Daniel Kaplan and Carl Black
Westinghouse Savannah River Company
Aiken, SC 29808

Available for a processing fee to U.S. Department of Energy and its contractors, in paper, from: U.S. Department of Energy, Office of Scientific and Technical Information, P.O. Box 62, Oak Ridge, TN 37831-0062,  phone: (865 ) 576-8401,  fax: (865) 576-5728,  email:  reports@adonis.osti.gov

Cover Photograph: Provided by Wally Walliser. Packaging of Spent GT-73 Resin
Generated from the Effluent Treatment Facility. The Tan Granular Material is
Water Absorbent Placed at the Bottom of B-12 Disposal Box and within each
Polyethylene Bag Holding the Spent GT-73 Resin, the Darker Brown Material.

Laboratory tests were conducted for the Solid Waste Division to provide guidance as to whether resins shipped to the Nevada Test Site (NTS) would satisfy their Waste Acceptance Criteria (WAC) that waste must contain <1 vol-% free liquid. The vibration test used in this study is an operationally defined parameter that was not expected to simulate precise conditions during spent-resin transport between the Savannah River Site (SRS) and the NTS. However, the laboratory tests were expected to provide information about trends related to free moisture release. Only 0.11 wt-% (~0.12 vol-%) free moisture was measured in test resin containing the same total moisture content as spent resins sampled from B-12 boxes. This is well below the free moisture WAC at NTS of 1 vol-%. Furthermore, the total moisture content of the GT-73 waste resin was well below that expected to release >1 vol-% free moisture. Additional protection against the formation of free moisture during shipment will be provided by including water absorbing materials to the bottom of the B-12 shipping boxes and in between the polyethylene bags containing the spent resin.

In summary, these analyses indicate that the spent GT-73 resin generated at the Effluent Treatment Facility is de-watered and packaged adequately to prevent the release of unacceptable levels of free moisture during the shipment of resins to the NTS.

Solid Waste Division is presently evaluating whether to transfer spent resin generated from the Effluent Treatment Facility (ETF) to the Nevada Test Site (NTS). One of the criteria for the waste to be accepted at the NTS is that the waste must not contain more than 1 vol-% free liquid. This criterion reduces the amount of liquid, a primary vector for subsurface contaminant migration (along with colloids), introduced into the repository. This criterion also serves to reduce the chance of an accidental spill during transport of the waste to the NTS. On December 15, 1997, a shipment from Fernald to the NTS leaked some liquid waste onto a highway in Kingman, Arizona, resulting in a Type B Accident Investigation (Bradburne 1998a, 1998b). The direct cause of the leak was attributed to broken welds related to the use of substandard containers.

The overall objective of this study was to provide guidance as to whether the spent GT-73 resin would meet the free moisture WAC set by the NTS. There is no easy test available to provide such information, short of actually shipping a B-12 box to the NTS and then measuring the free moisture collected in the box. This was done with mock waste from the F- and H-Area Ground Water Treatment Facility (discussed in Kaplan and Iversen 2001a). In that demonstration, Dowex 21K and CG-8 resins released 1.53 and 3.02 wt-% free moisture, respectively. When an absorbent was added to the B-12 boxes, no free moisture was measured after the shipment. Kaplan and Iversen (2001a) also conducted free moisture determinations using the standard vibration test (ASTM D999-96) on those same wastes. The laboratory tests correctly predicted that the CG-8 resin would release more free moisture than the Dowex 21K and that the absorbent (SP 400) would retain all the free moisture released from the two resins during the actual shipment.

The general approach used in this study was to conduct a series of vibration tests with the test resins adjusted to contain varying total moisture contents. This provided data for a free moisture (y-axis) versus total moisture content (x-axis) diagram. Then using the measured total moisture content of spent GT-73 resin, the free moisture content was estimated. The advantage of this indirect method of determining free moisture (i.e., as opposed to simply measuring the free moisture of the spent resin) is that it puts the results of the vibration test in context, letting us know whether we are near the critical total moisture content where we may expect to exceed the free moisture WAC. In previous tests (Kaplan and Iversen 2001a; 2001b), a critical total moisture content was identified, above which the amount of free moisture released by the resins during the vibration tests increased dramatically, i.e., proportional to total moisture content. Again, the standardized vibration test provides only an estimate of how much free moisture will be released from the waste during transit to the NTS, and as such, should be treated only as an index and not an absolute value.

