary Ca–M–OH complexes, as discussed in section 4.4.
values derived using both SIT and Pitzer approaches are in excellent agreement. The value of β(0) resulting from the Pitzer fit is also in good agreement with the estimate calculated following the approach described by Grenthe et al.44 (β(0) = −0.32 kg mol−1).§
Fig. 11 compares the experimental and calculated logK′s,Tc3O52+ for NaCl and MgCl2 systems, using both SIT and Pitzer approaches. The figure clearly shows that both activity models describe very well experimentally determined logK′s,Tc3O52+ values in dilute to concentrated saline systems, confirming again the good performance of SIT well beyond Im > 3.5 m.
TcO2·0.6H2O(s) + 0.4H2O(l) ⇔ TcO(OH)2(aq) | (7) |
logK′s,TcO(OH)2(aq) = log [TcO(OH)2(aq)] | (8) |
(9) |
SIT and Pitzer ion interaction coefficients for the neutral TcO(OH)2(aq) species are considered equal to zero. Thus, is calculated as the average mTc measured within 4 ≤ pHm ≤ 11, accounting also for the small contribution of water activity in eqn (9). The resulting value is slightly lower but agrees within the uncertainty with the current NEA–TDB selection .
Note that the formation and predominance of polyatomic species of the type TcnOm(OH)4n–2m(aq) are also consistent with the available experimental evidence. Although the definition of the monomeric TcO(OH)2(aq) species is favoured in the present work in agreement with the NEA–TDB selection, a definitive proof-of-concept for the predominance of this species is still missing.
TcO2·0.6H2O(s) + 1.4H2O(l) ⇔ TcO(OH)3− + H+ | (10) |
logK′s,TcO(OH)3− = log[TcO(OH)3−] + log[H+] | (11) |
(12) |
Conditional solubility constants (logK′s,TcO(OH)3−) are determined based on experimental solubility data in 0.1–5.0 M NaCl according to eqn (11). The use of eqn (12) allows the extrapolation of logK′s,TcO(OH)3− to I = 0 and the determination of the corresponding SIT/Pitzer ion interaction parameters.
(13) |
The linear regression (logK′s,TcO(OH)3− − 2D − 1.4logaw) vs. mNaCl (SIT-plot) is shown in Fig. 12. The resulting solubility constant at I = 0, , is in excellent agreement with the current NEA–TDB selection , and represents a very significant contribution in decreasing the associated uncertainty. The ion interaction coefficient ε(TcO(OH)3−, Na+) = (0.09 ± 0.02) kg mol−1 is calculated from the slope of the linear regression (−Δε = −ε(TcO(OH)3−, Na+) − ε(H+, Cl−) = (−0.21 ± 0.02) kg mol−1), considering ε(H+, Cl−) = (0.12 ± 0.01) kg mol−1 as reported by Guillaumont et al. (2003).18 This value is in moderate agreement with SIT ion interaction coefficients expected for a typical monovalent anion ε(X−, Na+) = −(0.05 ± 0.10) kg mol−1.42 Note that positive SIT ion interaction coefficients have been previously reported for anionic hydrolysis species of metal cations with similar ionic radii (e.g. Zr,21 Sn45).
Excellent agreement is obtained between values determined using SIT and Pitzer approaches. The extrapolation of this value to higher ionic strengths using the Pitzer activity model derived in this work results in a very good agreement with experimental logK′s,TcO(OH)3− (Fig. 13). In the case of SIT, minor deviations (≈0.1 log-units) appear between experimental and calculated logK′s,TcO(OH)3− at [NaCl] ≥ 3.0 M.
