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Title: Influence of Iron Redox Transformations on Plutonium Sorption to Sediments

Abstract

Plutonium subsurface mobility is primarily controlled by its oxidation state, which in turn is loosely coupled to the oxidation state of iron in the system. Experiments were conducted to examine the effect of sediment iron mineral composition and oxidation state on plutonium sorption and oxidation state. A pH 6.3 vadose zone sediment containing iron oxides and iron-containing phyllosilicates was treated with various complexants (ammonium oxalate) and reductants (dithionite-citrate-bicarbonate) to selectively leach and/or reduce iron oxide and phyllosilicate phases. Mössbauer spectroscopy was used to identify initial iron mineral composition of the sediment and monitor dissolution and reduction of iron oxides. Sorption of Pu(V) was monitored over one week for each of six treated sediment fractions. Plutonium oxidation state speciation in the aqueous and solid phases was monitored using solvent extraction, coprecipitation, and XANES. Mössbauer spectroscopy showed that the sediment contained 25-30% hematite, 60-65% Al-goethite, and <10%Fe(III) in phyllosilicate; there was no detectable Fe(II). Upon reduction with a strong chemical reductant (dithionite-citrate buffer, DCB), much of the hematite and goethite disappeared and the Fe in the phyllosilicate reduced to Fe(II). The rate of sorption was found to correlate with the 1 fraction of Fe(II) remaining within each treated sediment phase. Pu(V) wasmore » the only oxidation state measured in the aqueous phase, irrespective of treatment, whereas Pu(IV) and much smaller amounts of Pu(V) and Pu(VI) were measured in the solid phase. Surface-mediated reduction of Pu(V) to Pu(IV) occurred in treated and untreated sediment samples; Pu(V) remained on untreated sediment surface for two days before reducing to Pu(IV). Similar to the sorption kinetics, the reduction rate was correlated with sediment Fe(II) concentration. The correlation between Fe(II) concentrations and Pu(V) reduction demonstrates the potential impact of changing iron mineralogy on plutonium subsurface transport through redox transition areas. These findings should influence the conceptual models of long-term stewardship of Pu contaminated sites that have fluctuating redox conditions, such as vadose zones or riparian zones.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1000116
Report Number(s):
PNNL-SA-70518
30449; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Radiochimica Acta, 98(9-11):685-692
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Hixon, Amy E., Hu, Yung-Jin, Kaplan, Daniel I., Kukkadapu, Ravi K., Nitsche, Heino, Qafoku, Odeta, and Powell, Brian A. Influence of Iron Redox Transformations on Plutonium Sorption to Sediments. United States: N. p., 2010. Web. doi:10.1524/ract.2010.1769.
Hixon, Amy E., Hu, Yung-Jin, Kaplan, Daniel I., Kukkadapu, Ravi K., Nitsche, Heino, Qafoku, Odeta, & Powell, Brian A. Influence of Iron Redox Transformations on Plutonium Sorption to Sediments. United States. doi:10.1524/ract.2010.1769.
Hixon, Amy E., Hu, Yung-Jin, Kaplan, Daniel I., Kukkadapu, Ravi K., Nitsche, Heino, Qafoku, Odeta, and Powell, Brian A. 2010. "Influence of Iron Redox Transformations on Plutonium Sorption to Sediments". United States. doi:10.1524/ract.2010.1769.
@article{osti_1000116,
title = {Influence of Iron Redox Transformations on Plutonium Sorption to Sediments},
author = {Hixon, Amy E. and Hu, Yung-Jin and Kaplan, Daniel I. and Kukkadapu, Ravi K. and Nitsche, Heino and Qafoku, Odeta and Powell, Brian A.},
abstractNote = {Plutonium subsurface mobility is primarily controlled by its oxidation state, which in turn is loosely coupled to the oxidation state of iron in the system. Experiments were conducted to examine the effect of sediment iron mineral composition and oxidation state on plutonium sorption and oxidation state. A pH 6.3 vadose zone sediment containing iron oxides and iron-containing phyllosilicates was treated with various complexants (ammonium oxalate) and reductants (dithionite-citrate-bicarbonate) to selectively leach and/or reduce iron oxide and phyllosilicate phases. Mössbauer spectroscopy was used to identify initial iron mineral composition of the sediment and monitor dissolution and reduction of iron oxides. Sorption of Pu(V) was monitored over one week for each of six treated sediment fractions. Plutonium oxidation state speciation in the aqueous and solid phases was monitored using solvent extraction, coprecipitation, and XANES. Mössbauer spectroscopy showed that the sediment contained 25-30% hematite, 60-65% Al-goethite, and <10%Fe(III) in phyllosilicate; there was no detectable Fe(II). Upon reduction with a strong chemical reductant (dithionite-citrate buffer, DCB), much of the hematite and goethite disappeared and the Fe in the phyllosilicate reduced to Fe(II). The