PNNL-19681

Prepared for the U.S. Department of Energy

under Contract DE-AC05-76RL01830

Tc-99 Ion Exchange Resin Testing

MM Valenta
KE Parker
EM Pierce

August 2010
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i
 PNNL-19681

Tc-99 Ion Exchange Resin Testing

MM Valenta
KE Parker
EM Pierce

August 2010

Prepared for
the U.S. Department of Energy
under Contract DE-AC05-76RL01830

Pacific Northwest National Laboratory

Richland, Washington 99352

i
 Executive Summary

The Hanford Site is a Federal facility in southeastern Washington State that manufactured nuclear
materials for national defense between 1943 and 1988. In 1989, certain areas of the Hanford Site,
including the 200-ZP-1 operable unit, were placed on the National Priorities List pursuant to the
Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA).

Among the contaminants of concern in groundwater beneath 200-ZP-1 was technetium-99 (99Tc), a
radioisotope with a half-life of 210,000 years. Between April 26, 2007, and December 20, 2007, an ion
exchange pilot-scale treatability test was performed to evaluate 99Tc removal in a pump-and-treat system
that would be installed as part of site cleanup. CH2M Hill Central Plateau Remediation Company
(CHPRC) is responsible for the design and construction of the pump-and-treat system that will be
installed at the Hanford site to support treatment of groundwater beneath 200-ZP-1. To support the large-
scale design of the system, two pilot-scale ion exchange columns were tested previously on groundwater
collected from two different wells, one column per well. The column used to treat water from well 299-
W15-765 contained the highest 99Tc concentration as well as a nitrate concentration very similar to that
expected in the influent of a full-scale treatment facility. The resin used to treat the groundwater in the
pilot-scale test was Purolite A530E anion-exchange resin—known for its relatively high anion selectivity.
Purolite A530E is a monofunctional anion-exchange resin with triethylammonium exchange sites and the
polystyrene backbone cross-linked with divinyl-benzene. This resin was chosen because there is a
chemical bias toward exchanging TcO4- preferentially over the other anions in an aqueous solution.

Pacific Northwest National Laboratory was contracted by CHPRC to evaluate the release of 99Tc from
spent resin used to treat water from well 299-W15-765 and stored for several years. The key questions to
be answered are as follows:
1) Does 99Tc readily release from the spent ion exchange resin after being in storage for several years?
2) If hot water stripping is used to remove the co-contaminant carbon tetrachloride, will 99Tc that has
been sequestered by the resin be released?
3) Can spent resin be encapsulated into a cementitious waste form? If so, how much 99Tc would be
released from the weathering of the monolith waste form?

The results from the long-term stability leach test results confirm that the resin is not releasing a
significant amount of the sequestered 99Tc, which is evident by the less than 0.02% of the total 99Tc
loaded being identified in the solution. Furthermore, it is possible that the measured 99Tc concentration is
the result of 99Tc contained in the pore spaces of the resin. In addition to these results, analyses conducted
to examine the impact of hot water on the release of 99Tc suggest that only a small percentage of the total
is being released. This suggest that hot water stripping to remove carbon tetrachloride will not have a
significant effect on the resin’s capability to hold-on to sequestered 99Tc. Finally, encapsulation of spent
resin in a cementitious material may be a viable disposal option, but additional tests are needed to
examine the extent of physical degradation caused by moisture loss and the effect this degradation
process can have on the release of 99Tc.

iii
 Acknowledgements

The authors wish to acknowledge Mark E. Byrnes and Sally A. Simmons at CH2M Hill Plateau
Remediation Company (Richland, Washington) for providing project funding and technical guidance.
The authors would also like to acknowledge the technical support of Jim Mavis from CH2M Hill Seattle
Office. The authors also would like to thank S.R. Baum, E.T. Clayton, and I.V. Kutnyakov (all from
PNNL) for helping carry out various aspects of the work described in this report. We are particularly
grateful to Wayne Cosby (PNNL) for completing the editorial review of this technical report.

v
 Acronyms and Abbreviations

ANS American Nuclear Society

ANSI American National Standards Institute
CERCLA Comprehensive Environmental Response, Compensation, and Liability Act of
1980
CHPRC CH2M Hill Plateau Remediation Company
DI deionized (water)
DOE U.S. Department of Energy
EDS energy dispersive spectrometry
EPA U.S. Environmental Protection Agency
EQL estimated quantitation limit
HIC high integrity container
IC ion chromatography
ICP-MS inductively coupled plasma mass spectroscopy
IDF Integrated Disposal Facility
LI Leachability Index
LLW low-level waste
MDL minimum detection limit
MS mass spectroscopy
TM
PDF powder diffraction file
pH measure of the acidity of a solution, where pH is the negative of the logarithm of
the activity of H+ in solution
PNNL Pacific Northwest National Laboratory
SEM scanning electron microscopy
XRD X-ray diffraction

vii
 Units of Measure

θ angle of incidence (Bragg angle)

Å angstrom (10-10 m or 10-1 µm)
°C temperature in degrees Celsius [T(°C) = T(K) – 273.15]
cm centimeter
pCi picocuries
g gram
µ micro (prefix, 10-6)
µm micrometer
M molarity, mol/L
mL milliliter
λ wavelength
wt% weight percent

ix
 Contents

Executive Summary .............................................................................................................................. iii

Acknowledgements ............................................................................................................................... v
Acronyms and Abbreviations ............................................................................................................... vii
Units of Measure ................................................................................................................................... ix
Contents ................................................................................................................................................ xi
1.0 Introduction .................................................................................................................................. 1.1
1.1 Ion Exchange Resin.............................................................................................................. 1.1
1.2 Overview-Review of Disposal Options for Spent Resins .................................................... 1.2
1.3 Review of Cement Solidification of Spent Resins ............................................................... 1.3
1.4 Purpose and Scope ............................................................................................................... 1.4
1.5 Report Contents and Organization ....................................................................................... 1.5
2.0 Materials and Methods ................................................................................................................. 2.1
2.1 Sampling of the Ion Exchange Resin ................................................................................... 2.1
2.2 Ion Exchange Resin Moisture and Re-hydration ................................................................. 2.1
2.3 Long Term Stability ............................................................................................................. 2.2
2.4 Stability in Heated Water ..................................................................................................... 2.2
2.5 Resin Stabilization for Disposal ........................................................................................... 2.3
2.5.1 EPA Method 1315 ..................................................................................................... 2.4
3.0 Results and Discussion ................................................................................................................. 3.1
3.1 Ion Exchange Resin Moisture and Re-hydration ................................................................. 3.1
3.2 Long-Term Stability ............................................................................................................. 3.1
3.3 Stability in Heated Water ..................................................................................................... 3.3
3.4 Resin Stabilization for Disposal ........................................................................................... 3.3
3.5 Solids Characterization ........................................................................................................ 3.3
3.6 EPA 1315 Monolith Results ................................................................................................. 3.8
3.7 Discussion ............................................................................................................................ 3.8
4.0 Conclusions and Recommendations ............................................................................................. 4.1
5.0 References .................................................................................................................................... 5.1
Appendix A ........................................................................................................................................... A.1
Appendix B ........................................................................................................................................... B.1

xi
 Fig u re s
2.1. Schematic of 1315 Test Method ................................................................................................... 2.4
3.1. Results of the Long-Term Stability Leach Tests at Varying Solid-to-Solution Ratios................. 3.2
3.2. Results of the Additional Leach Test with Replacement of Deionized Water ............................. 3.2
3.3. Results of the Long-Term Stability Tests at Varying Temperatures ............................................ 3.3
3.4. X-Ray Diffraction Patterns for Raw Materials—Fly Ash (left) and Portland Cement
Type II (right) ............................................................................................................................... 3.5
3.5. Fly Ash SEM Images and EDS Spectrum .................................................................................... 3.6
3.6. Portland Cement SEM Images and EDS Spectrum ...................................................................... 3.7

