Environ. Sci. Technol.
2005, 39, 4117-4124
Neptunium(V) Partitioning to
Uranium(VI) Oxide and Peroxide
Solids
M A T T H E W D O U G L A S , †,‡ S U E B . C L A R K , * ,†
JUDAH I. FRIESE,‡ BRUCE W. AREY,‡
EDGAR C. BUCK,‡ AND
BRADY D. HANSON‡
Washington State University, Department of Chemistry,
Pullman, Washington 99164-4630, and Radiochemical Science
and Engineering Group, Pacific Northwest National
Laboratory, Richland, Washington 99352
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Metaschoepite, [(UO2)8O2(OH)12]‚10H2O, and metastudtite,
Downloaded via HARBIN ENGINEERING UNIV on June 27, 2022 at 03:06:27 (UTC).
UO4‚4H2O, are alteration phases anticipated in a spent nuclear
fuel repository following the moist oxidation of UO2 on a
geologic time scale. Dissolved concentrations and hence
potential mobility of other radionuclides in the fuel, such as
the neptunyl cation (NpO2+), will likely be determined by
the extent of their partitioning into these U(VI) solids.
237Np is of particular interest due to its potential high
mobility and long half-life (2.1 × 106 years.) In this study,
metaschoepite has been precipitated and subsequently
transformed to studtite in the presence of dissolved Np. The
metaschoepite and studtite solids that formed initially
contained <10 and 6500 ppm Np, respectively. Batch
dissolution studies of these solids at pH 6 demonstrate
release of Np that exceeds congruent dissolution of U from
metastudtite; furthermore, the released Np cation remains
in solution. Thus, although the Np partitions into the
metastudtite solid initially, it is released to solution over
time, indicating that metastudtite is not likely to serve as a
host solid for Np incorporation or sorption of the neptunyl
cation on long time scales.
Introduction
Secondary uranium (U) solids are expected to be the long-
term solubility limiting phases in cases of subsurface U
contamination (1) and at geological repository sites for the
disposal of U-based spent nuclear fuel (SNF) (2). SNF is 95%
UO2 (tetravalent U) with the remainder composed of highly
radioactive fission and activation products (3). Under the
moist, oxidizing environment expected at Yucca Mountain,
the proposed repository site in the United States, a para-
genetic sequence of hexavalent U oxides and silicates is
expected to form (4). Such U(VI) solids may limit dissolved
concentrations of trace level radionuclides which dominate
the level of SNF radioactivity.
The uranyl oxide hydrate metaschoepite, [(UO2)8O2-
(OH)12]‚10H2O, has been identified as an initial precipitate
on the surface of natural U ore deposits and on SNF following
corrosion studies using an oxidizing groundwater (5-8). Its
presence at the boundaries of exposed U ores indicates its
* Corresponding author current address: Pacific Northwest
National Laboratory, Richland, WA; phone: (509)335-1411; fax:
(509)335-8867; e-mail: s_clark@wsu.edu.
† Washington State University.
‡ Pacific Northwest National Laboratory.
10.1021/es0405169 CCC: $30.25  2005 American Chemical Society
Published on Web 05/04/2005
long-term stability, and it has been shown to persist for
hundreds of thousands of years in the environment (9).
Studtite, UO4‚4H2O, and metastudtite, UO4‚2H2O, are
uranyl peroxide hydrates and have received increased
attention recently (10-13). As the only known peroxide
minerals in nature, they are occasionally observed in
association with U deposits and are thought to occur when
secondary uranyl solids incorporate peroxide generated by
radiolysis of water. Because of the high radiation field
surrounding a geologic repository of SNF, production of
peroxide in sufficient quantity to precipitate uranyl peroxide
solid phases is possible (11). Studtite has been observed on
the surface of SNF following its immersion in deionized water
for two years (10) and as a component of alteration rinds
(assemblages of secondary U phases following oxidative
corrosion) on SNF stored at the Hanford site in the United
States (14).
Burns et al. (15-17) have evaluated the crystal chemistry
of the U(VI) minerals and predicted the incorporation of
transuranium elements into their structures. Partitioning into
uranyl phases was suggested to result in decreased mobility
of actinides following their release during the alteration of
SNF. Using bond-valence arguments, likely mechanisms of
incorporation were hypothesized depending on the ionic
radius and valence state of the non-U cation. Because it
adopts a similar dioxo cation geometry, Np(V) could sub-
stitute for U(VI) in the structures of various U solids, provided
that a charge-balance mechanism exists to compensate for
the difference in cationic charge. Two proposed mechanisms
for charge balance are the substitution of O2- by OH- and/or
incorporation of additional low valence cations, such as
Na+, into the interlayer (17).
