Chapter 7

Uraniuin Sorption onto

Natural Sands as a Function
of Sediment Characteristics
and Solution pH

Jeffrey J. Rosentreter/ H. Swantje Quarder/ Robert W. Smith,^

and Travis McLing^
^Idaho State University, Department of Chemistry, Pocatello, Idaho; ^Idaho National
Engineering Laboratory, Idaho Falls, Idaho

This chapter describes ongoing research to characterize the relation-

ships between physical and chemical properties of selected sediments
and their sorptive properties, permeability, and porosity. Specifically
described are determinations of partition coefficients (K^ values) as a
function of p H for uranyl sorption on 25 sediment samples collected
from a sand borrow pit. In our evaluation of this data, several physi-
cal and chemical characteristics of the sediments were identified as
having both significant and insignificant influences on the sediment's
uranium sorptive capabilities. Significant correlations between surface
area and surface area surrogates were identified. Conversely, mineral-
ogy and grain size had essentially no influence on the sorptive capa-
bilities of these sediments. In our evaluation of the K^ data, we were
able to identify and justify a linear relationship between the log Reval-
ues and equilibrium solution p H values. These applied equally well to
all the sediments in our sample set. It eventually allowed for the de-
velopment of two simple predictive equations that, based on either
surface area or extractable metal concentrations, provided an effective
indirect means of evaluating a sediment's sorptive behavior with re-
spect to uranium.
Adsorption of Metals by Geomedia
Copyright © 1998 by Academic Press. All rights of reproduction in any form reserved. 181
182 Rosentreter et ah

I. INTRODUCTION
Mixtures of contaminants including radionuclides, toxic metals, organic sol-
vents, and complexants have been released to the subsurface, leading to potential
or actual contamination of groundwater resources. The risk to human health and
the environment arising from contaminant transport in the groundwater must be
clarified in order to develop cost-effective and technically defensible remediation
strategies for groundwater and vadose zones and to determine sites for new waste
storage and disposal facilities. Mechanistic knowledge of the interactions between
aqueous adsorbing contaminants and multiple mineral surfaces (e.g., sorption) in
heterogeneous media and knowledge of how rapidly water flows (residence time)
through the porous media are key to understanding the fate and transport of con-
taminants in the unsaturated and saturated subsurface. The relationships between
the flow domain and sorptive intensity of multiple mineral surfaces determine the
velocity at which contaminants migrate. Although the role of physical medium het-
erogeneity on transport has received significant attention, similar investigation of
chemical (reactive) medium heterogeneity, and the correlation of physical and
chemical heterogeneity, is yet to be fully explored.
This chapter describes ongoing research to characterize the relationships be-
tween physical and chemical properties of selected sediments and their sorptive
properties, permeability, and porosity. Specifically described are determinations of
partition coefficients (K^ values) as a function of pH for uranyl (U^^) sorption on
25 sediment samples collected from a sand borrow pit located on the southern tip
of the Delmarva Peninsula in Virginia, near the village of Oyster. One criterion for
the selection of the field site was that the reactivity of the sediment would be con-
trolled by variability in the abundance of hydrous oxide coatings on the sediments.
The borrow pit consists of weakly consolidated cross-bedded sand with secondary
hydrous metal oxides associated with primary depositional features and is strati-
graphically located in the lower portion of the Butlers Bluff Member of the Pleis-
tocene age Nassawadox Formation. The Butlers Bluff Member averages about 18
m in thickness and consists of clean, cross-bedded, fine to coarse sand and gravel
and is thought to have formed either as a barrier-spit or a shoal complex adjacent
to the mouth of ancestral Chesapeake Bay (Mixon, 1985). The sediment samples
were collected to span the range of variability in detrital mineralogy, amounts of
secondary hydrous ion oxides (geochemistry), and grain size (surface area).

11. EXPERIMENTAL
A. PROCEDURES FOR BATCH EXPERIMENTS

Well-established batch reaction techniques were implemented to determine so-

lution concentrations before and after equilibration with the sediments and solid
Uranium Sorption onto Sands 183

loading concentrations. Four experimental sets were completed with initial pH

values of 3, 4, 5, and 6. All experimental sets included operational blanks, re-
agent blanks, and replicate samples.