Ta b le s
1.1. General Properties of Anion Exchange Resins ............................................................................. 1.2
1.2. Oxide Composition of ASC Specialty and Ordinary Portland Cements....................................... 1.4
2.1. Schedule for Long Term Stability Tests ....................................................................................... 2.2
2.2. Schedule for Stability in Heated Water Test................................................................................. 2.3
2.3. Recipe Encapsulation Monoliths .................................................................................................. 2.4
2.4. Schedule for Resin Stability (Method 1315) Experiment ............................................................. 2.5
3.1. Moisture Content Results for the as-Received and Re-Hydrated Resin ....................................... 3.1
3.2. Chemical Composition, in µg/g, of Raw Materials Used for Monolith Samples—Fly Ash
and Portland Cement ..................................................................................................................... 3.4
3.3. Average Diffusivity and LI Values for Encapsulated Spent Resin ............................................... 3.8
3.4. Kd Results of the Long-Term Stability Leach Tests at Varying Solid to Solution Ratios ............ 3.9
3.5. Kd Results of the Long-Term Stability Tests at Varying Temperatures ....................................... 3.9
3.6. Kd Results from the Long-Term Stability Leach Test .................................................................. 3.10
3.7. Kd Results of the Additional Leach Test with Replacement of Deionized Water ........................ 3.10

xiii
 1.0 Introduction
The Hanford site is a Federal facility in southeastern Washington State that manufactured nuclear
materials for national defense between the years of 1943 and 1988. In 1989, certain areas of the Hanford
Site, including the 200-ZP-1 operable unit, were placed on the National Priorities List pursuant to the
Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA).

Among the contaminants of concern in groundwater beneath 200-ZP-1 was technetium-99 (99Tc), a
radioisotope with a half-life of 210,000 years. Between April 26, 2007, and December 20, 2007, an ion
exchange pilot-scale treatability test was performed to evaluate 99Tc removal in a pump-and-treat system
that would be installed as part of site cleanup.

Two pilot-scale ion exchange columns were tested, each using groundwater from a different well.
The pilot test column treating water from well 299-W15-765 contained the higher 99Tc concentration of
the two wells as well as having a nitrate concentration very similar to that expected in influent to a full-
scale treatment facility.

The ion exchange column that was tested with water from 299-W15-765 was stored for future
examination and testing for purposes of waste characterization before disposal. The pending testing
provides an opportunity to evaluate the stability of the ion exchange resin during long-term storage, to
evaluate its ability to retain 99Tc during hot water stripping of carbon tetrachloride, and to assess its
stability when grouted for disposal in a permanent, onsite waste disposal facility.

1.1 Ion Exchange Resin

Ion-exchange technology has been widely used for various separation processes, such as industrial
processing of semi-conductors, water softening, and wastewater and groundwater treatment (Batista et al.
2000, Tripp and Clifford 2000, Helfferich 1995, Melis et al. 1996, Marina et al. 1996, Tao and Xiao 1996,
Sorg et al. 1999, and Guseva et al. 1988). The ion-exchange mechanism is generally known as being the
result of simple electrostatic interaction, although factors such as the size and nature of counter-ions, their
hydration energy, and the types of functional groups on resin surfaces significantly impact the
thermodynamics and kinetics of the exchange reactions (Moyer and Bonnesen 1997, Gu et al. 2000b,
Brown et al. 2000). The optimal design and operation of an ion-exchange system thus require accurate
knowledge of the thermodynamics and equilibria of the exchange reactions among various ions and
counter ions in the system. Typical approaches for acquiring these data include measuring multi-
component ion exchange equilibria and developing thermodynamic models which, based on multi-
component equilibrium data, can predict multi-component exchange reactions. An overview of the
various types of anion-exchange resins and their properties is provided in Table 1.1.

1.1
 Table 1.1. General Properties of Anion Exchange Resins
AEC(a)
Resin Type Amine Group (mequiv/g)
Purolite A530E Polystyrene (ethyl)3N/(hexyl)3N 2.2
WBR109 Polystyrene (ethyl)3N/(butyl)3N 2.9
Purolite A520E Polystyrene (ethyl)3N 2.8
Purolite A500 Polystyrene (methyl)3N 3.5
Dowex 1-X8 Polystyrene (methyl)3N 3.2
Purolite A850 Polyacrylic, gel (methyl)3N 3.9

(a) AEC—anion-exchange capacity (dry weight equivalent).

In this report, we examine the stability of spent Purolite A530E anion-exchange resin—known for its
relatively high anion selectivity—that was used in a pump-and-treat system to remove 99Tc from
contaminated groundwater at Hanford. Purolite A530E is a monofunctional anion-exchange resin with
triethylammonium exchange sites and the polystyrene backbone cross-linked with divinyl-benzene. It
was previously demonstrated that this material has the capability to remove significant amounts of
perchlorate (ClO4-) and pertechnetate (TcO4-) from contaminated groundwater (Gu et al. 2000a, Bonnesen
et al. 2000). In fact, Purolite A530E is currently being used to remove TcO4- from the contaminated
groundwater at the U.S. Department of Energy’s Paducah Gaseous Diffusion Plant site in Kevil,
Kentucky (Gu et al. 2000b). Because TcO4- is larger and has a lower hydration energy than most of the
other anions encountered in groundwater (such as Cl-,HCO3-, SO42-, NO3-), there is a chemical bias toward
exchanging TcO4- preferentially over the other anions in an aqueous solution (Gregor et al. 1955). This
bias can be enhanced by chemical modification of the resin, including altering the size and shape of the
cationic exchange sites and the polymer cross-linking density. It was found that resin selectivity for
TcO4- sorption increased with the radius of the immobilized alkyl chain length of the quaternary
ammonium groups on resin beads; however, the increase in radius also resulted in an overall decrease in
the exchange capacity and rate of anion exchange (Bonnesen et al. 2000).

1.2 Overview-Review of Disposal Options for Spent Resins

A review of the current practices for ultimate disposal of spent organic-based resins yielded several
observations. Although cement solidification of spent ion-exchange resins is still being considered or
actively practiced in countries such as China, Serbia, and Turkey, currently spent resins at U.S.
commercial low-level waste (LLW) burial grounds are disposed of (after dewatering) in either steel
containers for Class A wastes or in high-density polyethylene high-integrity containers (HICs) for Class C
wastes. The following synopsis was obtained in telephone conversations with an environmental health
physicist at one of the few commercial LLW burial grounds in operation within the United States.(a) The
Class C dewatered spent resins within HICs are placed within concrete boxes to provide structural support

(a) This information was obtained during two phone conversations with Bob Haight, Environmental Health
Physicist with U.S. Ecology Washington, Inc., Richland, Washington, in August 2009.

1.2
after burial. Most states that regulate commercial LLW burial grounds do not allow any credit for the
integrity of the steel containers once they are buried in the subsurface sediments. Hence, only Class A
designated dewatered spent resin wastes can be transported and disposed of in the steel containers. State
regulators give the concrete boxes a lifetime of at least 1000 years and also assume that the high-density
polyethylene HICs provide additional containment. The concern with the HICs is that they cannot take
the overburden pressures of the sediment that is used to backfill the trenches. Thus, the HICs are
overpacked with the concrete boxes to provide the rigidity needed to keep the overburden compressive
forces from crushing the HICs. Herbst (2002) also concluded that the best option for disposing of spent
ion-exchange resins generated as a secondary waste stream from vitrification of sodium-bearing waste
from the Idaho Nuclear Technology and Engineering Center was dewatering, placement in HICs, and
disposal in shallow-land burial facilities. A current draft report that collates the types and quantities of
secondary wastes that are to be produced at the Hanford Tank Waste Treatment and Immobilization Plant
(WTP) suggests that the spent resorcinol-formaldehyde resins are to be placed in HICs and, because of
the high dose rates, need to be remotely handled during transit and burial in the Integrated Disposal
Facility (IDF) (see Gehner et al. 2009). There is no mention whether the HICs are to be high-density
polyethylene or some other material. If high-density polyethylene HICs are used, placing the HICs in
concrete overpacks as is done for Class C commercial waste would be advised.