Experimentally, there is conflicting evidence for incor-
poration of Np into metaschoepite. Buck et al. (18) reported
that dehydrated schoepite, a phase with the same sheet
structure as metaschoepite with formula (UO2)O0.25-x(OH)1.5+2x,
(0 < x <0.25) (19), retained Np at ∼550 ppm concentration
during SNF corrosion studies. In these studies, Yucca
Mountain groundwater was dripped onto SNF at the rate of
0.75 mL every 3.5 days. The solids were then examined for
evidence of secondary phase formation at various intervals.
In contrast, another study characterized alteration products
from SNF by XAS to establish an upper limit for Np in
dehydrated schoepite of 200-333 ppm (20). Finch et al. (21)
defined an upper limit of 2 mol % (∼20 000 ppm) Np
incorporation into dehydrated schoepite following analyses
of solids generated during aqueous corrosion of unirradiated
Np-bearing U-oxides. A recent study by Burns et al. (13)
suggests that very little Np(V) is partitioned into synthetic
metaschoepite. A small fraction of the Np in solution was
removed during formation of metaschoepite; however, a
30-second rinse with 0.5 M acetic acid removed virtually all
Np from the bulk solid, suggesting it had been surface sorbed.
In this work, we investigated the transformation of
metaschoepite to studtite in the presence of dissolved Np.
Our objectives were to (i) measure bulk properties of the
solids including phase identification, morphology, and the
concentration of Np partitioned into the solid phase(s);
(ii) seek evidence for the formation of discrete Np solids; and
(iii) evaluate the possibility of Np release from the solids
with time. We report the characterization of solid phases by
X-ray powder diffraction (XRD), gamma spectrometry (GS),
and scanning electron microscopy with energy-dispersive
X-ray spectroscopy (SEM/EDS), and results of batch dis-
solution studies of the solids.
VOL. 39, NO. 11, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4117
Materials and Methods
Experimental Procedures. Solid-Phase Synthesis. To poly-
ethylene tubes containing 30 mL of 0.010 M uranyl acetate,
a solution of NpO2+ in 5% HNO3 was added, resulting in a
Np/U mole ratio of 0.02. The U/Np solution was adjusted to
pH 5.5 using NaOH to hydrolyze the uranyl and precipitate
metaschoepite. After 48 h at room temperature, a bright
yellow precipitate had settled on the walls and bottom surface
of the tubes and the pH had decreased to approximately 5.
Aliquots of the supernatant were passed through 0.45-µm
filters and diluted in 0.5 M HNO3 for subsequent analysis of
U and Np concentrations. Isolated solids were washed three
times with room-temperature deionized water and dried at
room temperature. To duplicate samples, 15 mL of 30% H2O2
(resulting in ∼4 M H2O2) was added to initiate metaschoepite
transformation to studtite. After 3 days, the pH of each sample
had decreased to pH 4.6. The sample to which Np had been
added was composed of an orange/brown precipitate that
was aggregated into large (∼1 mm diameter) particles. The
sample without Np was composed of a finely divided yellow
powder. The samples were left to continue reacting at room
temperature with daily agitation for an additional 3 days to
ensure transformation to studtite was complete. At the
conclusion of this time period, the samples were centrifuged
and the supernatant was sampled as above. The solids were
washed three times with room-temperature deionized water
and dried at room temperature. Solid-phase characterization FIGURE 1. (a) Staggered XRD patterns obtained from the uranyl
was completed using the techniques described below. solids precipitated from a pH 5.5 solution with and without the
Batch Dissolution Studies. Well-characterized solids were presence of Np. Lines of the metaschoepite reference PDF 29-1376
employed in batch dissolution studies using a procedure match the diffractograms resulting from the two solids. (b) Staggered
established by Giammar and Hering (22, 23). Duplicates of XRD patterns obtained from the solids resulting from the addition
a known mass (2-14 mg) of each solid sample were placed of H2O2 to the solids in (a), with and without the presence of Np.