rate of sorption was found to correlate with the 1 fraction of Fe(II) remaining within each treated sediment phase. Pu(V) was the only oxidation state measured in the aqueous phase, irrespective of treatment, whereas Pu(IV) and much smaller amounts of Pu(V) and Pu(VI) were measured in the solid phase. Surface-mediated reduction of Pu(V) to Pu(IV) occurred in treated and untreated sediment samples; Pu(V) remained on untreated sediment surface for two days before reducing to Pu(IV). Similar to the sorption kinetics, the reduction rate was correlated with sediment Fe(II) concentration. The correlation between Fe(II) concentrations and Pu(V) reduction demonstrates the potential impact of changing iron mineralogy on plutonium subsurface transport through redox transition areas. These findings should influence the conceptual models of long-term stewardship of Pu contaminated sites that have fluctuating redox conditions, such as vadose zones or riparian zones.},
doi = {10.1524/ract.2010.1769},
journal = {Radiochimica Acta, 98(9-11):685-692},
number = ,
volume = ,
place = {United States},
year = 2010,
month =
}
  • Here, Pu(IV) and Pu(V) sorption to goethite was investigated over a concentration range of 10 –15–10 –5 M at pH 8. Experiments with initial Pu concentrations of 10 –15 – 10 –8 M produced linear Pu sorption isotherms, demonstrating that Pu sorption to goethite is not concentration-dependent across this concentration range. Equivalent Pu(IV) and Pu(V) sorption Kd values obtained at 1 and 2-week sampling time points indicated that Pu(V) is rapidly reduced to Pu(IV) on the goethite surface. Further, it suggested that Pu surface redox transformations are sufficiently rapid to achieve an equilibrium state within 1 week, regardless of themore » initial Pu oxidation state. At initial concentrations >10 –8 M, both Pu oxidation states exhibited deviations from linear sorption behavior and less Pu was adsorbed than at lower concentrations. NanoSIMS and HRTEM analysis of samples with initial Pu concentrations of 10 –8 – 10 –6 M indicated that Pu surface and/or bulk precipitation was likely responsible for this deviation. In 10 –6 M Pu(IV) and Pu(V) samples, HRTEM analysis showed the formation of a body centered cubic (bcc) Pu 4O 7 structure on the goethite surface, confirming that reduction of Pu(V) had occurred on the mineral surface and that epitaxial distortion previously observed for Pu(IV) sorption occurs with Pu(V) as well.« less
  • Well-defined solid sources of Pu(III) (PuCl3), Pu(IV) (Pu (NO3)4 and Pu (C2O4)2), and Pu(VI) (PuO2(NO3)2) were placed in lysimeters containing vadose zone sediments and exposed to natural weather conditions for 2 or 11 years. The objective of this study was to measure the release rate of Pu and the changes in the Pu oxidation states from these Pu sources with the intent to develop a reactive transport model source-term. Pu(III) and Pu(IV) sources had identical Pu concentration depth profiles and similar Pu release rates. Source release data indicate that PuIV(C2O4)2 was the least mobile, whereas PuVIO2(NO3)2 was the most mobile.more » Synchrotron X-ray fluorescence (SXRF) revealed that Pu was very unevenly distributed on the sediment and Mn concentrations were too low (630 mg kg-1) and perhaps of the wrong mineralogy to influence Pu distribution. The high stability of sorbed Pu(IV) is proposed to be due to the formation of a stable hydrolyzed Pu(IV) surface species. Plutonium X-ray absorption near-edge spectroscopy (XANES) analysis conducted on sediment recovered at the end of the study from the PuIV(NO3)4- and PuIIICl3-amended lysimeters contained essentially identical Pu distributions: approximately 37% Pu(III), 67% Pu(IV), 0% Pu(V), and 0% Pu(VI). These results were similar to those using a wet chemistry Pu oxidation state assay, except the latter method did not detect any Pu(III) present on the sediment but instead indicated that 93-98% of the Pu existed as Pu(IV). This discrepancy was likely attributable to incomplete extraction of sediment Pu(III) by the wet chemistry method. Although Pu has been known to exist in the +3 oxidation state under microbially induced reducing conditions for decades, to our knowledge, this is the first observation of steady-state Pu(III) in association with natural sediments. On the basis of thermodynamic considerations, Pu(III) has a wide potential distribution, especially in acidic environments, and as such may warrant further investigation.« less