1.3 Review of Cement Solidification of Spent Resins

In the past, spent resins often were solidified into cement waste forms, but several problems have
caused this solidification process to be mostly abandoned, at least in the United States. The benefits for
solidification of spent ion-exchange resins in cement include the use of simple equipment and ease of
scale-up. Low temperatures are adequate for solidification, the final products are relatively resistant to
physical deformation from overburden pressures after burial or during transport to the burial ground, and
the costs are relatively low. A major drawback to solidification of spent resins into cement is the loading
limitations, which are in the range of 20% wet resins, to the dry blend of solidification agents. For
example, an optimum recipe used in China in the 1990s (Pan et al. 2001) to solidify spent resins was blast
furnace slag (BFS) 24 wt%, fly ash 24 wt%, OPC 8 wt%, 24 wt% of spent resin, and 20 wt% water.
These limitations are necessary to prevent swelling and cracking of the product after or during short-term
curing (Li and Wang 2006).

Compared to many liquid and solid radionuclide-bearing wastes, spent ion-exchange resins are more
difficult to solidify. Ion-exchange beads that are not already saturated with water swell when contacted
with water, generating internal pressures that can reach 50 MPa. Even when water-saturated resins are
used, if the ratio of resin to other ingredients rises much above 25%, swelling and cracking is generally
observed. The most likely cause is that the resins and hydrating cement phases compete with each other
for free water. Neilson and Columbo (1982) found that cement solidification of ion-exchange resins,
especially large cement right-cylinder monoliths, deteriorated after several weeks when monoliths were
leached in water. Hairline cracks developed and then widened with time. The authors hypothesized that
heat generated during cement hydration built up internally and drove water out of the resins, which
caused swelling pressures in the larger specimens. Sperazini and Buckley (1981) recommended that
spent organic exchange resins first be incinerated to form ash before solidification into cement to avoid
swelling and cracking. They found that incineration of resins to ash improved 137Cs leach resistance of
the final cement product by over a factor of 10.

1.3
 In China, a new type of cement, ASC, with higher aluminum and sulfur oxide content, less silicon and
calcium oxides (see Table 1.2), and a mixture of zeolites has been found to be superior for encapsulating
spent ion-exchange resins (Li et al. 2005). Li et al. (2005) recommend a recipe of 35-wt% ASC cement,
7-wt% zeolite, 42-wt% spent resins (that have a gravimetric moisture content of 50%, i.e., close to
saturated), and 16-wt% water. The zeolite helps in sequestering radionuclides (e.g., 137Cs and 60Co) that
desorb from the spent resins during the cement hydration reactions that generate high-ionic-strength pore
waters.

Table 1.2. Oxide Composition of ASC Specialty and Ordinary Portland Cements
ASC OPC
Oxide (wt%)
SiO2 9.21 24.19
A12O3 31.36 4.87
CaO 40.9 58.23
MgO 3.79 2.64
Fe2O3 3.28 5.19
SO3 9.45 1.96
TiO2 1.21 0.26
Na2O ND 0.44
K2O ND 0.65
Ign. Loss 0.55 1.31
Total 99.75 99.74
ND = No data

The spent ion-exchange resins do not interact with the crystalline and amorphous gel minerals that
form upon cement hydration; rather, they are simply physically encapsulated within the cement or grout
solids (Li and Wang 2006). The diffusion of constituents from a cement or grout that solely physically
encapsulates waste can be reduced by decreasing the pore sizes, pore throat sizes, and pore connectivity
(i.e., increased tortuosity) in the cement matrix. The porosity can be altered by varying the types of solid
oxides and minerals and their amounts used in the dry blend. However, lowering the porosity of the
hardened product by changing the dry blend generally leads to lowered compressive strength of the
hardened cement. Although encapsulation in a cementitious material is not the current practice at the one
LLW facility in the US, evaluation of this option is needed to support a disposal decision that will be
needed for any of the Hanford sites LLW facilities (e.g., ERDF and/or IDF).

1.4 Purpose and Scope

The purpose of Pacific Northwest National Laboratory’s (PNNL’s) work documented in this report is
to conduct an evaluation of 99Tc release from spent ion exchange resin. This document describes the
results collected as part of an analysis of spent resin stability and stabilization for disposal. As part of the
pilot scale treatability test, CH2M Hill Plateau Remediation Company (CHPRC) has contracted PNNL to

1.4
conduct experiments on the Purolite A530E ion exchange resin used to treat groundwater from well 299-
W15-765.

1.5 Report Contents and Organization

The ensuing sections of this report document the materials and steps used to sample, rehydrate, and
determine the moisture content of the as-received and rehydrated spent resin (Section 2.0). The materials
and steps used to evaluate 99Tc release from the spent resin after aging, after being exposed to heated
water, and after being stabilized in a cement-based waste form. The results collected from these methods
are presented, discussed, and summarized in Sections 3.0. The conclusions and recommendations are
provided in Sections 4.0.

1.5
 2.0 Materials and Methods

2.1 Sampling of the Ion Exchange Resin

Approximately 2 liters of ion exchange resin sampled from the top of the ion exchange column was
shipped to PNNL from CHPRC. Because the pilot tests were conducted in a down-flow mode, CHPRC
removed aliquots of resin from the top of the column because it was expected to contain the highest
concentration of 99Tc. After being sampled, these materials were packaged and shipped to PNNL.

2.2 Ion Exchange Resin Moisture and Re-hydration

Due to long-term storage of the spent ion exchange columns, re-hydration of the resin was conducted
before performing experiments. Before re-hydrating, a subsample (~10 g) of the as received resin was
collected to analyze for the moisture content. To re-hydrate the resin, the resin was placed in a vacuum
and a 1000 mg/L NaCl solution was introduced to the resin. The resin and NaCl solution were kept under
vacuum over night to verify that the resin was completely saturated by the NaCl solution. Once complete,
the vacuum was slowly released to allow the resin to pull the saline solution into the beads. A subsample
of the solution from this process was analyzed for 99Tc and other major and minor cations.
Approximately 400 to 500 grams of resin was rehydrated for subsequent experiments.

The moisture content of the as received and hydrated ion exchange resin was determined. The
moisture content measurement allows for the amount of water contained in the resin to be subtracted from
the total mass of sample used. Determining the concentration of 99Tc per gram of dry resin allows for the
rate of release to be corrected based upon the loading. To obtain residual moisture content, approximately
10 grams of ion exchange resin was placed into a pre-tared container, weighed, and dried in an oven at
105°C until constant weight was achieved (in triplicate). At least two weighings, each after a 24-hour
heating, was performed to verify that all moisture was removed.

In addition to the moisture analyses, a series of resin digestion experiments were conducted in an
attempt to quantify the total amount of 99Tc retained on the ion exchange resin. After several iterations
and attempts to dissolve the resin using varying concentrations of H2O2 mixed with 0.025 moL/L
Fe(NO3)3 and applying heat, the resin beads did not dissolve. Previous exchange analyses were conducted
using samples of spent resin from the pilot scale treatability test and the results suggest a 99Tc loading
value of 2.08 × 105 pCi/g (~12.5 µg/g 99Tc). This value will be used as the total 99Tc loaded on the resin
for the purposes of these experiments.

2.1
2.3 Long Term Stability
Due to long-term storage of the re-hydrated spent ion exchange resin columns, the resin may have
degraded and released some of the 99Tc adsorbed on the resin. Because 99Tc is highly mobile and
generally non-adsorptive, 99Tc that is released from the resin because of degradation is assumed to be
leachable with deionized water (Krupka and Serne 2002). To evaluate whether the 99Tc has desorbed
from the spent resin, a series of leaching tests was conducted using deionized water extractions. The
extracts were prepared by adding a known weight to approximately 5 to 20 grams of resin at 1:1, 1:2 and
1:5 solid-to-solution ratios (see Table 2.1). The weight of deionized water needed was calculated,
accounting for the existing moisture in the resin based on measurements obtained from moisture content
tests. An appropriate amount of deionized water was added to screw cap jars containing a known amount
of resin. The jars were then sealed and placed on a mechanical orbital shaker for 2 hours of contact.
The supernatant was decanted and filtered and submitted for 99Tc analysis by inductively coupled plasma
mass spectroscopy (ICP-MS).