into polyethylene vials containing 50 mL of 0.010 M NaNO3 Lines of the studtite reference PDF 16-206 match the diffractograms
and 0.005 M 2-(N-morpholino)ethanesulfonic acid (MES) resulting from the two solids. Arrows indicate diffraction maxima
buffer at pH 6.0, resulting in an average solid/solution ratio attributed to Al2O3, added as an internal standard. The initial
of 0.17 g/L. The vials were maintained at 30 °C in a waterbath concentrations of Np for each sample are listed in Table 1, and all
for the four month duration of the study and were only diffractograms are labeled with Np concentrations determined in
the bulk solids by GS.
removed for the brief periods required for sampling. Aliquots
of the suspension were withdrawn at periodic time intervals
such that the solid/solution ratio remained constant through- Scanning Electron Microscopy/Energy-Dispersive X-ray
out the experiment. The supernatant was filtered using Spectroscopy. Samples to be analyzed by SEM/EDS were
0.2-µm membrane filters and acidified with 2% HNO3 prior mounted on stainless steel stubs and carbon sputter-coated.
to subsequent analysis of dissolved concentrations of U and Using a JEOL 840 scanning electron microscope with
Np by ICP-MS. Robinson backscatter detector and an Oxford ISIS 300 energy-
Analytical Techniques. X-ray Powder Diffraction Analysis. dispersive spectrometer at 20 kV accelerating voltage, images
Solid samples were ground in a mortar and pestle with were obtained showing the morphology of crystallites within
corundum, Al2O3, added as an internal standard. A collodian/ each sample. Qualitative EDS was performed on numerous
amyl acetate mixture was used to adhere the powder to a crystallites in each sample (at 29 kV accelerating voltage) to
glass slide. Using a Scintag PAD V diffractometer, data were examine whether variable elemental compositions existed
collected between 2θ angles of 5-65° at 0.02° steps and 20-s among the crystallites. Bremsstrahlung radiation limits the
count times. JADE6 software from Materials Data, Inc. was sensitivity of this technique, and EDS has an approximate
used to plot the diffraction patterns, identify d-values, and detection limit of 0.1 wt % for each element analyzed (24).
fit reference patterns to identify the phase(s) present. The
Inductively Coupled Plasma-Mass Spectrometry Analysis.
International Centre for Diffraction Data Powder Diffraction
Dissolved U and Np were analyzed with a Hewlett-Packard
File (ICDD-PDF) database of reference patterns was used to
4500 quadrupole mass analyzer with an inductively coupled
identify phases present in samples. Detection of minor phases
argon plasma ionization source. A four-point calibration
(less than 2-3 wt %) and amorphous phases by this method
curve was prepared using matrix matched standards. Nep-
is not possible, an inherent limitation of powder XRD.
tunium was standardized following separation from its
Gamma-Ray Spectrometry. Solid samples were weighed
daughter products using Eichrom TEVA extraction chro-
into glass scintillation vials and counted on a Ge(Li) detector
matographic resin (25) and subsequent GS and liquid
for variable lengths of time to obtain acceptable counting
scintillation counting. The calculated concentration resulted
statistics. The software program GENIE 2000 was used to
in a calibration slope for Np that was consistent with the
identify 237Np based on gamma-ray peak energies (86.48,
slope of the U calibration curve, indicating similar ionization
92.29, 95.87, and 108.00 keV) and calculate concentrations
efficiency and detection of U and Np.
present in samples based on sample mass, energy calibra-
tions, and measured detector efficiencies. On the basis of
counting times of 16 h, detection limits were approximately Results and Discussion
2.88 × 10-6 µCi/mL (0.031 µg/mL, 1.3 × 10-7 M) and Solid-Phase Characterization. Diffractograms of precipitated
2.54 × 10-3 µCi/g (10 µg/g) for 237Np in the supernatants and solid phases collected by XRD indicated the solids isolated
solids, respectively. prior to addition of H2O2 were metaschoepite (PDF 29-1376),

4118 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 11, 2005
TABLE 1. Np Activity Measured by GS for Initial and Final Supernatants and Isolated Solidsa
total reaction initial supernatant final supernatant % Np remaining bulk solid phase
sample time (days) final pH [Np] (M) [Np] (M) in solution [Np] (µg/g)
Metaschoepite, 2 mol % Np 2 5.0 (1.94 ( 0.13) × 10-4 (1.47 ( 0.13) × 10-4 76 ( 4 <10
Metaschoepite, 0 mol % Np 2 4.9 N/A N/A N/A N/A
Studtite, 2 mol % Np 8 4.6 (1.31 ( 0.06) × 10-4 <1.31 × 10-7 <0.03 6500 ( 200
Studtite, 0 mol % Np 8 4.6 N/A N/A N/A N/A
a Reported errors are 2σ.

