HLE-TTR-2010-004, Rev. 7

Attachment A

1.0 INTRODUCTION

The Savannah River National Laboratory (SRNL) is to:

Provide sample preparation and analysis of the Tanks 5 and 6 final characterization samples and report the results.

Perform a technical review of the task output documents in accordance with Procedure 2.60 in the E7 Manual, or equivalent method, to:

o Ensure the validity, accuracy, and completeness of the task output documents. o Validate inputs and assumptions used in the completion of the TTR and

ensure they are properly documented. Compile and provide sample analysis records to support a third party independent

validation of 5 analyte packets for one final characterization sample collected from Tank 5 and one final characterization sample collected from Tank 6. The data validation reports will be due by the end of FY2012

Revise the Task Specific Quality Assurance (QA) Plan for Tanks 5 and 6 (Document No. SRNL-RP-2010-01695), as required.

2.0 FINAL SAMPLE ANALYSIS

The Savannah River National Laboratory (SRNL) is to provide sample preparation and analysis of the Tanks 5 and 6 final characterization samples and report the results. Two (2) types of samples were collected from Tank 5, samples of the residual material on the floor of the tank and samples of the vertical cooling coils. For Tank 6, only samples of the residual material on the floor of the tank were collected. Detailed summaries of the number and types of samples collected from Tanks 5 (SRR-LWE-2010-00285, SRR-LWE-2010-00340) and the number and types of samples collected from Tank 6 (SRR-LWE-2010-00300) are provided below.

Tank 5

Fifteen (15) samples consisting of: o One (1) surface and two (2) sub-surface samples from the accumulation area

beneath Riser 1. o One (1) surface and two (2) sub-surface samples from the accumulation area

beneath Riser 5. o Nine (9) scrape samples from the other areas of the tank floor.

Two (2), twenty-four inch (24) samples of vertical sections of the cooling coils.

Tank 6

Fourteen (14) samples consisting of: o Five (5) samples from the accumulation area beneath Riser 5. o One (1) sub-surface sample from the accumulation area beneath Riser 5. o Five (5) scrape samples from accumulations in the eastern edge of the tank. o Three (3) scrape samples from the other areas of the tank floor.

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2.1 Tank 5 Sample Locations, Identification, Composition, and Preparation

2.1.1 Composite Sample Locations, Sample Location Identifiers, and Sample Composition

Figure 1 identifies the three (3) areas in Tank 5 (i.e., A, B, and C) where fifteen (15) samples of the residual solids on the floor of the tank were collected and the respective sample locations within each area. Table 1 provides the corresponding sample ID numbers and the proportions to be used to create three (3) volume-proportioned composite samples for Tank 5 (SRR-CWDA-2011-00067).

Table 1: Tank 5 Composite Samples Volumetric Distribution

Region Location

Composite Sample 1 2 3

Vol% Sample ID Vol% Sample ID Vol% Sample ID

1 Accumulation under Riser 1

50% 5-A1a-U 55% 5-A2a-BM 44% 5-A3a-BM

2 Accumulation under Riser 5

42% 5-B2a-MD 38% 5-B3a-BM 43% 5-B1a-U

3 Remainder of

the Tank

2.67% 5-C1a 2.33% 5-C1b 4.33% 5-C1c 2.67% 5-C2b 2.33% 5-C2c 4.33% 5-C2a 2.67% 5-C3c 2.33% 5-C3a 4.33% 5-C3b

Total 100% 100% 100% For example: 50 vol% of Composite Sample 1 should come from sample 5-A1a-U

2.1.2 Composite Sample Preparation and Residual Sample Preservation

The following customer specified preparations are required to be completed by SRNL prior to SRNL initiating analysis of the samples.

Determine the “as received” and dry bulk densities of each sample. Individually dry, grind, and homogenize each sample for compositing and return the

samples to their respective sample vials. Create three (3) weight-proportioned composite samples based on the volume

proportions specified in Table 1. Note, Table 1 reflects a compositing scheme that differs from the compositing scheme provided in the Tank 5 Sampling and Analysis Plan (SRR-LWE-2010-00285). The revised compositing scheme was developed based on:

o Lessons learned from unsuccessful efforts undertaken to collect core samples from beneath Risers 1 and 5, which resulted in the development of a revised sampling strategy (SRR-LWE-2010-00340).

o Building the volume uncertainty directly into the composite samples, thus eliminating the need to adjust for uncertainty in the sample analysis results (SRR-CWDA-2011-00067).

o Avoiding confusion with the sample identification scheme. The sample identification scheme was based on incorporating a sample set number to uniquely identify the samples supporting the sample composite sample (e.g., a “1” for samples associated with the 1st composite sample). The sample identification scheme was disrupted when additional samples needed to be collected to address unsuccessful efforts to collect core samples from Tank 5.