The slope of +3 observed in the experimental solubility data indicates the release of 3H+ in the chemical reaction controlling the solubility of Tc(IV) in systems with [CaCl2] ≥ 1.0 M and pHm ≥ 8. Provided the predominance of the solid phase TcO2·0.6H2O(s), a new aqueous species holding the moiety [TcO(OH)5]3− must be defined. Experimental data collected in NaCl–NaOH systems strongly argue for TcO(OH)3− as limiting hydrolysis species forming under alkaline to hyperalkaline pH conditions. The moiety [TcO(OH)5]3− has not been reported in NaCl media and is thus specifically stabilized by Ca2+ or Mg2+, either involving the formation of ternary species of the type Can/Mgn[TcO(OH)5]2n−3 or by strong ion interaction processes. Previous studies focussing on the solubility of Ln(III), An(III/IV/V) and Zr(IV) in concentrated CaCl2 systems have provided unequivocal indications on the formation of ternary Ca–Ln/An/Zr–OH complexes under alkaline pH conditions.21,34,35,46 In most cases, the formation of these species was accompanied by the full occupancy of the coordination sphere of the central metal atom, as also occurs in the moiety [TcO(OH)5]3− (CNTc(IV) = 6). Based on the previous evidence available for An(IV) and Zr(IV), the formation of ternary complexes of the type CanTcO(OH)(2n−3)5 in concentrated CaCl2 solutions is postulated for Tc(IV). The chemical reaction (14) is thus proposed to control the solubility of Tc(IV) under these conditions:
TcO2·0.6H2O(s) + nCa2+ + 3.4H2O(l) ⇔ CanTcO(OH)(2n−3)5 + 3H+ | (14) |
(15) |
(16) |
Conditional stability constants for reaction (14) are determined according to eqn (15) from Tc(IV) experimental solubility data gained in 1.0 M, 2.0 M and 4.5 M CaCl2 systems. The value of logK° is calculated by extrapolating the results in high ionic strength to I = 0 according to eqn (16). DFT calculations support the formation and stability of ternary complexes of the type CanTcO(OH)(2n−3)5 with n = 3 (see section 3.4.4). In spite of this and to gain further confidence in the chemical model controlling the chemistry of Tc under these conditions, Tc(IV) solubility data in concentrated [CaCl2] systems with pHm ≥ 8 have been evaluated considering four different chemical models based on eqn (16) with n = 1–4 to justify the quality of the adopted chemical model. Although it is postulated that the stabilization of the moiety [TcO(OH)53−] requires the formation of a new aqueous complex involving the participation of Ca2+, the fifth case with n = 0 is also evaluated for comparison purposes. In the first step, logK° values and ion interaction coefficients are calculated using the SIT approach. In the second step, the best chemical model selected accordingly with the criteria described below, was used to derive and ion interaction coefficients according to the Pitzer formalism.
Species | logK′experimentala | Outcome of SIT – plot | |||||
---|---|---|---|---|---|---|---|
I | 1.0 M | 2.0 M | 4.5 M | logKo | j | ε(i,j) | Quality |
a Uncertainty of logK′ values determined as ± 0.3. | |||||||
[TcO(OH)5]3− | −40.70 | −39.00 | −36.00 | −44.69 ± 0.3 | Ca2+ | −1.93 ± 0.10 | Δ = 0.10 |
Ca[TcO(OH)5]− | −40.71 | −39.32 | −36.72 | −41.71 ± 0.3 | Ca2+ | −1.61 ± 0.10 | Δ = 0.10 |
Ca2[TcO(OH)5]+ | −40.72 | −39.64 | −37.44 | −40.65 ± 0.3 | Cl− | −0.60 ± 0.10 | Δ = 0.04 |
Ca 3 [TcO(OH) 5 ] 3+ | −40.73 | −39.97 | −38.16 | −41.53 ± 0.3 | Cl − | −0.37 ± 0.10 | Δ = 0.00 |
Ca4[TcO(OH)5]5+ | −40.74 | −40.30 | −38.88 | −44.32 ± 0.3 | Cl− | −0.08 ± 0.20 | Δ = 0.11 |
Table 5 summarizes and ε(Can[TcO(OH)5]2n−3, Ca2+/Cl−) determined for the five chemical models evaluated, involving the formation of the binary/ternary CanTcO(OH)(2n−3)5 species with n = 0–4. Table 5 also shows the “quality parameter” (Δ), which is calculated as and analyses the goodness of the fit. The final selection of the chemical model for Tc(IV) in concentrated alkaline CaCl2 solutions is based on the criteria described below. Note that a similar strategy was successfully applied by Fellhauer for the evaluation of the ternary system Ca–Np(V)–OH in dilute to concentrated CaCl2 solutions.46,47
– Minimization of the “quality parameter” (Δ, Table 5).