  • The sorption of /sup 54/Mn/sup 2 +/ in concentrations equal to 4 x 10/sup -5/ and 3.3 x 10/sup -11/ M by iron(III) oxide and iron(III) hydroxide in 1 M NaNO/sub 3/ and NaCLO/sub 4/ and 5 M NaCl has been studied as a function of the ambient pH, and the pH ranges for the concentrating of the radionuclide have been found. In a solution of /sup 54/Mn/sup 2 +/ with a concentration corresponding to the isotope without a carrier, /sup 54/Mn(III) and /sup 54/Mn(IV) have been discovered in an amount corresponding to 25% of the original /sup 54/Mn/sup 2more » +/ by sorption on Fe/sub 2/O/sub 3/ and Fe(III) hydroxide. A method for studying the influence of the temperature on the sorption process has been developed. Experimental data on the changes in the sorption of /sup 54/Mn/sup 2 +/ on Fe/sub 2/O/sub 3/ at 26, 40, and 50/sup 0/C and the temperature factor method have been used to evaluate ..delta..G/sup 0/, ..delta..S/sup 0/, and ..delta..G/sup 0/ for the sorption process, which were found to be equal to -12.6 kJ/mole, -34 J/mole x deg, and -55.2 kJ/mole, respectively. The process of the sorption of /sup 54/Mn/sup 2 +/ on Fe/sub 2/O/sub 3/ and iron(III) hydroxide has been interpreted as an interaction between the hydroxo complex MnOH/sup +/ and the surface of the sorbent with the formation of an hydroxyl bridge between the sorbent and the sorbate.« less
  • Microbial iron reduction is an important biogeochemical process that can affect metal geochemistry in sediments through direct and indirect mechanisms. With respect to Fe(III) (hydr)oxides bearing sorbed divalent metals, recent reports have indicated that (1) microbial reduction of goethite/ferrihydrite mixtures preferentially removes ferrihydrite, (2) this process can incorporate previously sorbed Zn(II) into an authigenic crystalline phase that is insoluble in 0.5 M HCl, (3) this new phase is probably goethite, and (4) the presence of nonreducible minerals can inhibit this transformation. This study demonstrates that a range of sorbed transition metals can be selectively sequestered into a 0.5 M HClmore » insoluble phase and that the process can be stimulated through sequential steps of microbial iron reduction and air oxidation. Microbial reduction experiments with divalent Cd, Co, Mn, Ni, Pb, and Zn indicate that all metals save Mn experienced some sequestration, with the degree of metal incorporation into the 0.5 M HCl insoluble phase correlating positively with crystalline ionic radius at coordination number = 6. Redox cycling experiments with Zn adsorbed to synthetic goethite/ferrihydrite or iron-bearing natural sediments indicate that redox cycling from iron reducing to iron oxidizing conditions sequesters more Zn within authigenic minerals than microbial iron reduction alone. In addition, the process is more effective in goethite/ferrihydrite mixtures than in iron-bearing natural sediments. Microbial reduction alone resulted in a ~3× increase in 0.5 M HCl insoluble Zn and increased aqueous Zn (Zn-aq) in goethite/ferrihydrite, but did not significantly affect Zn speciation in natural sediments. Redox cycling enhanced the Zn sequestration by ~12% in both goethite/ferrihydrite and natural sediments and reduced Zn-aq to levels equal to the uninoculated control in goethite/ferrihydrite and less than the uninoculated control in natural sediments. These data suggest that in situ redox cycling may serve as an effective method for mitigating divalent metal contamination in subsurface environments.« less
  • Technetium is an important environmental contaminant introduced by the processing and disposal of irradiated nuclear fuel and atmospheric nuclear tests. Under oxic conditions technetium is soluble and exists as pertechnatate anion (TcO4-), while under anoxic conditions Tc is usually insoluble and exists as precipitated Tc(IV). Here we investigated abiotic Tc(VII) reduction in mineralogically heterogeneous, Fe(II)-containing sediments. The sediments were collected from a 55 m borehole that sampled a semi-confined aquifer at the Hanford Site, USA that contained a dramatic redox transition zone. One oxic facies (18.0-18.3 m) and five anoxic facies (18.3-18.6 m, 30.8-31.1 m, 39.0-39.3 m, 47.2-47.5 m andmore » 51.5-51.8 m) were selected for this study. Chemical extractions, X-ray diffraction, electron microscopy, and Mössbauer spectroscopy were applied to characterize the Fe(II) mineral suite that included: Fe(II)-phyllosilicates, pyrite, magnetite and siderite. The Fe(II) mineral phase distribution differed between the sediments. Sediment suspensions were adjusted to the same 0.5 M HCl extracted Fe(II) concentration (0.6 mM) for Tc(VII) reduction experiments. Aqueous Fe was low in all sediment suspensions (<2 μM) and below the Fe(II)aq detection limit (10 μM). Technetium(VII) reduction occurred in all anoxic sediments at depths greater than 18.3 m and reaction time differed significantly between the sediments (8-219 d). Mössbauer analysis of the Tc-reacted, 30.8-31.1 m sediment confirmed that Tc(VII) was reduced by solid-phase Fe(II), with siderite and Fe(II)-containing phyllosilicates implicated as redox reactive phases. Technetium-XAS analysis demonstrated that Tc associated with sediments was in the Tc(IV) valence state and immobilized as clusters of a TcO2·nH2O-like phase. The speciation of redox product Tc(IV) was not affected by reduction rate or Fe(II) mineralogy.« less