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There was a concern that using a consistent sample identification scheme for some samples, but not for others, could be confusing to those building the compositing samples and lead to errors. Since it was possible to use equivalent samples from each of the regions, mixing of the sample identifications was used to avoid confusion.

Determine the weight percent (Wt%) solids for each composite sample.

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Figure 1: Tank 5 Sample Locations

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2.1.3 Cooling Coil Sample Locations and Sample Location Identifiers

Two (2) samples of a vertical cooling coil in Tank 5 were obtained from Riser 1 (Refer to Figure 1), with one (1) sample from a section of a vertical cooling coil located above the 45 elevation of the tank (designated as Sample ID Number 5-R1-A45) and the other sample from a vertical section of a cooling coil located below the 45 elevation of the tank (designated as Sample ID Number 5-R1-B45).

2.1.4 Cooling Coil Sample Preparation and Residual Sample Preservation

No customer specified preparations are required for the cooling coil samples prior to analysis.

2.2 Tank 6 Sample Locations, Identification, Composition, and Preparation

2.2.1 Composite Sample Locations, Sample Location Identifiers, and Sample Composition

Figure 2 identifies the three (3) areas in Tank 6 (i.e., A, B, and C) where fourteen (14) samples of the residual solids on the floor of the tank have been collected and the respective sample locations within each area. Table 2 provides the corresponding sample ID numbers and the volume proportion to be used to create three (3) volume-proportioned composite samples for Tank 6. [SRR-CWDA-2011-00172] Section 2.6 provides an example of the Volume Proportional Composite Sample Calculation.

Table 2: Tank 6 Sample ID Numbers and Composite Sample Proportions

Composite Sample 1 2 3

Region Location Vol% Sample ID Vol% Sample ID Vol% Sample ID

1 SW

Accumulation 31% 6-A1a 27% 6-A2a 25% 6-A3a 31% 6-A1b 27% 6-A2b 25% 6-A3b

2 East

Accumulation 11.5% 6-B1a 13% 6-B2a

31% 6-B3b 11.5% 6-B1b 13% 6-B2b

3 Remainder of

the Tank 15% 6-C1a 20% 6-C2a 19% 6-C3a

Total 100% 100% 100% c See Reference 6 on how to accommodate the lack of sample B3a being delivered to SRNL for analysis.

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Figure 2: Tank 6 Sample Locations

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2.2.2 Composite Sample Preparation and Residual Sample Preservation

The following customer specified preparations are required to be completed by SRNL prior to SRNL initiating analysis of the samples.

Determine the “as received” and dry bulk densities of each sample. Individually dry, grind, and homogenize each sample for compositing and return the

samples to their respective sample vials. Contact Closure Project Engineering to obtain the final volume proportions to be used

to create the three (3) weight-proportioned composite samples from the samples. The final volumetric proportions are provided in Tables 1 and 2. [SRR-CWDA-2011-00067, SRR-CWDA-2011-00172]

For SRNL standard sample preparation activities, which need to be initiated before the final volume proportions are available, refer to the preliminary volume proportion estimates specified in Table 2.

Create three (3) weight-proportioned composite samples based on the final volume proportions specified by Closure Project Engineering.

Determine the weight percent (Wt%) solids for each composite sample.

2.3 Control and Tracking of Tanks 5 and 6 Samples at SRNL

When the Tanks 5 and 6 samples are delivered to the Shielded Cells Control, tracking of the samples is to be maintained by the SRNL in accordance with the requirements specified in Procedure 2.33 of the SRNL L1 Manual. When the Tanks 5 and 6 samples are sent from the Shielded Cells to the Analytical Development (AD) group, a unique AD Laboratory Information Management System (LIMS) Number is obtained and cross-referenced to the Tank 5 Sample ID Number.

2.4 Sample Analysis

For the Tank 5 and 6 composite samples, SRNL will perform triplicate analyses for the target radiological analytes specified in Table 3 and for the chemical and elemental analytes specified in Table 4. For the Tank 5 cooling coil samples, SRNL will perform triplicate analyses of radionuclides on the cooling coil samples for the target radiological analytes specified in Table 5. SRNL is to develop new or modified analytical methods to meet the requested detection limits specified in Tables 3 and 5, as required.