FIGURE 2. Scanning electron micrographs show the morphologies of the metaschoepite solid (a) precipitated in the absence of Np and
(b) in the presence of a Np/U mole ratio of 0.02. Although Np could not be detected in the bulk solid, the crystallites in (b) appear to have
been altered by its presence (see text for details). The morphologies of the studtite solid (c) transformed from metaschoepite in the absence
of Np and (d) in the presence of a Np/U ratio of 0.02. The solid in (c) was pale yellow, while that in (d) was orange-brown. While the
aggregates in (d) appear somewhat larger than those in (c), neither occurs as acicular crystallites, the described morphology of studtite,
even though XRD confirms the identity of the phase as such.

while those reacted with the hydrogen peroxide were studtite
(PDF 16-206) (Figure 1). No differences were seen in the
diffraction patterns for solids formed in the presence and
absence of Np.
The Np activity was measured by GS for both the final
supernatants and isolated solids (Table 1.) Most of the Np
(∼76%) remained in the supernatant following contact with
the metaschoepite. As the solid was transformed to studtite,
however, the concentration of Np remaining in the super-
natant was below the detection limit (1.3 × 10-7 M) for GS.
Loss of Np from solution was observed while the pH of the
supernatant changed very little (decreased by 0.4 pH units)
during formation of the studtite. Precipitation of a hydrolysis
product of Np, such as NpO2(OH) or Np2O5‚xH2O, seems
unlikely based on reported solubilities of these Np solids
and the lack of significant change in pH. The concentration
of Np associated with the metaschoepite solid was below the
detection limit of 10 µg Np/g solid. However, the studtite
that resulted from the transformation of metaschoepite in
the presence of Np contained 6500 µg Np/g solid.
The morphologies of all solids are shown in Figure 2.
Although Np could not be detected in the isolated meta-
schoepite solid by GS, the presence of the Np may have had
an influence on the morphology of the solid. While the
metaschoepite formed in the absence of Np exhibits the usual
fine-grained, sphere-like crystallite morphology expected for
metaschoepite (19) (Figure 2a), the metaschoepite precipi-
tated with Np(V) present is composed of lepispherically
shaped aggregates (Figure 2b). EDS analysis of the meta-
schoepite solids indicates only U and O are present, in
addition to a minor amount of Na. The Na may indicate the
presence of an impurity Na-uranyl oxide hydrate (amorphous

VOL. 39, NO. 11, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4119
or not in sufficient quantity to be observed in the XRD
pattern.)
The morphologies of the studtite samples are shown in
scanning electron micrographs at varying magnification
(Figure 2c and d). Although natural samples of studtite are
described as pale yellow acicular crystals (26), the solids
obtained in our work were composed of fine, spherically
shaped particles. This may be a result of the rapid precipita-
tion and short aging times used in our synthesis. No
significant differences were seen between the solids syn-
thesized with and without Np at this scale. However, the
solids differed in color. Studtite precipitated from solution
without Np appeared pale yellow, while the solid containing
6500 ppm Np was orange-brown. Although GS demonstrated
that the solid contained Np, it could not be detected by EDS,
even after analysis of numerous aggregates and particles. If
Np precipitated as a discrete solid such as Np2O5, its
concentration within that particle should exceed the detec-
tion limit of EDS. The fact that Np could not be detected by
EDS indicates that it was likely distributed throughout the
solid phase. Although every effort was made to sample large
numbers of solid-phase aggregates, it is possible that a
discrete particle containing Np was overlooked.
This study reinforces previous observations that meta-
schoepite and studtite differ in their affinity for Np (13, 27).
Metaschoepite is composed of layered two-dimensional
sheets of polymerized uranyl polyhedra (28), whereas meta-
studtite contains chains of uranyl polyhedra linked by
peroxide units (11). The uranyl adopts a pentagonal bi-
pyramidal coordination geometry in metaschoepite and a
pseudohexagonal bipyramidal geometry in studtite and
metastudtite. These sheets and chains of polyhedra are
electrostatically neutral in both phases, and water molecules
provide a hydrogen bonding network that holds the two
structures together (11, 29). Thus, it is not clear why the two
solids have such different affinities for Np.