– Consistency of SIT ion interaction coefficients. ε(i,j) are known to correlate with the charge of the ion,42 although significant deviations from this trend are expected for polyatomic species or voluminous ternary complexes. ε(Can[TcO(OH)5]2n−3, Ca2+/Cl−) values calculated in the present work (Table 5) are compared with ε(i,j) values reported for Ca–An(III/IV/V)–OH and Ca–Zr(IV)–OH complexes.
– Shape of the plot logKs,CanTcO(OH)5(2n−3)vs. CaCl2 concentration. The plot should give a smooth shape without jumps or turning points (Fig. A3†).
All the chemical models result in a smooth shape of the plot logK′svs. mCaCl2 (Fig. A3†). Chemical models involving the formation of the [TcO(OH)5]3−, Ca[TcO(OH)5]− and Ca4[TcO(OH)5]5+ species led to very large and clearly unrealistic values of ε(i,j) and/or Δ, and consequently were disregarded. The Ca2[TcO(OH)5]+ species shows a relatively low Δ, but retains a very negative SIT ion interaction coefficient. The chemical model including the species Ca3[TcO(OH)5]3+ species has the lowest Δ and holds a less negative SIT ion interaction coefficient (ε(Ca3[TcO(OH)5]3+, Cl−) = −(0.37 ± 0.10) kg mol−1). The latter value is very discrepant with respect to the value estimated according to the charge-analogy concept (ε(M3+,Cl−) = (0.25 ± 0.10) kg mol−1). As discussed above, the applicability of charge analogies for the estimation of ε(i,j) in the case of voluminous complexes has been previously challenged in the literature and is also disregarded in the present case.
Based on the discussion above and considering the clear inputs obtained from DFT calculations (see section 3.4.4), the chemical model involving the formation of the ternary Ca3[TcO(OH)5]3+ species is selected in the present work.
The same chemical model is considered for the interpretation of experimental observations in concentrated MgCl2 solutions with pHm ≥ 8. Due to limitations in pHm caused by the precipitation of Mg(OH)2(s) or Mg–OH–Cl(s) (pHmax ≈ 9), the increase of Tc(IV) solubility with the slope of +3 is only observed in 4.5 M MgCl2. This allows the only calculation of logK′s,Mg3TcO(OH)53+ for this ionic strength. In order to overcome the limited data set available, ε(Mg3[TcO(OH)5]3+, Cl−) is considered ≈ε(Ca3[TcO(OH)5]3+, Cl−), and is accordingly calculated using the SIT approach.
This value is significantly higher than , thus reflecting the earlier (lower pHm values) increase in solubility observed in MgCl2 systems.
The value of β(0) can also be estimated for M3+:X− interactions according to β(0)MX = 0.366 + εMX·(ln 10)/244 and using ε(Ca3[TcO(OH)5]3+, Cl−) = −0.37 ± 0.1 kg mol−1 as determined in the present study. The resulting estimate (β(0) = −0.0599) is in good agreement with the value obtained in the fit. Fig. 14 shows that both SIT and Pitzer models explain very well logK′s,Ca3TcO(OH)53+ values determined from the experimental solubility data.
As in the SIT approach, Pitzer ion interaction parameters determined for Ca3[TcO(OH)5]3+ are used for Mg3[TcO(OH)5]3+ to extrapolate the conditional stability constant at 4.5 M MgCl2 to I = 0 and to calculate . This value agrees within their uncertainties with determined using the SIT approach.