Table 2.1. Schedule for Long Term Stability Tests

Solid:Solution Resin (dry) mass
Sample Ratio (g)
S01 1:1 20
S02 1:2 10
S03 1:5 5
Note: samples conducted in duplicate

An additional leach test was conducted to evaluate whether 99Tc measured in the solutions from the
leach tests was a contribution from the 99Tc that desorbed from the resin or 99Tc that was contained in the
interstitial pore water. The extract was prepared using a solid-to-solution ratio of 1:2. The extract was
prepared the same as the previous leach tests, but after 2 hours of contact, the solution was decanted, and
new deionized water (the same amount) was added back to the resin. The jars were sealed and returned to
the mechanical orbital shaker. Decanting and replacing the deionized water contacted with the resin took
place over a period of 4 days with sampling and water replacement occurring at 2 hours, 6 hours, 1 day,
2 days, 3 days, and 4 days. After decanting the deionized water, the solution was filtered and submitted
for 99Tc analysis by ICP-MS.

2.4 Stability in Heated Water

During operation, the ion exchange resin will be treated with a combination of hot water and air
sparging to remove adsorbed carbon tetrachloride. The temperature of the heated water is expected to fall
between ~40 and 75°C and last an estimated 16 hours at these temperatures. The Purolite A530E resin
can withstand temperatures from 100°C to -40°C (Purolite 2007, 2009). To evaluate the resin’s stability
under heated conditions, a series of leaching tests at 40, 60, and 80°C was conducted (in duplicate).
Approximately 5 grams of resin was contacted with 10 grams of deionized water and put into an oven at
temperatures of 40, 60, and 80°C. Additional samples were prepared (a total of 6 samples at each
temperature) to evaluate the release as a function of time (6, 12, and 24 hours) at each temperature. At

2.2
the end of each time interval, the samples were removed from each oven, and the heated supernatant was
filtered, acidified, and analyzed for 99Tc using ICP-MS (Table 2.2).

Table 2.2. Schedule for Stability in Heated Water Test

Temperature Contact time Resin (dry) mass
Sample (°C) (hours) (g)
T01-6 40 6 5
T01-12 40 12 5
T01-24 40 24 5
T02-6 60 6 5
T02-12 60 12 5
T02-24 60 24 5
T03-6 80 6 5
T03-12 80 12 5
T03-24 80 24 5
Note: samples were conducted in duplicate

2.5 Resin Stabilization for Disposal

One option of stabilizing spent ion exchange resin is encapsulation in Portland cement or an
alternative near-neutral stabilizing material, such as magnesium potassium phosphate, before placement
in a permanent storage impoundment or disposal facility. The components used to prepare the monolith
waste form are listed in Table 2.3 and include sulfate-resistant Portland Type I/II cement, a pozzolanic
material (Class F fly ash), and deionized (DI) water. The Portland cement was obtained from LaFarge
North America, Inc. (Herdon, Virginia), and the fly ash was obtained from Lonestar (Seattle,
Washington).

The encapsulation monoliths (1-inch diameter by 1.8-inch height) were prepared by adding the
components in the following order: cement, fly ash, spent ion exchange resin, and DI water. The amount
of resin used was a maximum of 20% of the final cement mix. The dry materials were blended for
5 minutes using a planetary mixer set at low speed. After the dry material was homogeneous, the spent
ion exchange resin and water were added to the blended dry mixture. The materials were mixed for
5 minutes to verify homogeneity. Polycarbonate sleeves were used as molds for casting monoliths. The
molds were partially filled in the vertical position and vibrated until a significant decrease in the release
of air bubbles was observed. Then, the molds were filled again with additional wet slurry and vibrated
until no air bubbles were observed. This process was repeated until the molds were completely filled.
The molds were stored in a 100% relative humidity chamber for 5 days, at which time the encapsulated
monoliths were removed from the molds. The monoliths were subsequently stored in the humidity
chamber for an additional 23 days for a total curing time of 28 days.

After the 28-day cure time, it was noted that the monolith samples prepared using the initial receipe
were crumbly in texture. Therefore, a revised recipe was created with an increase in the amount of
Portland cement and fly ash (Table 2.3). After the 28-day cure time, the U.S. Environmental Protection
Agency (EPA) Method 1315 was repeated for this second set of monolith samples. Only the samples
collected from the final recipe were analyzed and reported here.

2.3
 Table 2.3. Recipe Encapsulation Monoliths
Initial Recipe Quantity Final Recipe
Material (g) Quantity (g)
Resin 20 20
Fly ash 48 51
Portland cement 9 18
Water 10 11

2.5.1 EPA Method 1315

The high pH of the most common stabilizing agents—for example, cementitious material, nominally
~12.5,—may cause the release of 99Tc from the spent ion exchange resin. To evaluate the effect of
immobilizing spent resin in Portland cement, EPA Draft Method 1315, Mass Transfer Rates of
Constituents in Monolith or Compacted Granular Materials Using a Semi-Dynamic Tank Leaching Test,
was used to provide more detailed information on 99Tc release from a stabilized form. The EPA Method
1315 is a semi-dynamic leach experiment that consists of submerging a monolithic sample (with a fixed
geometry) in DI water at a fixed liquid volume-to-solid surface area ratio and sampling at fixed periods of
time as cumulative leaching times (EPA 2009c). At each sampling interval, the leaching fluid is removed
and replaced with fresh fluid. A schematic of this process is shown in Figure 2.1. Here we performed a
shorter duration test for 14 days in duplicate to evaluate 99Tc release.

Figure 2.1. Schematic of 1315 Test Method

The geometric surface area is used in this test method and is calculated based on the cylindrical
dimensions of the sample. The average calculated geometric surface area was 0.0046 ±0.0001 m2. At
each of the seven pre-determined leaching intervals, the sample mass was recorded, and the leaching
solution was changed. This method is similar to the American National Standards Institute/American
Nuclear Society (ANSI/ANS) 16.1 (ANSI 1986), but the leaching intervals are modified, and the process
of mass transfer can be interpreted by more complex release models that account for physical retention of
the porous medium and chemical retention at the pore wall through geochemical speciation modeling.

2.4
 The cylindrical monolith sample (1-inch diameter by 1.8-inch height) was placed into the center of a
leaching vessel and mixed with DI water to maintain a solid-to-solution ratio of 10 ±1 mL of eluant per
cm2 of sample. The sample stand and holder were used to maximize the contact area of the sample with
the leaching solution. In between the sampling/replacement intervals, the experimental vessels were
covered with a lid. An example of the experimental setup and sample specimens in the leaching vessels is
shown in Figure 2.1. The leaching times at which solution exchanges were made for these experiments
were 0.08, 0.25, 1, 2, 7, and 14 days. Leachate samples collected during these intervals were used to
measure pH. Before submitting for chemical analyses, the samples were also filtered using a 0.45-μm
syringe filter.

Table 2.4. Schedule for Resin Stability (Method 1315) Experiment

Interval duration Interval duration Cumulative leaching
Sample (hours) (days) time (days)
T01 2.0 ± 0.25 0.08
T02 23.0 ±0.5± 1.0
T03 23.0 ± 0.5 2.0
T04 5.0 ± 0.1 7.0
T05 7.0 ± 0.1 14.0
Note: samples will be conducted in duplicate

The observed diffusivity for each constituent was calculated using the analytical solution, Equation
(2.1), for simple radial diffusion from a cylinder into an infinite bath as presented by Crank (1986):

2
 M ti 
Di = π  
( )
(2.1)
 2 ρ Co ti − ti −1 
 

where Di = observed diffusivity of a specific constituent for leaching interval i [m2/s]

Mti = mass released during leaching interval i [mg/m2]
ti = cumulative contact time after leaching interval, i [s]
ti-1 = cumulative contact time after leaching interval, i-1 [s]
Co = initial leachable content [mg/Kg]
ρ = sample density [Kg-dry/m3].