The target detection limits for analytes in Table 3 denoted with a double asterisk are expected to be confirmatory in nature and a significant challenge due to interfering species in the sludge. Special emphasis will be placed on achieving these target detection limits for at least one composite sample. Only one replicate per sample is required for these analytes.

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Table 3: Radiological Analytes for Composite Sample Analysis

Analytes

Target Detection

Limit Unit Analytes

Target Detection

Limit Unit H-3 1.0E-01 Ci/g Ac-227** 1.3E-04 Ci/g C-14 1.0E-01 Ci/g Th-229** 1.0E-03 Ci/g

Al-26* 1.0E-03 Ci/g Th-230** 1.0E-03 Ci/g Cl-36* 1.0E-03 Ci/g Pa-231** 1.0E-03 Ci/g K-40* 1.0E-03 Ci/g U-232 1.0E-03 Ci/g Ni-59 9.0E-02 Ci/g U-233 1.0E-03 Ci/g Ni-63 1.0E-01 Ci/g U-234 1.0E-03 Ci/g Co-60 1.0E-03 Ci/g U-235 1.0E-04 Ci/g Se-79 1.0E-03 Ci/g U-236 1.0E-03 Ci/g Sr-90 1.0E-03 Ci/g U-238 1.0E-03 Ci/g Y-90 1.0E-03 Ci/g Np-237 1.0E-03 Ci/g Zr-93 1.0E-03 Ci/g Pu-238 1.0E-03 Ci/g

Nb-94** 3.0E-03 Ci/g Pu-239 1.0E-03 Ci/g Tc-99 1.0E-03 Ci/g Pu-240 1.0E-03 Ci/g

Pd-107* 1.0E-03 Ci/g Pu-241 1.0E-03 Ci/g Sn-126 1.0E-03 Ci/g Pu-242 1.0E-03 Ci/g Sb-126 1.0E-03 Ci/g Pu-244 1.3E-04 Ci/g

Sb-126m 1.0E-03 Ci/g Am-241 1.0E-03 Ci/g I-129 1.0E-04 Ci/g Am-242m 1.0E-03 Ci/g

Cs-135 5.0E-02 Ci/g Am-243 1.0E-03 Ci/g Cs-137 1.0E-03 Ci/g Cm-243 2.0E-02 Ci/g

Ba-137m 1.0E-03 Ci/g Cm-244 1.0E-03 Ci/g Sm-151 3.0E+00 Ci/g Cm-245 2.0E-02 Ci/g Eu-152 7.0E-03 Ci/g Cm-247 1.3E-04 Ci/g Eu-154 1.0E-03 Ci/g Cm-248 1.3E-04 Ci/g

Pt-193*,** 1.0E-03 Ci/g Cf-249 5.0E-03 Ci/g Ra-226** 5.0E-03 Ci/g

* Tank 5 only ** While analysis of these isotopes is needed, meeting the detection limits for these isotopes is a lower priority than meeting detection limits for the other specified isotopes.

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Table 4: Elemental and Chemical Analytes for Composite Sample Analysis

Ag Hg Al I* As Mn B Mo Ba Ni Cd Pb Co Sb Cr Se Cu Sr F U Fe Zn

Chloride Sulfate Nitrate Phosphate Nitrite

SRR-CWDA-2011-00162 * Tank 6 only

Table 5: Radiological Analytes for Cooling Coil Analysis

Analytes

Target Detection

Limit Unit Co-60 8.3E-06 Ci/ft2

Sr-90 5.9E-02 Ci/ft2 Cs-137 4.2E-03 Ci/ft2 U-233 1.1E-07 Ci/ft2 U-234 7.8E-08 Ci/ft2 U-235 2.7E-09 Ci/ft2 U-236 4.6E-07 Ci/ft2 U-238 7.8E-08 Ci/ft2

Np-237 1.1E-07 Ci/ft2 Pu-238 6.5E-05 Ci/ft2 Pu-239 1.5E-05 Ci/ft2 Pu-240 3.3E-06 Ci/ft2 Pu-241 1.5E-05 Ci/ft2 Pu-242 4.6E-07 Ci/ft2 Pu-244 2.3E-09 Ci/ft2 Am-241 2.7E-04 Ci/ft2

SRR-CWDA-2009-00045

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2.5 Reporting Sample Analysis Results

SRNL is to provide separate written reports of the results of the Tank 5 residual solids sample analyses, Tank 5 cooling coil sample analyses, and Tank 6 residual solids sample analyses. The reports are to reflect the respective Tank Sample ID Numbers and the corresponding SRNL Sample ID Number(s), if applicable, and LIMS Number(s) associated with each result. In addition, the date each sample is received should be reported.