1. Solution Preparation
All solutions were prepared using American Chemical Society (ACS) certified
reagent grade chemicals. Deionized water with a resistance of 16 Mfl or higher
was used as the diluent. The adjustment of pH was accomplished using trace met-
als grade nitric acid and reagent grade sodium hydroxide. Uranium concentrations
were adjusted through the addition of an ACS certified uranium standard. The re-
action solution was 0.01 mol*L~^ calcium perchlorate containing 250 |jLg-L~^ of
uranium. The initial pH of the reaction solution was adjusted with additions of con-
centrated nitric acid and sodium hydroxide as needed. The pH adjustments pro-
vided solutions with a pH of ±0.04 pH units, which were stable within that range
for a minimum of 48 hr. Operational blanks consisted of aliquots of the reaction
solution that were not reacted with the geologic materials.

2. Reaction Procedure
The sorption studies were carried out using batch reaction techniques in 50-ml
polyethylene centrifuge tubes. The geologic samples were subsplit to 4.0 ± 0.5 g
using a riffle splitter to avoid bias. Sorption studies were carried out using 24.0 ml
of reaction solution.
Mixing was achieved by rotating the sealed centrifuge tubes on a vertical rota-
tor. No attempt was made to exclude or control CO^ in the experiments. The sam-
ples were gently agitated at four rotations per minute for 72 hr while maintained
at 25°C. The liquid phase was separated from the solid phase at the end of the equi-
libration period by centrifugation for 10 min at 3000 rpm in head with a center axis
to mid tube radius of 10 cm. Final pH was measured and the samples were then
preserved by the addition of trace metals grade nitric acid to a pH of less than 2.0.
Experimental precision in each set was determined by analysis of duplicate
samples for each sediment equilibrated with reaction solution. Two types of blanks
were also analyzed. The first, an operational blank, consisted of the reaction solu-
tion without sediment to account for sorption on and desorption from the contain-
er walls. The second, a reagent blank, consisted of deionized water samples used
in the preparation of the reaction solutions.

3. Analytical Methods
Reaction solutions, duplicates, and blanks were analyzed for pH and uranium
content just prior to and following the equilibration period. Uranium determina-
tions were accomplished using kinetic phosphorimetry. AChemcheck Instruments
184 Rosentreter et ah

KPA-11 Phosphorescence Analyzer provided rehable uranium detection in the

sub-part-per-bilHon concentration range. An instrument detection Hmit of 0.05
|xg-L~^ was typical in our study (with the time gate set at 240 |jLsec). The overall
percent relative standard deviation (%RSD) for analytical replicates measured
throughout the experiments ranged from 0.3 to 7.0%. Measurements of pH were
performed on a Model 25 Fisher Scientific pH/Ion-meter. Using a five-point cali-
bration curve, various pH standard solutions provided measured pH values with
%RSD values of below 0.1%.

B. GEOLOGIC MATERIALS

Characterization of the sediments included determination of bulk mineralogy,

surface area, and extractable Fe"^ and Al concentrations. Bulk mineralogy was de-
termined by petrographic examination of acid washed and stained grain mounts.
Surface area was determined by BET analysis using a Micromeritics Gemini 2360
Multipoint Rapid Surface Area Analyzer. Reducible Fe was determined using a bi-
carbonate buffered dithionite-citrate extraction (Mehra and Jackson, 1960). Read-
ily extractable Al was determined using an oxalate extraction (McKeague and Day,
1966). The mineralogical, physical, and chemical characteristics of the sediment
samples are listed in Table I.

III. RESULTS AND DISCUSSION

A. DETERMINATION OF K^ VALUES A N D THE EFFECT OF pH

Values of K^ were calculated from the measured loss of uranium from solution
using
Kd = (Ci-c,)•V•(c,•W)-^ [1]
where c. and c^ are the initial and final aqueous concentrations of uranium, re-
spectively, V is the volume of the aqueous phase (24 ml), and W is the mass of the
solid (~4 g). Because K^ values calculated using Eq. [1] depend only on mea-
surements of aqueous concentrations, the values are particularly sensitive to sys-
tematic errors due to uranium losses by mechanisms other than sorption onto the
sediments (e.g., sorption onto the reaction vessel). Possible systematic errors were
minimized by the use of several reaction blanks with each experimental set. As
used in this paper, K^ is a measure of partitioning of a solute between an aqueous
and a solid phase; it does not imply hnear reversible adsorption.
The effects of pH on the K^ values are shown in Figure 1. As may be seen in
this figure, adsorption increases with increasing pH, consistent with behavior of
 d d d d c 5 d c 5 d o o d d d o d o d d o o o d o d d
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185
186 Rosentreter et ah