The mean observed diffusivity for each constituent can be determined by taking the average of the
interval observed diffusivity with the standard deviation. The Leachability Index (LI), the parameter
derived directly from immersion test results, evaluates diffusion-controlled contaminant release with
respect to time. The LI is used as a performance criterion to assess whether solidified/stabilized waste
will likely be acceptable for subsurface disposal in waste repositories. In most cases, the solidified waste
is considered effectively treated when the LI value is equal to or greater than nine. The LI is calculated
with Equation (2.2).

 D 
LI n = − log  n2  (2.2)
 cm s 

2.5
where LI is the leach index, and Dn is the effective diffusivity for elements of interest (cm2/s) during the
leach interval n.

2.6
 3.0 Results and Discussion

3.1 Ion Exchange Resin Moisture and Re-hydration

The results from the moisture contents conducted on the as-received and re-hydrated resin are shown
in Table 3.1. After long-term storage, the moisture content results confirm that the resin became
dehydrated while it was being stored. Analysis of the saturating solution used to re-hydrate the resin
resulted in 9.6E+3 pCi of 99Tc. However, it is not known whether the 99Tc contained in the re-hydrating
solution was desorbed from the resin or was contained in the interstitial pore spaces of the resin.

Table 3.1. Moisture Content Results for the as-Received and Re-Hydrated Resin

Moisture Standard
Content (%) Deviation
as-received 0.78 1.62E-02
re-hydrated 1.4 4.03E-02

3.2 Long-Term Stability

The results for the long-term stability leach tests are shown in Figure 3.1. The concentration of 99Tc
detected in the different solid-to-solution ratios resulted in 26 to 37 pCi/g of 99Tc. With respect to the
starting concentration of 99Tc in the resin, these results indicate that less than 0.02% of the total amount of
99
Tc was released from the resin during the leach tests. Additionally, the follow-up leach tests with the
replacement of the deionized water over a 4-day time period are shown in Figure 3.2. There was a slight
decrease in the concentration of 99Tc each time the deionized water was replaced, with the largest
decrease occurring after the 2-hour exchange. This decrease indicates that there was a likely a small
contribution of 99Tc that came from 99Tc remaining in the pore spaces of the resin. However, the total
amount of 99Tc found in the solution was less than 0.005% of the total 99Tc contained in the resin.

3.1
 50

Tc-99 concentration (pCi/g)

40

30

20

10

0
1 to 1 1 to 2 1 to 5
solid to solution ratio
Figure 3.1. Results of the Long-Term Stability Leach Tests at Varying Solid-to-Solution Ratios

12
Tc-99 Concentration (pCi/g)

10

0
0 20 40 60 80 100
hours
Figure 3.2. Results of the Additional Leach Test with Replacement of Deionized Water

3.2
3.3 Stability in Heated Water
The results for the long-term stability leach tests conducted at different temperatures are displayed in
Figure 3.3. The largest increase in 99Tc concentration occurred in the 80°C samples. The difference
between the 6-hour and 24-hour 99Tc concentrations at 80°C yielded a 14% difference. However, even
the highest concentration of 99Tc found at 80°C, 24 hours, is less than 0.02% leached of the total starting
99
Tc found in the resin. The percent leached from the heated water leach tests ranges from 0.013% to
0.019%.

45
40
Tc-99 Concentration (pCi/g)

35
30
25 40°C
20 60°C
15 80°C
10
5
0
6 hours 12 hours 24 hours

Figure 3.3. Results of the Long-Term Stability Tests at Varying Temperatures

3.4 Resin Stabilization for Disposal

In this section, we discuss the results obtained from immobilizing spent ion exchange resin in a
mixture of Portland cement and fly ash. We begin by discussing the results obtained from characterizing
the raw materials (e.g., portland cement and fly ash) used to prepare the monolith samples of encapsulated
resin. This section is followed by a presentation of the results obtained from EPA Method 1315.

3.5 Solids Characterization

The raw materials used to prepare the waste forms and the 28-day cured portland cement samples
were characterized with respect to their crystalline and chemical composition using a variety of
techniques, including chemical digestion, X-ray diffraction (XRD), and scanning electron microscopy
(SEM) with energy dispersive spectrometry (EDS). The results from these analyses are discussed in the
sections that follow.

3.3
Table 3.2. Chemical Composition, in µg/g, of Raw Materials Used for Monolith Samples—Fly Ash and
Portland Cement

Elements Fly Ash Portland Cement

(a)
Tc NA NA
Al 4.87E+03 8.97E+04
Ag 2.05E+00 2.20E+00
As <7.99E-03 1.50E+01
Ba 2.45E+02 2.18E+03
Ca 4.67E+05 4.74E+04
Cd <1.32E-03 <1.32E-03
Cr 6.87E+01 3.60E+01
Cu 1.16E+02 1.20E+02
Fe 2.01E+04 3.97E+04
Hg 7.14E-02 6.69E-02
I <5.75E-01 <5.75E-01
K 2.13E+03 4.17E+03
Mg 5.70E+03 7.69E+03
Mn 5.16E+02 3.22E+02
Na 3.74E+03 3.23E+04
P 6.16E+02 4.06E+03
Pb 2.15E+01 2.13E+01
S 1.24E+04 1.01E+03
Si 1.01E+05 2.02E+05
Sn 6.01E+02 9.16E+01
Sr 1.20E+03 3.10E+03
Ti 1.59E+03 2.34E+04
V 9.05E+01 4.88E+02
Zn 6.87E+02 1.91E+02
Zr 3.88E+02 8.93E+02

Powder XRD measurements were performed on the raw ingredients used to prepare the encapsulation
monolith samples. The measured XRD patterns are shown in Figure 3.4 along with the standard mineral
powder diffraction files (PDF™). The fly ash (Figure 3.4) XRD pattern suggests that this material is
amorphous with minor amounts of crystalline phases. The peak near 26.7 °2θ was identified as quartz
(PDF#00-046-1045, SiO2). The identification of the peak near 35.5 °2θ may be magnetite (PDF# 00-019-
0629, Fe3O4). However, this is not certain. The portland cement type I/II XRD pattern suggests that this
raw ingredient contains a significant amount of crystalline material. Calcium silicate (PDF# 00-055-
0740, Ca3SiO5) was the dominant crystalline phase identified in the XRD pattern (see Figure 3.4), which
is typical of portland cement. Although additional Rietveld refinements (Rietveld 1969) are needed for
conclusive identification, these results further suggest that the dominant form of calcium silicate present

3.4
is the monoclinic type-2 polymorph. Additionally, a minor amount of dolomite (PDF# 98-000-0200,
MgCa(CO3)2) was also observed in the portland cement.

(c) Portland Cement Type I/II

Fly Ash (b)

Relative Intensity
Relative Intensity

Quartz

10 20 30 40 50 60 10 20 30 40 50 60
2°θ 2°θ

Figure 3.4. X-Ray Diffraction Patterns for Raw Materials—Fly Ash (left) and Portland Cement Type II
(right)

A low magnification image of a cluster of fly ash grains is shown in Figure 3.5. This image reveals
that the morphology of the unreacted fly ash is primarily spherical with a range of particle sizes. The
shape and the morphology of the fly ash particles are typical and are the results of how these particles are
produced. Fly ash is a residue material generated in the combustion of coal and solidifies while
suspended in exhaust gases. The EDS spectrum reveals a high silicon and Al content for the spherical
particles that contain a minor amount of calcium, iron, sodium, magnesium, and titanium. Based upon the
amorphous XRD pattern, chemical digestion, and SEM/EDS, one can conclude that these spherical
particles are mainly an amorphous SiO2 phase that has become a host matrix for other cations and mineral
phases.

3.5
Figure 3.5. Fly Ash SEM Images and EDS Spectrum. The top image is a low-magnification (~300 µm)
image of fly ash with an increased magnification of multiple spheres at 30 µm (center left).
The additional image (center right) was used to collect EDS spectra of a sphere of fly ash
(bottom).