Similarly to the U(VI) in metaschoepite, Np(V) has also
been shown to adopt a pentagonal bipyramidal geometry in
crystalline solids (13). A comparison of uranyl and neptunyl
bond lengths for axial and equatorial oxygen atoms when
these ions adopt the pentagonal bipyramidal geometry shows
size differences of less than 5%. Average bond lengths for
uranyl pentagonal bipyramids were 1.79(4) and 2.37(9) Å for
axial and equatorial O bond lengths, respectively (1-sigma
error bars are indicated for the last decimal place) (17).
Evaluation of neptunyl pentagonal bipyramids gave an
average of 1.83(2) and 2.46(5) Å for these bond lengths,
respectively (13). On the basis of evaluation of bond lengths
alone, substitution of U(VI) by Np(V) in the structure of
metaschoepite is predicted. Evidence to the contrary may
indicate that lack of a charge-balance mechanism hindered
incorporation of Np(V).
One possible explanation considered for enhanced Np
concentrations in the studtite was a change in the oxidation
state from Np(V) to Np(VI). Although not monitored during
the experiment, it is possible that the Np(V) in solution was
oxidized to Np(VI) by the H2O2 used in the transformation
of metaschoepite to studtite. Because the geometry of the
NpO22+ ion is very similar to that of the UO22+ ion, including
coordination bond lengths (30), it is plausible that Np(VI)
was incorporated into the structure of the precipitate during
the transformation of metaschoepite to studtite.
Initial speculation for the oxidation of Np(V) to Np(VI)
was due to (i) the known oxidizing properties of H2O2 and
(ii) solutions of Np(VI) reportedly having a pale pink color
and halide solids of Np(VI) having been reported to range
from orange to brown (31, 32), possibly resulting in the
observed color differences for the solids we produced.
However, this alone is not conclusive evidence for Np(VI).
A review of the literature concerning Np interaction with
4120 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 11, 2005
FIGURE 3. Dissolved U concentrations from the metaschoepite
dissolution measured over (a) the first 10 days, and (b) the entire
four month study. Grey squares represent results for which no Np
was present in the synthesis; black diamonds represent the
metaschoepite samples synthesized in the presence of Np. Error
bars indicate the range observed for duplicate samples.
H2O2 has not uncovered any evidence supporting its oxidation
to Np(VI). A study by Zielen et al. (33) found that in a
perchloric acid medium containing Np(VI), H2O2 reduced
Np(VI) to Np(V). Another investigation showed reduction of
a fraction of total Np(V) to Np(IV) following reaction with
H2O2 in 2-6 M HNO3 (34). Although two other studies
(35, 36) demonstrate oxidation of Np(III) and Np(IV) by H2O2
to Np(V) in 1 M HClO4, respectively, no evidence for the
existence of Np(VI) was reported. As reduction of Np(V) has
been observed in some systems following reaction with H2O2,
it should be noted that Np(IV) oxides also have a brown
color and cannot be ruled out. Thus, although no studies at
pH similar to that of our work could be found, there is no
basis on which to suggest oxidation to Np(VI) during
formation of studtite, and reasons for higher levels of Np
associated with studtite compared to metaschoepite remain
unclear at this time.
As observed for other hydrated uranyl phases (19, 37), the
studtite sample readily dehydrated. In this case, dehydration
occurred during storage at room temperature. Approximately
a year after its synthesis, analysis of the solid phase by XRD
indicated transformation from studtite (PDF 16-206) to
metastudtite (PDF 35-571) following loss of noncovalently
bound water. Its appearance was unchanged and these
metastudtite solids were subsequently used in the batch
dissolution study, the results of which are described below.
Batch Dissolution Studies. Metaschoepite. The meta-
schoepite solids were contacted with a pH 6, 0.010 M NaNO3
solution for 4 months to measure release of U and Np. The
dissolution of metaschoepite, when introduced to the leach-
ing solution, was rapid enough that the rate of dissolution
was not captured by the sampling intervals used; the U
concentration was at its maximum value by the first
measurement. The maximum quantity of dissolved U
observed differed for the two samples, e.g., metaschoepite
with and without Np present during its formation (Figure 3).