Sample Number
3.0 1 1 — ^ — ^ — , — , — 1 — , — j
D one ^ fourteen

2.5 - O two X fifteen

A four < sixteen

W 2.0 O three B seventeen

m five • eighteen
i 1.5 L *
r ^ • six + nineteen

\i
• ® seven * twenty
o> 1.0
o V eiglit B twenty^one
r "'"^ J Q « twenty-two
0.5
1 • J nine

^ ten H twenty-three
r °
1 1 1— 1 • 1 1 ^ eleven • twenty-four
0.0
4.0 5.0 6.0 7.0 8.0 > twelve • twenty-five
D thirteer
pH
Figure 1 Measured K^ versus equilibrium pH for each of the sediment samples as recorded from the
four experimental sets.

uranium in the pH range considered. This behavior is quaUtatively the same as that
observed by Hsi and Langmuir (1985) for uranyl adsorption onto ferric oxides, by
Lieser and Thybuech (1988) for uranyl adsorption onto titanium oxide, and by
Lieser et al (1992) for uranyl adsorption onto hydrous siHca. At higher pH values
(i.e., 7), the formation of U^^ carbonate species results in decreasing adsorption.
Because one of the goals of this study is to elucidate the role of mineralogical char-
acteristics of the sediments in controlling K^, it is desirable to have K^ values for
each sediment at a common pH. This was accomplished using least-squared lin-
ear regression techniques. Initially, a regression of pH and log K^ values for each
sample (i.e., four points) was conducted. The results of these analyses were that
the slopes (i.e., d log K^-d pH~^) for all samples were similar. As a result, a re-
gression analysis was done simultaneously on all 100 points constrained so that
the slope for all samples was the same. The resulting equation is
log K^. = b. + 0.47(0.02)-pH, [2]

where b. is the intercept for the ith sample. The value in parentheses reflects the
standard error associated with the fit coefficient. The similar pH dependency of log
K^ for all samples is consistent with behavior that has been observed for uranyl
adsorption on synthetic oxides (cf. Lieser et al, 1992) and suggests that the shape
of the pH versus log K^ curve is dominated by aqueous speciation and that the
stoichiometry of the sorption reaction is independent of the solid.
Uranium Sorption onto Sands 187

B. MiNERALOGICAL CHARACTERISTICS AFFECTING

SoRPTivE P R O P E R T I E S

A goal of this study was to define the key characterization measurements re-
quired to describe natural variation of the sorptive properties of sediments. The
sediment characteristics considered included bulk mineralogy, extractable Fe°^
extractable Al, and BET surface area. Additional characterization to describe the
relationship between physical and hydrological properties (i.e., permeabiUty,
porosity, and grain size) was also collected and is the subject of a future commu-
nication. Smith et al (1996) provide a discussion of the theoretical basis of corre-
lated physical and geochemical heterogeneities.
Values of K^ for each of the 25 samples at a pH of 5 were estimated by
log K^,i,5 = log K^,i,pH - 0.47(0.02)-[pH. - 5]. [3]
The average and standard deviation for each of the samples are reported in Table
I. The K^ values reported in Table I were used to evaluate the relationships be-
tween sorption and the mineralogical characteristics of the sediments.
No correlation was observed between K^ values and the bulk mineralogy of the
sediments. This observation is not surprising given that a criterion for field site se-
lection was that the reactivity be controlled by variability in the abundance of hy-
drous oxide coatings. A series of single-variable regression analyses were con-
ducted using surface area and extractable Fe^^^ plus Al as independent variables.
The results of these analysis are presented in Figures 2 and 3. Because surface area

*f-U « 1 " 1 I 1 . 1 .

b
CM' D
^ 3.0 D J
(0
0) D J
V.
< «^
2.0 " nqb "1

(D
O
CO
3 ^ ^
§
</) 1.0
1- r
©n H

ui TP-H
tn Q • • . J I i 1 . 1

0 20 40 60 80 100
Fe [|ULmolg 1
Figure 2 Measured surface area versus extractable Fe™ for the 25 sediment samples.
188 Rosentreter et at.