The report documenting the sample analysis results should include the following:

A description of any abnormalities concerning sample receipt, preparation, analysis, or calculations. A brief description and resolution of the abnormality is sufficient.

A summary of the results for each constituent for mean and standard deviation. In addition, the individual replicate results should be included, in an appendix is acceptable.

Any results from additional constituents not requested here should also be included in the report.

Analysis results reported in terms of µCi/g or Ci/ft2 for radiological constituents and Wt% for non-radiological constituents.

Separate tables for each composite sample’s analysis results. The radiological, elemental, and leached results should be reported separately. Reporting tables should be sorted based on the constituent alphabetically or by atomic number and mass.

Density measurements of individual replicate analyses for "as received" and "homogenized" bulk density for each sample.

2.6 Volume Proportional Composite Sample Calculation Example

The composite sample would be constructed using a volume-proportioning scheme. The composite sample is initially assumed to have a volume of 70 ml with an assumed density of 1.0 g/ml. This 70 ml = 70 g assumption can be used to estimate the approximate composite sample mass needed for a sample location. This provides a conservative composite sample volume since the expected composite sample density is greater than 1.0 g/ml.

To calculate the actual sample mass required for a sample location, the volume must be corrected for the measured sample density using the following formula. For this example, the composite sample mass results in 101.47 grams.

Where:

= Volumetric sample mass (grams)

= Composite sample volume (ml)

= Tank volume proportion at sample location (%)

= “as received” bulk density (g/ml)

The ratio of the mass for each sample location to the 101.47 gram total sample mass times the 70 gram total composite sample volume is then used to calculate the Required Sample Mass for Compositing from each sample.

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Table 6 provides an example using the hypothetical sample densities, which are to be replaced with the actual densities when determined by the SRNL.

Table 6: Example of Volume-Proportional Composite Sample Calculation

Sample Location

Composite Sample

Proportion of Tank Volume

(%)

Measured “As Received” Bulk Density (g/ml)

Volumetric Sample Massa

(grams)

Required Sample Mass

for Compositinga

(Grams) Accumulation under

Riser 5 30 1.42 29.82 20.57

Accumulation under Riser 5 30 1.55 32.55 22.45

Floor (NE) 15 1.36 14.28 9.85 Floor (N) 15 1.53 16.07 11.09 Floor (S) 10 1.25 8.75 6.04

Total Mass 101.47 70.0 a Hypothetical values

2.7 Statistical Analysis of Sample Analysis Results

A statistical analysis of the three composite sample analysis results should be performed for the constituents listed in Table 7. The analysis should be performed on the results reported in the sample analysis report. This analysis should include a comparison of the sample to sample variance component to the measurement error (typically an ANOVA). The mean concentrations standard deviations and one-sided upper 95% confidence limits for the mean concentrations for each radiological constituent listed in Table 7 should be determined.

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Table 7: Tanks 5 and 6 Constituents for Statistical Evaluation

Density Eu-152 Ra-226 Ag Mn Ac-227 Eu-154 Sb-126 Al Mo Al-26* H-3 Sb-126m As Ni

Am-241 I-129 Se-79 B NO2-1

Am-242m K-40* Sm-151 Ba NO3-1

Am-243 Nb-94 Sn-126 Cd Pb Ba-137m Ni-59 Sr-90 Cl-1 PO4

-3 C-14 Ni-63 Tc-99 Co Sb

Cf-249 Np-237 Th-229 Cr Se Cl-36* Pa-231 Th-230 Cu SO4

-2 Cm-243 Pd-107* U-232 F Sr Cm-244 Pt-193* U-233 Fe U Cm-245 Pu-238 U-234 Hg Zn Cm-247 Pu-239 U-235 I** Wt% Solids Cm-248 Pu-240 U-236 Co-60 Pu-241 U-238 Cs-135 Pu-242 Y-90 Cs-137 Pu-244 Zr-93

* Tank 5 only ** Tank 6 only

2.8 Sample Retention

All samples should be retained until sample analysis reports are issued for both tanks. Once the sample analysis is complete, the discrete samples, including the cooling coil samples, no longer need to be retained, except where noted below for Tank 5. Once both tanks are grouted, the composite sample material no longer needs to be retained. In a future revision, the amount of each composite sample to be retained will be provided.