As shown in the SEM images (Figure 2), the metaschoepite
precipitated in the absence of Np was much finer grained
and heterogeneous in morphology. Consequently, one would
expect the finer grained material yield a greater dissolved U
concentration, as observed. This solid may also have
contained more amorphous materials. The U concentration
resulting from dissolution of this solid decreased for 2 days,
and from that point forward, U concentrations were con-
sistent with the metaschoepite precipitated in the presence
of Np. The decrease of U was consistent with reprecipitation
of a more crystalline metaschoepite and/or formation of
another secondary U solid. Unfortunately, due to the small
quantity of solid remaining at the conclusion of the dis-
solution period, no reliable XRD pattern could be obtained.
Control samples of dissolved U and Np were prepared in
the absence of an initial solid to measure loss to the container
walls over the course of the experiment. While the U
concentration decreased linearly, the Np concentration
remained unchanged throughout the experiment (data not
shown). The rate of decrease in U concentration observed
during metaschoepite dissolution was greater than that in
the control experiments, making sorption alone an unlikely
cause of the decrease.
The metaschoepite solid precipitated in the presence of
Np initially had a dissolved U concentration of 3.8 mg/L
which slowly decreased to 2 mg/L during the 4 month study.
No significant Np could be measured in solution by ICP-MS.
At the conclusion of the dissolution study, the small amount
of solid phase that remained was analyzed by XRD. A
diffraction maximum consistent with the basal plane spacing
of metaschoepite was observed (data not shown). Unfor-
tunately, very little sample remained following the dissolution
study, thereby preventing unequivocal identification of the
solid as metaschoepite. Metaschoepite dissolution in NaNO3
investigated by Giammar and Hering (23) showed evidence
of clarkeite (Na[(UO2)O(OH)](H2O)) formation after 484 h. FIGURE 4. Dissolved U and Np concentrations of metastudtite
The identification of clarkeite in that study was made using dissolution study: (a) U concentration during the first 10 days,
a single diffraction maximum at 15° 2θ. We observed no such (b) U concentration during the entire four month study, and (c) Np
diffraction maximum in this region of the diffractogram after concentration during the entire four month study. Grey squares
represent results for which no Np was present in the synthesis;
3122 h, the only time at which the solid phase was analyzed.
black diamonds represent the metastudtite samples synthesized in
Metastudtite. The metastudtite samples prepared with and the presence of Np. Error bars indicate the range observed for
without Np were also subjected to batch dissolution studies duplicate samples.
in pH 6, 0.010 M NaNO3 solutions. The initial rate of
metastudtite dissolution was slower than that observed for concentration with time in our work. It is possible the quantity
metaschoepite. The dissolved U concentration increased for of material used for XRD analysis differed before and after
the first 48 h of the dissolution and appeared to reach a the dissolution; thus, the evidence for improved crystallinity
steady-state concentration near 3 mg/L for the next 10 days is not conclusive.
(Figure 4). The concentration of U in solution then decreased Interestingly, Np was released from the metastudtite solid
linearly during the remaining sampling intervals. This and did not appear to reprecipitate, as observed for U (Figure
decrease could be due to ripening of the studtite, precipitation 4c). Instead, Np was released rapidly for the first 48 h, and
of a secondary U-phase, or sorption to the walls of the its concentration continued to increase slowly over the next
container. The rate of decrease in U concentration was several months. The release of Np was considerably higher
approximately the same as that of control experiments. Thus, than that predicted based on congruent dissolution of the
sorption to the container may account for some of the U solid. At the measured bulk concentration of 6500 ppm
observed decrease in U. The final concentration of U in this Np, and assuming the ideal composition of studtite (63.6 wt
system was approximately 0.5 mg/L (and still decreasing at % U), a mole ratio of 0.01:1 (Np/U) in the solid was calculated.
the end of the study), which is less than the apparent Using a thermodynamic description of a solid solution (39),
equilibrium concentration of metaschoepite at approximately the solubility of a trace component is proportional to its
2.0 mg/L. mole fraction in the solid phase. Thus, a molar solution
The XRD pattern resulting from the material recovered at concentration for Np 2 orders of magnitude less than that
the conclusion of the metastudtite dissolution showed that of U is predicted. However, the observed Np concentration
it was unchanged from the initial solid phase used (Figure was 1 order of magnitude greater than this estimate,
5). Only peaks attributed to the metastudtite diffraction e.g., roughly 1 order of magnitude below that of U. If one
pattern were identified; no peaks attributed to other uranyl neptunyl ion was released into solution for every 100 ions
solids which could form under these solution conditions, of uranyl, an estimated concentration of 0.03 mg/L Np in
such as metaschoepite or clarkeite, were observed. The peaks equilibrium with 3 mg/L U is expected. In our system,
are more intense than those of the initial solid, possibly approximately 0.5 mg/L Np was present with a 3 mg/L U
indicating that the crystallinity improved during aging in concentration.