4.0 —'—1—'—1 '1 — 1 1- 1 '

CM'
E 3.0 Y °D J
(0 n j
< 2.0 h ^
0) \ ^ D
o

r niP
LU
CD
h^o° -
0.0 1 . 0 . . i I L. 1

0 20 40 60 80 100
E [|Limolgi]
Figure 3 Measured surface area versus extractable Fe"^ plus A1(E) for the 25 sediment samples.

and extractable metals were highly correlated (Fig. 3), regression analyses that in-
cluded both surface area and the abundance of hydrous metal oxides were not in-
cluded. Regression that included Al or Fe, or both Fe and Al as independent vari-
ables, resulted in poorer fits than those shown in Figures 2 and 3. In addition, an
analysis that included surface area and the ratio of extractable Fe"^ to Al was test-
ed. The resulting coefficient for the ratio was not statistically different from 0, in-
dicating that for the range of Fe-to-Al ratios observed for Oyster sediments, the K^
is insensitive to compositional variations in hydrous oxide coatings (i.e., the K^
for extractable Fe"^ oxides is not significantly different than the K^ for extractable
Al oxides). In order to interpret the results of these regression analyses, a simpli-
fied model of sorption at constant pH is considered.
General reactions for the sorption of uranyl ion onto sediments with variable
amounts of mineralogically similar hydrous oxide coatings can be written as
UO|+ + nSOH <^ (S0)^-U0^2-n) + J^H+ [4]
Q4 = [(SO)„-UOf-">]-[H+]"-{[UO|^]-[SOH]}-^ [4a]
SOH <=> S O - + H+ [5]
Q5 = [SO-]-[H+]-[SOH]-i [5a]
SOH + H+ « SOH+ [6]
+n-i
Q6 = [SOH+]-{[SOH]-[H+]} [6a]
Uranium Sorption onto Sands 189

S^ = [SOH] 4- [SO-] + [SOH+] + n-[(SO)^-UOf-'^>] [7]

S^ = r-S^-W, [7a]
where [SOH], [SOH^], and [SO"] are the molar concentrations of the neutral, pro-
tonated, and deprotonated surface sites, respectively; [(SO)^-UO^^-"^] is the mo-
lar concentration of adsorbed uranium; Q4, Q5, and Q6 are conditional equilibri-
um quotients (e.g., dependent on experimental conditions) for the respective
reactions; S^ is the total molar concentration of reactive sites; F is the site densi-
ty (mol-m"^); S^ is the surface area of the sorptive phase (m^-g"^); and W is the
mass of the sorptive phase per liter of aqueous phase (g-L~^). The [UO|^] term
is related to the total aqueous uranium concentration, U^, by
[U0|+] = U,-U^, [8]
where U^ is the fraction of uranium that occurs as UO|"^ and accounts for aqueous
speciation. At constant pH and low surface coverage of UOl"^ (i.e., [SOH]-{1 +
Q5-[H+]-i + Q6-[H+]-i} » n-[(SO)^-UOf-">],Eq. [8] can be rearranged as
Q4T-S^-U,-{U3-[H+]-}-i = Cg-Uf 1 = K^-10-3 [9]
U3 = 1 + Q5-[H+]-i + Q6-[H+] [10]
1000-Q4-r-S^-Uf-{U3-[H+]-}-i = K^^-S^ = K^ [11]
logK^ = logK^^ + logS^, [12]
where U^ accounts for the surface speciation, K^ ^ is a surface-area-based distri-
bution coefficient, and Cg is the concentration of uranium on the solid. Inspection
of Eq. [11] indicates that K^ is a complex function of pH and is dependent on aque-
ous speciation (U^), the surface speciation (U^), and the stoichiometry of the ad-
sorption reaction. In addition to that, for mineralogically similar sediments, a plot
of log K^ versus log S^ (or any surrogate of S^ such as the amount of readily ex-
tractable surface coating metals) will have a slope of 1. The unit slope (calculated
for regressions using the total of extractable Fe^^^ plus Al) is the result of the pro-
portionality between surface area and the abundance of the hydrous metal oxide
coatings (Fig. 3). The dependence of K^ on surface area shown in Eq. [12], and Fig-
ure 4 highlights the importance of characterizing the spatial variability of surface
area, even at sites that appear mineralogically homogeneous, and indicates that sur-
face area may be a useful surrogate for the K^. Spatial variability of surface area is
significant for describing correlations between reactive properties such as K^ and
hydrologic properties such as porosity and permeability (Smith et al, 1996).
A simple predictive equation describing K^ for the sediments from the Oyster
site derived by linear regression of all K^ measurements is given by
log K^ = -0.8(0.1) + 0.46(0.02)-pH + log S^, r = 0.938 [13]
log K, = -2.5(0.2) + 0.47(0.02)-pH + log E, r = 0.920 [14]
190 Rosentreter et al.