Vibration tests were conducted on a Fritsch vibratory shaker (Idar-Oberstein, Germany) at 60-Hz at an amplitude of 2-mm for 10-min (ASTM D999-96, ASTM D4253-93). There are two parameters that can be changed in the vibratory shaker test: amplitude of the shaking and the duration that the sample is shaken. The standard method (ASTM D999-96) for the vibration test does not specify either in these parameters. The procedure leaves it to the discretion of the operator to select the appropriate levels of these two parameters to reflect the scenario of interest. The amplitude of the vibratory shaker can be set between 0 and 3-mm. Based in part on the guidance from the standard method and in part on intuition, we believed an amplitude of 1.5-mm would be appropriate, but selected an amplitude of 2-mm to provide some conservatism to the test. The duration of each vibration test was set for 10-min. This duration was selected based on guidance provided in the standard method and on convenience. The effect of shake duration on the amount of water released from a sample was evaluated by Kaplan and Iversen (2001a). The amplitude and the duration used in the present studies were identical to those used in previous tests (Kaplan and Iversen 2001a, 2001b).

Solid Waste personnel provided clean and spent resin. The total moisture content of the spent resin was determined by standard methods (EPA 1989, Marton et al. 1983, Pollie 1963, Sharma and Subramanian 1970, ASTM Method D 203-96, ASTM Method D 4017-96). Briefly, approximately 5-g of spent resin was weighed before and after drying in a 105 ° C oven. The measurement was conducted in triplicate and calculated using Equation 1:

where M_w and M_s is the mass of water and dry solid present to the test vessel, respectively.

For the vibration test, 10 volumes of water were added to 50-g dry resin to obtain final moisture contents of 30, 35, 40, 41.1, 45, 50, 55, 60, 65 and 70 wt-%. These moisture contents represent three values below, one value at, and six values above that of the spent resin (which was measured to be 41.1 ± 1.2 wt-%, discussed in more detail below). The percent free moisture content was calculated using Equation 2:

where M_w/vib is the mass of water released from the vibration test.

The objective of this task was to determine whether the total moisture content in GT-73 waste recovered from B-12 boxes exceeded 1 vol-% free moisture. Because the vibration test provides only an approximation of the free moisture released from the resins during travel to NTS, a less direct approach was taken with the specific objective to determine whether the total moisture content in the GT-73 waste was above or below the critical total moisture content. This is the total moisture content, above which, free moisture content increases rapidly. The results from this series of 10 vibration tests are presented in Figure 1 (and presented in tabular form in Appendix Table 1 in Appendix A). Among the total moisture contents tested was the average moisture content of an actual waste sample collected from a B-12 box; 41.1 ± 1.2 wt-%. This value is an average of three replicates; the raw data used to generate this value are presented in Appendix Table 2 in Appendix A. The critical total moisture content is ~64 wt-% and the total moisture content that would produce 1 wt-% free moisture is slightly higher, ~65 wt-%. Both these percentages are well above the total moisture content of the GT-73 waste, indicating that it is unlikely that the GT-73 waste would release much, if any, free moisture.

The free moisture WAC at NTS is 1 vol-%. To convert the wt-% values provided by the vibration tests into units of vol-%, we measured the bulk density of fresh GT-73 resin. The mass of resin that could be tightly packed into a 100-cm³ graduated cylinder was 105.3 g, yielding a bulk density of 1.053 g/cm³. The density of the free water was assumed to be 1 g/cm³. To make a conservative estimate (a large free moisture vol-% value) we assumed that the B-12 boxes will be full of waste resin, thereby not containing any void space or space taken up by plastic bags or water absorbent (see cover photograph). Finally, the free moisture measured in the test resin containing 41.1 wt-% total moisture was 0.11 wt-% (Appendix Table 1 and Figure 1). Based on these assumptions and input parameters, the 0.11 wt-% free moisture is equal to 0.12 vol-%:

. (3)

Figure 1. Total Moisture Content Versus Free Moisture of GT-73 Resin.