3.0 ANALYTICAL DATA PACKAGE COMPILATION FOR TANKS 5 AND 6 SAMPLES

SRNL is to compile and provide sample analysis records to support a third party validation of 5 analyte packets for one final characterization sample collected from Tank 5 and one final characterization sample collected from Tank 6. The five analyte packets for both tanks are a Mn packet, PuTTA packet (Pu-238, Pu-239 and Pu-240 combined, and Pu-241), I-129 packet, gamma packet, and Cs removed gamma packet. The gamma and Cs removed gamma packets should include isotopes common to both methods. The data packages will contain all that data and supplemental information to demonstrate data quality per the Measurement Performance Criteria (MPC) identified in the LWTRS QAPP. [SRR-CWDA-2011-00117] It should be noted that the Tanks 5 and 6 analyses preceded the LWTRS QAPP approval and that the MPC will be used as appropriate. SRNL is to:

Retrieve the final data packages from storage locations for the 5 analytes from Tank 5 Composite Sample No. 3 and Tank 6 Composite Sample No. 3.

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Compile and organize laboratory analytical records to support third party data validation (DV) for the 5 analytes.

Prepare a case narrative describing the processing and analysis for each sample and requested analyte, explain missing or not applicable DV elements, and describe deviations.

Provide copies of the calibration data associated with the respective analyses and compile results for respective quality control samples.

Provide documentation that explains the calculations provided on spreadsheets (i.e., how the raw data is converted to a final result).

Provide requested information and provide support to and respond to inquiries from the organization conducting the third party validation of the data packages.

Interact with EPA and/or SCDHEC, as required, to address additional comments and/or questions regarding the sample analysis records.

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4.0 REFERENCES

E7 Manual, Procedure 2.60, Technical Reviews, Savannah River Site, Aiken, SC, Revision 13, March 1, 2010.

L1 Manual, Procedure 2.33, Radioactive Sample Labeling and Tracking in the Shielded Cells, L1, Manual, Savannah River National Laboratory, Aiken, SC, Revision 2, November 18, 20

SRNL-RP-2010-01695, Oji, L. et. al., Task Technical and Quality Assurance Plan for Analysis of the Tank 5F and Tank 6F Final Characterization Samples-2011, Savannah River Site, Aiken, SC, Revision 1, December 7, 2011.

SRR-CWDA-2009-00045, Dean, B., F-Tank Farm Waste Tank Closure Inventory for Use in Performance Assessment Modeling, Savannah River Site, Aiken, SC, Revision 1, January 26, 2010.

SRR-CWDA-2011-00067, Dean, B., Tank 5 Composite Samples Volumetric Proportions, Savannah River Site, Aiken, SC, Revision 1, April 20, 2011.

SRR-CWDA-2011-00117, Pavletich, J., Liquid Waste Tank Residuals Sampling-Quality Assurance Program Plan, Savannah River Site, Aiken, SC, Revision 0, February 29, 2012.

SRR-CWDA-2011-00159, Martin, B., Justification for Adjustments to the Tank 6 Sample Plan, Aiken, SC, Revision 0, October 2011.

SRR-CWDA-2011-00162, Wiggins, A., Tanks 18 and 19 Chemical Screening for Residual Inventory Determination, Savannah River Site, Aiken, SC, Revision 0, October 2011.

SRR-CWDA-2011-00172, Dean, B., Tank 6 Composite Samples Volumetric Proportions, Savannah River Site, Aiken, SC, Revision 0, November 10, 2011.

SRR-LWE-2010-00285, Broaden, D., Tank 5 Sampling and Analysis Plan, Savannah River Site, Aiken, SC, Revision 1, November 15, 2010.

SRR-LWE-2010-00340, Broaden, D., Addendum to the Tank 5 Sampling and Analysis Plan, Savannah River Site, Aiken, SC, Revision 0, December 15, 2010.

SRR-LWE-2010-00300, Broaden, D., Tank 6 Sampling and Analysis Plan, Savannah River Site, Aiken, SC, Revision 1, January 5, 2011.

SRR-LWE-2011-00209, Hughes, W.M., Tank 6 Sampling and Analysis Plan Addendum, Savannah River Site, Aiken, SC, Rev. 0, August 29, 2011.

SRR-LWE-2011-00235, Carroll, P.E., Tank 6 Sampling and Analysis Plan Addendum #2, Savannah River Site, Aiken, SC, Rev. 0, October, 2011.