Figure 3.6 is a low-magnification micrograph that shows the morphologies, sizes, and surface textures
of typical portland cement particles. Analysis of the SEM micrographs indicates that the aggregates of
portland cement are made up primarily of a single phase. The EDS spectrum reveals a high calcium and

3.6
silicon content with minor amounts of aluminum, calcium, iron, magnesium, and sulfur. These results are
consistent with the XRD identification (Figure 3.4c) and chemical digestion results (Table 3.2).

Figure 3.6. Portland Cement SEM Images and EDS Spectrum. The top image is a low-magnification
(~300 µm) image of portland cement with an increased magnification of multiple spheres at
30 µm (center left). The additional image (center right) was used to collect EDS spectra of
portland cement (bottom).

3.7
3.6 EPA 1315 Monolith Results
The monoliths created for the Method 1315 experiments resulted in cylinders that have a mass of 37.7
to 38.9 grams, a surface area of 45.6 to 48.3 cm2, and a volume of approximately 0.02 liters. The first
monolith that was tested (recipe above in Table 2.3) resulted in 99Tc concentrations of approximately
17,000 pCi/g. These concentrations indicate that approximately 0.08% of the total 99Tc contained in the
resin was leached from the portland cement monoliths.

The second set of monoliths that contain an increase in the quantity of cement used (recipe in Table
2.3) resulted in monoliths that visually looked sturdier in construction and were not crumbling. The 99Tc
concentrations in these solutions were below the ICP-MS estimated quantification limit
(EQL = 0.02 µg/L). Using the EQL value, the upper limit for the diffusivity and LI was calculated for
these results, and the results are provided in Table 3.3. It is important to note that these are short-term
leach tests, and the intent of these results is to provide an initial indication as to whether solidification in a
cementitious waste form would be a viable option.

Table 3.3. Average Diffusivity and LI Values for Encapsulated Spent Resin

Cumulative Tc
Leaching Time Diffusivity
(days) (cm2/s) LI
0.08 <1.07E-14 14.0
1 <1.77E-15 14.8
2 <5.22E-15 14.3
8 <4.47E-16 15.3
14 <1.07E-15 15.0

3.7 Discussion
The distribution coefficient (Kd) is a measure of sorption and is defined as the ratio of the amount of
an adsorbate sorbed on a solid to the amount of adsorbate still in solution at equilibrium (EPA 1999). The
expression is as follows:
Ai
Kd = (3.1)
Ci

where Ai is the adsorbate on the solid at equilibrium (μg g-1), and Ci is the adsorbate remaining in solution
at equilibrium (μg mL-1).

The distribution coefficient (Kd) calculated for each experiment is shown below in Table 3.3 through
Table 3.6. In oxic environments, technetium is present as Tc(VII). Technetium(VII) is not adsorptive
and has high mobility, which results in Kd values of approximately 0 mL/g (Krupka and Serne 2002).

The Kd values ranged from 19,000 mL/g to 216,000 mL/g. The largest difference in the calculated Kd
values was in the long-term stability leach tests where the solid-to-solution ratio was varied. The smallest
Kd was calculated at the 1:1 solid-to-solution ratio, and the largest Kd was at the 1:5 solid-to-solution ratio.
This increase in Kd displays the high sorption capacity of the resin. Although there were more available

3.8
sorption sites with the additional water, the resin still continued to sorb more than 99.9% of the Tc as
shown by the increase in Kd values. The long-term stability leach tests resulted in a decrease in the Kd
values with an increase in heat. The average Kd value at 40°C was approximately 53,300 mL/g, the
average at 60°C was 50,600 mL/g, and the average at 80°C was 41,400 mL/g, resulting in a more than
10,000 mL/g difference in the Kd value from the lowest to the highest temperature. The 25% decrease in
Kd value at the higher temperature suggests that an increase in temperature causes the resin to release
more Tc at higher temperatures than at lower temperatures.

Table 3.4. Kd Results of the Long-Term Stability Leach Tests at Varying Solid to Solution Ratios

Solid:Solution
Ratio Kd (mL/g)
1:1 1.93E+04
1:1 2.21E+04
1:2 4.74E+04
1:2 5.37E+04
1:5 2.04E+05
1:5 2.16E+05

Table 3.5. Kd Results of the Long-Term Stability Tests at Varying Temperatures

Temperature Contact
(°C) time Kd (ml/g)
40 6 4.95E+04
40 6 5.44E+04
40 12 5.07E+04
40 12 5.81E+04
40 24 4.92E+04
40 24 5.80E+04
60 6 4.61E+04
60 6 5.20E+04
60 12 5.09E+04
60 12 4.51E+04
60 24 5.28E+04
60 24 5.67E+04
80 6 4.33E+04
80 6 4.39E+04
80 12 4.13E+04
80 12 4.22E+04
80 24 4.04E+04
80 24 3.75E+04

3.9
 Table 3.6. Kd Results from the Long-Term Stability Leach Test
Cumulative Time
Elapsed (hours) Kd (mL/g)
2 1.51E+05
2 1.77E+05
6 2.69E+05
6 2.97E+05
24 3.63E+05
24 4.48E+05
48 4.64E+05
48 5.73E+05
72 6.12E+05
72 5.56E+05
96 5.33E+05
96 7.36E+05

Table 3.7. Kd Results of the Additional Leach Test with Replacement of Deionized Water
Cumulative
Time (days) Kd (mL/g)
0.08 3.85E+06
0.08 3.38E+06
1 3.13E+06
1 2.97E+06
2 4.14E+06
2 3.79E+06
7 6.33E+06
7 5.02E+06
14 3.51E+06
14 5.04E+06

3.10
 4.0 Conclusions and Recommendations
The long-term stability leach test results were comparable to the heated stability test results. Both
yielded 99Tc concentrations that ranged from approximately 26 to 40 or 42 pCi/g, which is less than
0.02% of the total 99Tc loaded on the resin. The leach test that was performed to determine whether the
source of the 99Tc that was found in the leach solutions was from desorption of the resin or interstitial
pore spaces that yielded a maximum of 10 pCi/g (after 2 hours) and decreased over a 4-day time to
3 pCi/g. These low concentrations suggest that the resin was not releasing 99Tc during the leach tests and
there was likely only a small contribution of 99Tc that was coming from the solution remaining in the pore
spaces of the resin.

The resin stabilization for the disposal recipe had to be adjusted to accommodate the hygroscopic
nature of the resin. The initial recipe yielded monolith samples that were flaky in texture and consistently
leached approximately 0.08% of the total 99Tc contained in the resin over the 14-day test period. An
increase in the cement used in the recipe (double the amount) produced better monoliths that visually
appeared more sturdy (less flaky) and did not release any detectable 99Tc into the solution over the 14-day
test period. The second portland cement recipe is a more viable option for long-term stability and
disposal of the ion exchange resin.

All of the experiments that were performed on the ion exchange resin show that 99Tc is not easily
desorbed from the resin, even after long-term storage. The release of 99Tc is not largely affected by the
addition of heat. The lowest percentage of 99Tc release (0.013%) occurred at the 24-hour interval at 40°C,
and the largest percentage of 99Tc release (0.019%) occurred at the 24-hour interval at 80°C. The
difference in temperature yielded a small 0.006% increase in the release of 99Tc from the resin. During
operation, the ion exchange resin treatment will consist of a combination of hot water and air sparging to
remove adsorbed carbon tetrachloride. The temperature of the heated water is expected to fall between
~40 and 75°C and last an estimated 16 hours at these temperatures. The heated water treatment falls well
within the range of the experimental tests. Therefore, based on the experimental results, 99Tc release from
the resin during hot water treatment would be estimated to be <0.02% of the total 99Tc load.

4.1
 5.0 References
ANSI, 1986. Measurement of the Leachability of Solidified Low Level Radioactive Waste by a Short-
Term Test Procedure. In: Institute, A. N. S. (Ed.). American Nuclear Society, La Grange Park, IL.

Batista JR, FX McGarvey, and AR Vieira. 2000. “The removal of percholate from waters using ion-
exchange resins.” In: Perchlorate in the Environment. ET Urbansky, Ed.; Kluwer/Plenum: New York,
pp 135-145.