Chemical reactions | SIT | Pitzer |
---|---|---|
logK° | logK° | |
TcO2·0.6H2O(s) + 2/3 H+ ⇔ 1/3Tc3O52+ + 0.93H2O | −1.53 ± 0.15 | −1.50 ± 0.10 |
TcO2·0.6H2O(s) + 0.4H2O ⇔ TcO(OH)2 | −8.80 ± 0.50 | −8.80 ± 0.50 |
TcO2·0.6H2O(s) + 1.4H2O ⇔ TcO(OH)3− + H+ | −19.27 ± 0.06 | −19.32 ± 0.10 |
TcO2·0.6H2O(s) + 3Mg2+ + 3.4H2O ⇔ Mg3[TcO(OH)5]3+ + 3H+ | −40.55 ± 0.50 | −40.32 ± 0.50 |
TcO2·0.6H2O(s) + 3Ca2+ + 3.4H2O ⇔ Ca3[TcO(OH)5]3+ + 3H+ | −41.53 ± 0.30 | −41.65 ± 0.30 |
Species | SIT | Pitzer | |||||
---|---|---|---|---|---|---|---|
Binary parameters | Mixing parameters | ||||||
i | j | ε(i,j) | β (0) | β (1) | C (ϕ) | Θ ii′ | Ψ iji′ |
a Fixed value for the corresponding charge type, according to ref. 44. b Estimated value for the corresponding charge type, according to ref. 42. c Estimated value for the corresponding charge type, according to ref. 48. | |||||||
Tc3O52+ | Cl− | −0.41 ± 0.05 | −0.3681 | 2.6972 | 0.0063 | 0 | 0 |
TcO(OH)3− | Na+ | 0.09 ± 0.02 | −0.0087 | 0.3a | 0.035 | 0 | 0 |
Ca2+ | 0.15b | 0.3c | 1.7c | 0c | 0c | 0c | |
Ca3[TcO(OH)5]3+ | Cl− | −0.37 ± 0.1 | −0.074 | 4.3a | 0.015 | 0 | 0 |
Mg3[TcO(OH)5]3+ | Cl− | −0.37 ± 0.1 | −0.074 | 4.3a | 0.015 | 0 | 0 |
TcO(OH)2(aq) | Na+, Mg2+, Ca2+, Cl− | 0 | 0 | 0 | 0 | 0 | 0 |
TcO2·0.6H2O(s) is the solid phase controlling the solubility of Tc(IV) in all the evaluated systems, except under acidic conditions with a very high chloride concentration where the formation of a Tc(IV)–Cl solid phase is hinted from solubility experiments in agreement with the literature. The previously unreported formation of the polynuclear Tc3O52+ species under acidic pH conditions is accepted based on the slope analysis of solubility data gained in the present work and spectroscopic evidence available in the literature. The predominance of this species in the aqueous phase under acidic conditions (instead of TcO2+ + TcO(OH)+) properly explains the experimental observations from dilute to concentrated saline systems, except in very acidic systems with a high chloride concentration where the formation of binary Tc(IV)–Cl or ternary Tc(IV)–O/OH–Cl aqueous species is indicated by spectroscopic techniques. The pH-independent chemical reaction TcO2·0.6H2O(s) + 0.4 H2O(l) ⇔ TcO(OH)2(aq) controls the solubility of Tc(IV) under weakly acidic to alkaline pH conditions. The stability field of TcO(OH)2(aq) decreases in concentrated saline systems due to the greater stabilization of charged species and the formation of new ternary complexes in concentrated alkaline MgCl2 and CaCl2 systems. determined in the present work agrees well within the uncertainties with the value currently selected in the NEA–TDB. The solubility of Tc(IV) increases with a slope of +1 (logmTcvs. pHm) in NaCl systems with pHm ≥ 11, indicating the predominance of TcO(OH)3− as previously selected in the NEA–TDB and decreases about one order of magnitude with increasing ionic strength due to ion interaction processes. A very different behaviour of Tc(IV) is observed in concentrated alkaline MgCl2 and CaCl2 systems, where a steep increase of the solubility with a well-defined slope of +3 is observed. The formation of Mg3[TcO(OH)5]3+ and Ca3[TcO(OH)5]3+ species is proposed based on the slope analysis, model calculations and previous solubility and spectroscopic evidence available for An(IV) and Zr(IV). DFT calculations further support the key role of Ca2+ in stabilizing the highly charged [TcO(OH)5]3− moiety.
The comprehensive thermodynamic model derived in the present work for the system Tc4+–Na+–Mg2+–Ca2+–H+–Cl−–OH−–H2O at T = 25 °C provides an accurate and robust tool for the calculation of Tc(IV) solubility in a diversity of geochemical conditions. This new thermodynamic model represents a significant improvement and is highly relevant for calculating reliable Tc(IV) source term concentrations in the context of safety assessments for nuclear waste repositories.
Footnotes |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6dt00973e |
‡ The same trend is reported for the ionic radii of the corresponding metal cations: Tc(IV) = 0.645 Å (CN = 6), Zr(IV) = 0.72 Å (CN = 6), Th(IV) = 1.05 Å (CN = 8).48 |
§ β(0)MX = 0.15 + ε(M,X)·(ln10)/2 for M2+ − X– interactions, where ε(M,X) is the SIT ion interaction coefficient determined for the same species. |
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