2.5

,_, 2.0
O) •

ri
E
•o 1.5 -
^ .
O)
o 1.0 hi

1.0

log S A [m2/g]
Figure 4 Measured K^ versus surface area with errors from pH adjustment to pH 5. log K^ -
1.0(0.1)log S^ + 1.49(0.03), r = 0.878 (values in parentheses are the standard errors of the fit coeffi-
cients).

3.0 r 1 1 1 1 1 ' ' ^

pj-j rjB, ]

0)
a 2.0 h
(0
E
w • l ^ P^a
1.0 h
G)
O
j

0.0 £—i 1 1 1 1 . ... . . . 1 . . . .

0.0 1.0 2.0 3.0

log Kd [observed]
Figure 5 Multivariate predictive equation using pH and surface area, log K^ = 1.0(0.1)log S^ 4-
0.46(0.02)pH - 0.8(0.1), r = 0.941 (values in parentheses are the standard errors of the fit coefficients).
Uranium Sorption onto Sands 191

3.0 I . • •

0)
2.0 h
E
(0

.2L

o
0.0

log K^ [observed]
Figure 6 Multivariate predictive equation using pH and the surface area surrogate of extractable Fe
plus Al. log K^ = l.l(0.1)log E + 0.47(0.02)pH - 2.5(0.2), r = 0.938 (values in parentheses are the
standard errors of the fit coefficients).

where E is the sum of the extractable Fe plus Al. A comparison between values
predicted using Eqs. [13] and [14] and those measured is given in Figures 5 and 6.

IV. CONCLUSIONS
In this work, 100 partition coefficients were obtained based on 25 different sed-
iment samples. These K^ values were obtained using four different initial reaction
solution pH values. In our evaluation of this data, several physical and chemical
characteristics of the sediments were identified as having both significant and in-
significant influences on the sediment's uranium sorptive capabilities. Significant
correlations between surface area and surface area surrogates (namely, extractable
Fe"^ and Al for these sediments) were identified. Conversely, mineralogy, which
varied over only a somewhat limited range in the samples, and grain size, which
varied significantly, had essentially no influence on the sorptive capabihties of
these sediments. In our evaluation of the K^ data, we were able to identify and jus-
tify a linear relationship between the log K^ values and equilibrium solution pH
values. These appHed equally well to all the sediments in our sample set. This re-
lationship allowed for the further evaluation of the data set as a whole. It eventu-
ally allowed for the development of two simple predictive equations that, based
192 Rosentreter et ah

on either surface area or extractable metal concentrations, provided an effective

indirect means of evaluating a sediment's sorptive behavior with respect to urani-
um. The use of such indirect indicators, which are based on rapid and reproducible
laboratory procedures, may prove more useful for determining sorptive character-
istics of large sample sets than traditional laboratory batch processes.

REFERENCES
Hsi, C-K., and Langmuir, D. 1985. Adsorption of Uranyl onto Ferric Oxyhydroxides: Application of
the Surface Complexation Site-Binding Model. Geochim. Cosmochim. Acta 49:1931-1941.
Lieser, K. H., Quandt-Klenk, S., and Thybuech, B. 1992. Sorption of Uranyl Ions on Hydrous Silicon
Dioxide. Radiochim. Acta 57:45-50.
Lieser, K. H., and Thybuech, B. 1988. Sorption of Uranyl Ions on Hydrous Titanium Dioxide. Z. Anal.
Chem. 332:351.
McKeague, J. A., and Day, J. H. 1966. Dithionite- and Oxalate-Extractable Fe and Al as Aids in Dif-
ferentiating Various Classes of Soils. Can. J. Soil Sci. 46:13-22.
Mehra, P., and Jackson, M. L. 1960. Iron Oxide Removal from Soils and Clays by Dithionite-Citrate
System Buffer. Clays Clay Miner. 7:317-327.
Mixon, R. B. 1985. Stratigraphic and Geographic Framework of Uppermost Cenozoic Deposits in the
Southern Delmarva Peninsula, Virginia and Maryland. Prof. Paper 1067-J. U.S. Geological Sur-
vey, Reston, VI.
Smith, R. W., Schafer, A. L., and Tompson, A. F. B. 1996. Theoretical Relationships between Reactiv-
ity and Permeability for Monomineralic Porous Media. Mater. Res. Soc. Symp. Proc. 412:693-700.