Brown GM, PV Bonnesen, BA Moyer, B Gu, SD Alexandratos, V Patel, and R Ober. 2000. “The Design
of Selective Resins for The Removal of Pertechnetate And Perchlorate from Groundwater.” In:
Perchlorate in the Environment. ET Urbansky, Ed.; Kluwer/Plenum: New York, pp 155-164.

Bonnesen PV, GM Brown, LB Bavoux, DJ Presley, BA Moyer, SD Alexandratos, V Patel, and R Ober.
2000. “Development of Bifunctional Anion-Exchange Resins with Improved Selectivity and Sorptive
Kinetics for Pertechnetate: Batch-Equilibrium Experiments.” Environ. Sci. Technol. 34:3761-3766.

Crank 1986

EPA—U.S. Environmental Protection Agency. 1999. Understanding Variation in Partition Coefficient,

Kd, Values; Volume I: The Kd Model, Methods of Measurement, and Application of Chemical Codes.
Office of Radiation and Indoor Air and Office of Environmental Restoration, Washington, D.C.

Gehner P, RM Lowy, and G Dunford. 2009. Secondary Waste Treatment Quantity and Composition
(WTP Solid Waste Streams.) RPP-RPT-42519, Rev. A, Pacific Northwest National Laboratory, Richland,
Washington. Washington River Protection Solutions (WRPS), Richland, Washington.

Gregor H, J Belle, and R Marcus. 1955. “Studies on Ion-exchange Resins. XIII. Selectivity Coefficients
of Quaternary Base Anion-exchange Resins Toward Univalent Anions.” J. Am. Chem. Soc. 77:2713-
2719.

Gu B, GM Brown, SD Alexandratos, R Ober, JA Dale, and S Plant. 2000a. “Efficient Treatment of

Perchlorate (ClO4-)-Contaminated Groundwater with Bifunctional Anion Exchange Resins.” In:
Perchlorate in the Environment. ET Urbansky, Ed., Kluwer/Plenum: New York, pp 165-176.

Gu B, GM Brown, PV Bonnesen, L Liang, BA Moyer, R Ober, and SD Alexandratos. 2000b.

“Development of Novel Bifunctional Anion-Exchange Resins with Improved Selectivity for Pertechnetate
Sorption from Contaminated Groundwater.” Environ. Sci. Technol. 34:1075-1080.

Guseva, LI, GS Tikhomirova, GV Buklanov, ZZ Pkhar, and IA Lebedev (1988). “Separation and
Isolation of Transplutonium Elements from Other Actinides on Ionites from Aqueous and Aqueous-
Ethanol Solutions of Sulfuric Acid.” Radiokhimiya, Vol 30, No. 1, pp. 21-25.

Herbst AK. 2002. Testing and Disposal Strategy for Secondary Wastes from Vitrification of Sodium-
Bearing Waste at the Idaho Nuclear Technology and Engineering Center. NEEL/EXT-02-00007, Idaho
National Engineering and Environmental Laboratory, Idaho Falls, Idaho.

Helfferich F. 1995. Ion Exchange. Dover Publications, New York.

5.1
Krupka KM and RJ Serne. 2002. Geochemical Factors Affecting the Behavior of Antimony, Cobalt,
Europium, Technetium, and Uranium in Vadose Sediments. PNNL-14126, Pacific Northwest National
Laboratory, Richland, Washington.

Li J and J Wang. 2006. “Advances in Cement Solidification Technology for Waste Radioactive Ion
Exchange Resins: A Review.” Journal of Hazardous Materials B135:443-448.

Li JF, ZG Hao, and JL Wang. 2005. “Solidification of Low-Level-Radioactive Resins in ASC-Zeolite

Blends.” Nuclear Engineering and Design 235:817-820.

Marina ML, FJ Esteban, and C Poitrenaud. 1996. “Study of the influence of the co-ion nature on the
nitrate-chloride ion exchange in diluted and concentrated solutions.” React. Funct. Polym.
31:31-37.

Melis S, J Markos, G Cao, and M Morbidelli. 1996. “Multicomponent equilibria on ion-exchange

resins.” Fluid Phase Equilib. 117:281-288.

Moyer BA, and PV Bonnesen. 1997. “Physical Factors in Anion Separations.” In: Supramolecular
chemistry of anions; A Bianchi, K Bowman-James, and E Garcia-Espana, Eds., VCH, New York.

Neilson RM and P Columbo. 1982. Solidification of Ion Exchange Resin Wastes. BNL-51615,
Brookhaven National Laboratory, Upton, New York.

Pan LK, BD Chang, and DS Chou. 2001. “Optimization for Solidification of Low-Level-Radioactive
Resin Using Taguchi Analysis.” Waste Management 21:767-772.

Purolite. 2007. Purolite A530E Strong Base Anion Macroporous. Product Data Sheet, Bala Cynwyd,
Pennsylvania.

Purolite. 2009. The Storage, Transportation and Preconditioning of Ion Exchange Resins. Purolite
Product Bulletin, Bala Cynwyd, Pennsylvania.

Rietveld, HM 1969. A Profile Refinement Method for Nuclear and Magnetic Structures. Journal of
Applied Crystallography, Vol. 2, pp. 65-71.

Sorg TJ, MR Schock, and DA Lytle. 1999. “Ion Exchange Softening: Effects on Metal Concentrations.”
J. Am. Water Works Assoc. 91:85-97.

Speranzini RA and LP Buckley. 1981. Treatment of Spent Ion-Exchange Resins for Disposal. AECL-
7411, Atomic Energy Canada-Chalk River Nuclear Laboratories, Chalk River, Ontario, Canada.

Tao Z and R Xiao. 1996. “Studies on ion exchange equilibria and kinetics VI. Prediction of ion
exchange equilibria of UO22+ −Na+−H+ ternary system.” J. Radioanal. Nucl. Chem. 207:71-79.

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Technology.” In: Perchlorate in the Environment; ET Urbansky, Ed.; Kluwer/Plenum: New York, pp
123-134.

5.2
 Appendix A

Technetium-99 Analytical Results from Long-Term Stability Experiment

99
Solid:Solution Tc
Ratio (µg/L)
1:1 9.93E-01
1:1 8.67E-01
1:2 5.77E-01
1:2 5.34E-01
1:5 2.59E-01
1:5 2.32E-01

Technetium-99 Analytical Results from Stability in Hot Water Experiments

99
Temperature Contact Time Tc
(°C) (hours) (µg/L)
40 6 5.51E-01
40 6 5.33E-01
40 12 5.23E-01
40 12 4.78E-01
40 24 5.19E-01
40 24 4.70E-01
60 6 5.69E-01
60 6 5.40E-01
60 12 5.34E-01
60 12 5.61E-01
60 24 5.27E-01
60 24 4.92E-01
80 6 6.33E-01
80 6 6.04E-01
80 12 6.60E-01
80 12 6.52E-01
80 24 6.81E-01
80 24 7.34E-01

A.1
Technetium-99 Analytical Results from the Resin Leach Test Experiment

Time Elapsed
99
(hours) Tc (µg/L)
2 1.85E-01
2 1.59E-01
6 1.06E-01
6 9.48E-02
24 7.93E-02
24 6.38E-02
48 6.30E-02
48 4.85E-02
72 4.68E-02
72 4.99E-02
96 5.38E-02
96 3.79E-02

Technetium-99 Analytical Results from the Method 1315 Experiment

Cumulative
99
Time (days) Tc (µg/L)
0.08 <2.05E-02
1 <2.05E-02
2 <2.05E-02
8 <2.05E-02
14 <2.05E-02

A.2
 Appendix B

Results Obtained from Previous Analysis Conducted by WSCF Laboratory on the Resin.
Data Provide to PNNL by CHPRC