These tests provide indirect evidence that the spent GT-73 resin generated at the Effluent Treatment Facility is de-watered and packaged adequately to satisfy the free moisture content WAC for NTS.

1. ASTM Method DE 203 – 96, Standard Test Method for Water Using Volumetric Karl Fisher Titration (1996).
2. ASTM Method D 999-96, Standard Methods for Vibration Testing of Shipping Containers (1996).
3. Bradburne, J., "FDR Corrective Action Plan," C:00TP:98, Rev. 2, Transmission to Jack Craig on March 18, 1998, Fluor Daniel Fernald (1998a).
4. Bradburne, J., "Leaky White, Corrective Action Report, C:00TP:98.0115, Transmission to Jack Craig on January 19, 1998, Fluor Daniel Fernald (1998b).
5. EPA, Stabilization/Solidification of CERCLA and RCRA Wastes: Physical Tests, Chemical Testing Procedures, Technology Screening, and Field Activities, EPA/625/6-89/022, Center for Environmental Research Information and Risk Reduction Engineering Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Cincinnati, OH 45268 (1989).
6. Kaplan, D. I., and G. Iversen. 2001a. Evaluation of Free Moisture in Resins Used at the F- and H-Area Groundwater Treatment Units. WSRC-TR-2000-00532, Rev. 0. Westinghouse Savannah River Company, Aiken, SC.
7. Kaplan, D. I., and G. Iversen. 2001b. Free-Moisture Content and ¹²⁹I-Kd Values of Filtercake Material Generated from the F-Area Ground Water Treatment Unit. WSRC-TR-2001-00253, Rev. 0. Westinghouse Savannah River Company, Aiken, SC.
8. Marton, A., Kocsis E. and J Inczedy, 1983, Equilibrium and Calorimetric Study of the Hydration of Anion-Exchange Resins, Talanta, vol. 30, No. 9, pp. 709-712.
9. Pollie, F.X., 1963, Determination of Moisture in Ion- Exchange Resins by Karl Fisher Reagent, Analytical Chemistry, vol. 35, p.638.
10. Sharma, H.D. and N. Subramanian, 1970, Determination of Water in Ion-Exchange Resins: Anion Exchange Resins, Analytical Chemistry, vol 42, No. 11, pp. 1287-1290.

Appendix Table 1. Total Moisture Content vs.
Free Moisture Content: Data Presented in Figure 1.

Data Entry:	Dan Kaplan – 5/28/02
QA'ed	Dan Kaplan – 6/11/02
Moisture content of spent resin sample – 41.1%
Dry Wt of resin used in vibration test – 50 g
Desired Total Moisture Content (wt-%)	Water to Add to 50 g Dry Resin (g)	Water in Pan at End of Vibration Test (g)	Free Moisture (wt-%)
30	21.4	0.122	0.17
35	26.9	0.180	0.23
40	33.3	0.132	0.16
41.1	34.9	0.091	0.11
45	40.9	0.101	0.11
50	50.0	0.122	0.12
55	61.1	0.417	0.38
60	75.0	0.474	0.38
65	92.9	5.193	3.64
70	116.7	22.615	13.57

Appendix Table 2. GT-73 Dry Weight Determinations on Spent Resin Samples
Provided by Wally Walliser (SW-ETF Waste Management Facility Support).

	Conducted by Cathy Coffey						5/28/02
	QA'ed by Dan Kaplan						5/28/02
	Lab notebook/page						WSRC-NB-2000-00045/page 55
Sample ID		Empty Pan Plus Closed Container (g)		Wet Sample Plus Pan Plus Closed Container (g)		Net Weight of Wet Sample (g)		Dry Sample Plus Plan Plus Closed Container (g)			Sample Dry wt. (g)		Moisture in Sample (g)		% Moisture Content (wt-%)	% Solids (wt-%)
Gt-1		108.410		109.680		1.270		109.140			0.730		0.540		42.5	57.5
Gt-2		108.408		109.627		1.219		109.134			0.726		0.493		40.4	59.6
Gt-3		108.407		109.577		1.170		109.105			0.698		0.472		40.3	59.7
Average															41.1	58.9
Standard Deviation															1.2	1.2