u(vi) interactions with carbonates: spectroscopic studies richard j. reeder department of...
TRANSCRIPT
U(VI) interactions with carbonates:Spectroscopic studies
Richard J. Reeder
Department of Geosciences andCenter for Environmental Molecular ScienceState University of New York at Stony Brook
Collaborators: E. Elzinga, D. Tait, D. Morris
Support from NSF, DOE, Actinide Facility at ANL
Dissolved carbonate in environmental solutions
Derived from: Atmospheric CO2
RespirationWeathering of carbonate minerals
pH
3 4 5 6 7 8 9 10 11 12
% s
pec
ies
0
2e-5
4e-5
6e-5
8e-5
1e-4
H2CO3 HCO3-
CO32-
Why is this important? U(VI) has strong affinity for CO32-
Carbonate speciation is pH dependent
UO22+ aqueous speciation in carbonate solutions
Utot = 1 M, PCO2 = 10-3.5 bar, 25 oC
From Waite et al. (1994)
U(VI) adsorption on ferrihydrite
Influence of dissolved carbonate on U(VI) sorption: ferrihydrite
pH < 5 UO22+ dominant
pH 5-8 Hydroxyl species
pH >8 Carbonate species
Adsorption edges at:
low pH (4-5) high pH (8-9)
Uranyl carbonate complexeshave low sorption affinity
How does U(VI) interact with calcium carbonate?
• Potential binding sites at surface CO3 groups
• Calcium carbonate is moderately soluble (Ca2+, CO32-)
• Dissolved CO32- stabilizes aqueous uranyl complexes
Aragonite (Pmcn)Calcite (R3c)
Calcium carbonate-saturated solutions
Total dissolved carbonate (and Ca) depend on pH and PCO2
U(VI) aqueous speciation in calcium carbonate systems
Formation of Ca2UO2(CO3)3(aq) species favored in calcite-
equilibrated solutions (Bernhard et al., 1996, 2001)
15 M total U(VI) in calcite suspension
pH
5 6 7 8 9 10
U(V
I) s
pec
ies
(m)
0.0
2.0e-6
4.0e-6
6.0e-6
8.0e-6
1.0e-5
1.2e-5
1.4e-5
1.6e-5
Ca2UO2(CO3)3 UO2(CO3)3-4 UO2(CO3)2-2 UO2CO3 (UO2)2CO3(OH)3- UO2OH+ UO2(OH)2 UO2+2
U(VI) in Calcium Carbonate Phases
• Up to 1 wt.% U(VI) in calcite formed in leach tests of Portland cement-type grout (Fuhrmann et al., 2005)
• U(VI) in calcite formed in Hanford subsurface associated with releases of uranium waste (Wang et al., 2005)
• Synthetic U(VI) co-precipitation samples contain up to 1 wt.% U (Reeder et al., 2000)
• Natural CaCO3 minerals contain up to 300 ppm U (IV, VI)
Importance of Uranium Uptake by Carbonates
• Geochemical tracers (petrogenesis, diagenesis)
• Proxy for paleo-climate, paleo-ocean chemistry
• Role in geochemical cycles
• Potential for sequestration
Calcite is a highly effective sorbent for many metals.
Adsorption Co-precipitationSurface
precipitation
Mechanisms of Metal Uptake at the Mineral-Water Interface
Experiment: Characterize U(VI) sorbed at calcite surface in situ using EXAFS and luminescence spectroscopies
-3
-2.5
-2
-1.5
-1
-0.5
-5.5 -4.5 -3.5 -2.5
log (solution [U] in M)
log
(s
orb
ed
U i
n m
ole
/kg
)
Experimental conditions for sorption experiment
• Calcite: surface area ~10 m2/g (~2 m size)
• Calcite suspension pre-equilibration:
log P(CO2) = -3.5, 20–22 ºC, 4 weekspH 7.4–8.3, I = 0.0015–0.0025 m
• Total U(VI): 5 M–5 mM (added w/ and w/o CO3)
• Sorption equilibration – 24, 48, 72 h
• Wet pastes extracted for EXAFS, luminescence
U(VI) Sorption Isotherm on Calcite
pH 8.3
Ca surface sites
Total U(VI) (M)
0 1000 2000 3000
Sat
ura
tio
n in
dex
-3
-2
-1
0
1
2 Schoepite
-UO2(OH)2
Rutherfordine
Supersat.