Sample Numbers B234V2 & B1YCB6 Resin

WSCF20091238 W15-765 New Maximum
Constituent Units Result RQ MDL**
Anions
Fluoride mg/kg <1.49 DU 1.5
Chloride mg/kg 36.4 D 2.1
Nitrogen in Nitrate mg/kg 45.7 D 1.5
Phosphate by ion chromatography (IC) mg/kg <3.47 DU 3.5
Sulfate mg/kg <3.27 DU 3.3
Cyanide mg/kg 3,060 0.2
Hexavalent Chromium mg/kg 0.3 0.1
Metals
Antimony mg/kg <0.298 U 0.312
Arsenic mg/kg <0.398 U 0.416
Barium mg/kg <0.199 U 0.208
Beryllium mg/kg <0.399 U 0.399
Beryllium mg/kg <0.0498 U 0.052
Cadmium mg/kg <0.0995 U 0.104
Chromium mg/kg 9.56 0.52
Lead mg/kg 0.2 0.104
Mercury mg/kg <0.0498 U 0.052
Nickel mg/kg 0.31 0.208
Nitrogen in Ammonium mg/kg 12.1 8.47
Selenium mg/kg <0.298 U 0.312
Silver mg/kg 0.42 0.104
Thallium mg/kg <0.0995 U 0.104
Uranium mg/kg 0.24 0.052
Vanadium mg/kg 0.74 0.208
Zinc mg/kg <0.796 U 0.833
Volatiles
1,1,1-Trichloroethane µg/kg <5.0 U 5
1,1,2,2-Tetrachloroethane μg/kg <5.0 U 5
1,1,2-Trichloroethane μg/kg <5.0 U 5
1,1-Dichloroethane μg/kg <5.0 U 5
1,1-Dichloroethene μg/kg <5.0 U 5
1,2-Dichloroethane μg/kg <5.0 U 5
1,2-Dichloroethene μg/kg <5.0 U 5

B.1
 Results Obtained from Previous Analysis Conducted by WSCF Laboratory on the Resin.
Data Provide to PNNL by CHPRC

Sample Numbers B234V2 & B1YCB6 Resin

WSCF20091238 W15-765 New Maximum
Constituent Units Result RQ MDL**
1,2-Dichloropropane μg/kg <5.0 U 5
1-Butanol μg/kg <500 U 500
2-Butanone μg/kg <5.0 U 5
2-Hexanone μg/kg <5.0 U 5
Acetone μg/kg <5.0 U 5
Acetonitrile μg/kg <9.90 U 10
Benzene μg/kg <5.0 U 5
Bromodichloromethane μg/kg <5.0 U 5
Bromoform μg/kg <5.0 U 5
Bromomethane μg/kg <5.0 U 5
Carbon disulfide μg/kg <5.0 U 5
Carbon tetrachloride μg/kg 25,000 5
Chlorobenzene μg/kg <5.0 U 5
Chloroethane μg/kg <5.0 U 5
Chloroform μg/kg 1,800 5
Chloromethane μg/kg <5.0 U 5
cis-1,3-Dichloropropane μg/kg <5.0 U 5
Ethylbenzene μg/kg <5.0 U 5
Methylene chloride μg/kg <5.0 U 5
Styrene μg/kg <5.0 U 5
Tetrachloroethene μg/kg <5.0 U 5
Toluene μg/kg <5.0 U 5
trans-1,3-Dichloropropane μg/kg <5.0 U 5
Trichloroethene μg/kg 140 1
Vinyl Chloride μg/kg <5.0* U 5
Xylenes (total) μg/kg <5.0 U 5
Semi-Volatiles
1,2,4-Trichlorobenzene μg/L 100
1,4-Dichlorobenzene μg/L <80.0 U 80
2,4-Dinitrotoluene μg/L 25
2-Chlorophenol μg/L 25
2-methylphenol (cresol, o-) μg/L <25.0 U 25
3 & 4 Methylphenol Total μg/L <25.0 U 25
4-Chloro-3-methylphenol μg/L 25
4-Nitrophenol μg/L 150
Acenaphthene μg/L 140
Dibenz[a]anthracene μg/L <25.0 U 25

B.2
 Results Obtained from Previous Analysis Conducted by WSCF Laboratory on the Resin.
Data Provide to PNNL by CHPRC

Sample Numbers B234V2 & B1YCB6 Resin

WSCF20091238 W15-765 New Maximum
Constituent Units Result RQ MDL**
Diethylphthalate μg/L <100 U 100
Dimethyl phthalate μg/L <25.0 U 25
Di-n-butylphthalate μg/L <120 U 120
Kerosene μg/L <6,200 U 6,200
N-Nitrosodi-n-dipropylamine μg/L 30
Pentachlorophenol μg/L 50
Phenol μg/L <25.0 U 25
Pyrene μg/L 25
Total Pet HC μg/L <6,200 U 6,200
Radionuclides
Ac-228 pCi/g <57 U 57
Am-241 pCi/g <0.30 U 0.31
Am-241 pCi/g <47 U 54
Am-243 tracer by AEA pCi/g 20 0.18
Ba-133 by GEA pCi/g <11 U 11
Be-7 by GEA pCi/g <1 U 1
Bi-212 pCi/g <95 U 95
Bi-214 pCi/g <26 U 26
C-14 pCi/g 600 43.6
Ce-144 pCi/g <45 U 45
Cerium/Praseodymium-144 pCi/g <90 U 90
Co-60 pCi/g 475 0.7
Co-60 pCi/g 422 12
Cs-134 pCi/g <13 U 13
Cs-137 pCi/g <1.1 U 1.1
Cs-137 pCi/g <12 U 12
Eu-152 pCi/g <22 U 22
Eu-154 pCi/g <33 U 35
Eu-155 pCi/g <24 U 24
Gross Alpha pCi/g 4.8 2.1
Gross Beta pCi/g 17,200 2.8
H3 pCi/g 100 65.7
I-129 pCi/g <1.57 U 1.57
K-40 pCi/g <200 U 200
Nb-94 pCi/g <10 U 10
Ni-63 pCi/g <150 U 161
Np-237 pCi/g <5.01 U 18.6

B.3
 Results Obtained from Previous Analysis Conducted by WSCF Laboratory on the Resin.
Data Provide to PNNL by CHPRC

Sample Numbers B234V2 & B1YCB6 Resin

WSCF20091238 W15-765 New Maximum
Constituent Units Result RQ MDL**
Pa-231 pCi/g <0.100 U 0.13
Pb-212 pCi/g <14 U 14
Pb-214 pCi/g 26.9 16
Pu-238 pCi/g <0.32 U 0.32
Pu-239/240 by AEA pCi/g <0.085 0.096
Pu-242 pCi/g 30 0.098
Ra-226 pCi/g <26 U 26
Ra-228 pCi/g <57 U 57
Ru-103 pCi/g <9.6 U 9.6
Ru-106 pCi/g <91 U 91
Sb-125 pCi/g <2.6 U 2.6
Sb-125 pCi/g <24 U 24
Se-79 pCi/g 355 146
Sn-113 pCi/g <10 U 10
Sr-85 Tracer by Beta Counting % 94.7 0
Sr-89/90 pCi/g <84 U 100
Tc-99 pCi/g 208,000 9.96
Th-234 pCi/g <420 U 440
Tin-126 pCi/g <18 U 18
Tl-208 pCi/g <11 U 11
U-232 Tracer by AEA pCi/g 20 0.17
U-233/234 pCi/g 0.16 0.08
U-235 pCi/g <0.087 U 0.095
U-235 pCi/g <42 U 43
U-238 pCi/g <0.080 U 0.08
Zn-65 pCi/g <36 U 36
* the “< amount” indicates the Minimum Detection Limit (MDL) at the time of sampling
** the Resin Maximum MDL is the maximum MDL from the four composite samples
Note: W15-765 NEW canister was operational for 134 days.

B.4
 PNNL-XXXX

Dis trib u tio n

No of No. of
Copies Copies

EXTERNAL INTERNAL

2 DOE – Richland Operations 4 Pacific Northwest National Laboratory

John Morse (2) A5-11 KE Parker K3-62
E. M. Pierce K3-62
MM Valenta (2) P7-54
4 CH2M Hill Plateau Remediation Contractor
Sally Simmons (2) R3-60
Mark Byrnes (2) R3-60

Distr. 1