solution. As observed in another study (38), aged crystalline Although the system is not at equilibrium with respect to
solids often have decreased solubilities over freshly precipi- dissolved Np concentrations after 3000 hours, it is interesting
tated solids, which may explain the observed decrease in U to compare our observed concentrations of dissolved Np to

VOL. 39, NO. 11, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4121

FIGURE 5. XRD patterns of (a) the studtite solid after storage for
1 year in a sealed glass vial, and (b) the final solid from the
metastudtite dissolution study. PDF 35-571 (metastudtite) reference
lines are displayed at the bottom of (a) and (b). Arrows indicate
diffraction maxima attributed to A12O3, added as an internal standard.
No additional crystalline phases are observed in the solid at the
conclusion of the experiment, although the apparent crystallinity
of the solid may have increased.
that expected based on solubility of a discrete Np solid phase.
The solubility controlling phase for Np under the anticipated
conditions of the Yucca Mountain repository is Np2O5‚xH2O
(40); using the Ksp from Efurd et al., the equilibrium Np
concentration under our solution conditions would be
approximately 1 × 10-5 M (2.4 mg/L) Np. However, based
on the amount of solid used in the dissolution study and its
bulk Np concentration, the maximum attainable solution
concentration was approximately 7.3 × 10-6 M (1.7 mg/L)
Np, which still exceeds the level measured in our system by
a factor of 3.
We have also estimated total solution concentrations of
Np based on discrete Np(IV) containing solids, e.g., assuming
that Np(V) was reduced by H2O2. Using the speciation
modeling program Visual Minteq (41), equilibrium concen-
trations of Np(IV) species were determined based on finite
amounts of the solid phases NpO2 and Np(OH)4. The
equilibrium concentrations with dissolved Np(IV) species
for these two solids are ∼1 × 10-20 M and 3 × 10-9 M,
respectively. Because the measured dissolved Np in our
system was approximately 3 orders of magnitude higher than
the larger of these two values, a discrete tetravalent Np solid
seems unlikely.
Metastudtite was the only crystalline solid observed in
the sample following the conclusion of the dissolution
experiment (Figure 5). It is possible that the observed decrease
in the U concentration was due to dissolution and rep-
recipitation of a metastudtite solid with higher apparent
crystallinity than the starting material. In this case, it may
be that Np was excluded from the reprecipitated metastudtite.
The concentration of Np in the final solution during
dissolution (2.1 × 10-6 M) was higher than that measured in
the supernatant at the conclusion of the synthesis of the
4122 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 11, 2005
metastudtite (<1.3 × 10-7 M), indicating a change in the
Np-limiting solid. If the Np in the studtite was hexavalent,
it may have been reduced to Np(V) during dissolution (when
the H2O2 concentration was far lower than that during the
formation of the phase), making it incompatible in the studtite
structure during the reprecipitation phase.
The balanced reaction for the dissolution of pure meta-
studtite is (12)
[(UO2)O2(H2O)2] + 2H+ T UO22+ + H2O2 + 2H2O (1)
and the solubility product expression can be written
Ksp(metastudtite) ) {UO22+}{H2O2}/{H+}2 )
1.34 × 10-3 (2)
Although our system is not at equilibrium, it is interesting
to compare our observed concentrations of dissolved U to
this calculated amount. Assuming congruent dissolution of
uranyl and peroxide, at pH 6 the equilibrium activity of UO22+
is calculated to be 3.7 × 10-8 M (8.8 µg/L). Total U
concentrations measured in our system ranged between
1 and 3 mg/L (Figure 4). At pH 6 and ionic strength
∼0.01 M, only 2-4% of U should be in the form UO22+, which
corresponds to (1.9-2.8) × 10-7 M (46-68 µg/L) UO22+(aq).