Undersat.
w/o CO3
w/ CO3Calcite saturation maintained
Initial calcite saturation
U(VI) Solubility Limits near Calcite Saturation (pH 8.3)
(UO2CO3)
U L3-edge
R + (Å)
0 1 2 3 4 5 6 7 8
Fo
uri
er t
ran
sfo
rm m
agn
itu
de
0.0
0.1
0.2
0.3
U(VI):calcite
5 mM U(VI)
150 M U(VI)
15 M U(VI)
UO2(CO3)3 (aq)
Selected EXAFS Results for U(VI) Sorption on Calcite (pH 8.3)
Two types of EXAFS spectra (as seen in FT magnitude):
• Total U(VI) 500 M – single but broad equatorial peak• Total U(VI) 500 M – split equatorial peaks
4-
620600580560540520500480460
Emission Wavelength (nm)
No
rma
lize
d In
ten
sit
y 482
491
502510
523
532
547
100 M
20 M
10 M
5 M
Exc. 420 nm
100
50
0
Inte
nsit
y (
cp
s)
2.52.01.51.00.5
Time (msec)
10 M U(VI)Blue: single exp. = 150 ± 20 sBlack: double exp. 1 = 580 ± 240 s 2 = 125 ± 30 s
Time-resolved luminescence spectroscopy:
• Single uranyl species at lowest U concentration
• Additional species appears at higher U concentrations
Decay kinetics:
• Best fit with two exponentials
620600580560540520500480460
No
rmal
ized
Inte
nsi
ty
Emission Wavelength (nm)
10 M Sample; LN2 TempExc. 420 nm
delayed gate(0.700 --> 1.500 msec)
short gate(0.050 --> 0.100 msec)
482
503
524
546
533
511491
Resolution of component spectra using short and delayed “gates”
Distinct spectra indicate at least two uranyl species present
650600550500450
No
rma
lize
d I
nte
ns
ity
Emission Wavelength (nm)
484
502
523
548
482
502
523
547
484504
526
548
LN2 Temperatureexcite 420 nm
100 M sorbed sampledelayed gate
5 M sorbed samplefull gate
Uranyl in aragonite(triscarbonate monomer)full gate
• This species resembles aqueous UO2(CO3)34-
• Possibly sorbed Ca2UO2(CO3)3
Identification of “delayed gate” spectrum
650600550500450
492
512
533
493
513
534
Emission Wavelength (nm)
Inte
ns
ity
LN2 Temperature
100 M sorbed (short-gate)
U(VI) calcite (single xl)
Identification of “short-gate” spectrum
• Short-gate species resembles the UO2-doped calcite
• U(VI) possibly coprecipitated during sorption
What about U(VI) in Natural Calcium Carbonate Samples?
3 cm
Calcite speleothem, N. Italy (300 ppm U)
XRD, FTIR – only calcite in yellow band
20000
10000
0
Inte
nsi
ty (
cps)
600550500450
Wavelength (nm)
Spotl Calcite Long delay Short delay/short gate Full Gate
Time-resolved luminescence
• Double exponential decay kinetics two uranyl species
• Long gate – aragonite-like species
• Short gate – calcite-like species
What can we conclude ?
• At U(VI) < 10 M, uranyl carbonate complex adsorbs on calcite surface
• At U(VI) = 10–500 M, multiple sorbed uranyl species exist at calcite surface:
• One sorbed species is uranyl triscarbonate-like• Other may be a coprecipitate
• At U(VI) > 500 M, a surface precipitate forms
• Presence of multiple species may result in U(VI) retention with multi-phase behavior/kinetics
• Differences in experimental conditions for co-precipitation result in different local coordination of uranyl species.
• The use of complementary techniques (EXAFS and time-resolved luminescence) may provide better chance for characterizing complex environmental systems
Emission wavelength (nm)
450 500 550 600 650No
rma
lize
d l
um
ine
sc
en
ce
in
ten
sit
y
0
1Polycrystalline calcite
Aragonite
• Different uranyl species in polycrystalline calcite and aragonite
• Both exhibit single exponential decay kinetics
• Single uranyl species in each
Exc. 420 nmLN2
Time-resolved Luminescence Spectroscopy of CaCO3 Phases