This exceeds the calculated value by a factor of 5-7.5. Possible
explanations for the high solubility of our studtite could
include: (1) the system has not reached equilibrium, (2) the
presence of an amorphous U phase in the initial solid, and/
or (3) low apparent crystallinity which resulted in a high
surface area-to-volume ratio of the solid.
The equation for solid solution formation of hexavalent
Np in metastudtite may be written
[(UO2)O2(H2O)2] + NpO22+ T
[(NpO2)O2(H2O)2] + UO22+ (3)
(Np(VI) is used for convenience, but a similar equation could
be written for other oxidation states.) This leads to an
equilibrium constant expression which can be rearranged to
correspond to a distribution constant for Np between the
solid and liquid phases of a solid solution:
{(NpO2)O2(H2O)2} {UO22+}
K) )
{(UO2)O2(H2O)2} {NpO22+}
{NpO22+}
{(NpO2)O2(H2O)2}
{(UO2)O2(H2O)2} {UO22+}solid
≈ ) D (4)
{NpO22+} {NpO22+}
{UO22+} {UO22+}liquid
where {} represents the activity of the solid or dissolved
species, respectively. Ideally, solid solutions should have
D . 1, representing an enrichment of the minor element
into the solid phase compared to the liquid phase. This
corresponds to reduced solubility of trace elements when
they are minor constituents in a solid solution. If the ratio
of activities of Np to U in the solid phase is approximated
as the ratio of their mole fractions, and considering the bulk
Np concentration in the solid to represent all incorporated
Np, D in our case is calculated as ∼0.02. This suggests the
opposite situation exists: enrichment in the solution phase
compared to the solid phase, which would not be ideal for
the anticipated behavior of Np in a geological repository.
In summary, metaschoepite and studtite synthesized in
the presence of Np retain the structural characteristics of
these phases without Np (by XRD), although the surface
morphology may be affected. Our study indicates studtite
has a higher affinity for Np than does metaschoepite.
However, during the dissolution of metastudtite, release of
Np into solution was nearly a factor of 20 higher than that
expected if congruent dissolution of a true solid solution is
assumed. A possible explanation is that a significant fraction
of the Np was initially surface sorbed, and thus release into
solution occurred at a higher rate than for U, which required
matrix dissolution of the uranyl solid. We also cannot discount
amorphous phases, which may have been present in the
solid and contained a significant quantity of the total Np.
Another important reason to consider uranyl peroxides
in assessing the performance of geological repositories is the
lower dissolved U concentration during dissolution compared
to that of metaschoepite. Our dissolution study suggests
metastudtite is a stable secondary phase, even in a solution
depleted in H2O2. Following >4 months in a NaNO3 solution,
no additional secondary phase formation was detected by
XRD. No evidence for a uranyl oxide hydrate or Na-uranyl
oxide hydrate was found, possibly indicating that once they
are formed, uranyl peroxides may persist even without
replenished H2O2 in situations of limited transport of
dissolved species away from the reacting surface. This finding
is consistent with observations of studtite and metastudtite
in nature, sometimes in large quantities, even though the
levels of peroxide generated by radiolysis are not likely to be
significant (12, 26). Also, it appears likely that the Np released
during dissolution of the solid was excluded from re-
precipitation with the solid phase. If this is due to a change
in oxidation state in our system, it may not be a concern in
a repository environment with continuously generated
peroxide.
This work suggests that in some cases the solubility of Np
is not decreased by its association with a uranyl solid. While
retention by uranyl solids is cited as a mechanism for reducing
the mobility of radionuclides from a repository, this may not
be the case if they are partitioned into amorphous phases
or weakly sorbed to uranyl surfaces. Further study of these
solids is required to assess the mechanism of Np-association
with the metastudtite, as well as to determine its oxidation
state.
Acknowledgments
We thank Charles Knaack of the Geoanalytical Laboratory at
WSU for assistance with the ICP-MS measurements. Primary
funding for this work was provided by the U.S. Department
of Energy’s (DOE) Office of Science Basic Energy Sciences
program under contract DE-FG02-01ER15138. M.D. gratefully
acknowledges support from the NSF Integrative Graduate
Education and Research Training (IGERT) program in the
Center for Multiphase Environmental Research at Wash-
ington State University under grant DGE-9972817 and from
the Pacific Northwest National Laboratory Yucca Mountain
Project supported by DOE, Office of Civilian Radioactive
Waste Management.
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