LAB-RPT-18-00003 Revision 0 Plutonium Particle Examination by Scanning Electron Microscopy Analysis of Plutonium Finishing Plant Air Filters and Tech Smears Prepared for the US. Department of Energy Assistant Secretary for Environmental Management Contractor for the U.S. Department of Energy Of?ce of River Protection under Contract washington river protectionso/utions P.0. Box 850 Richland, Washington 99352 Approved for Public Release; Further Dissemination Unlimited Revision 0 Plutonium Particle Examination by Scanning Electron Microscopy Analysis of Plutonium Finishing Plant Air Filters and Tech Smears J.S.Page Washington River Protection Solutions Date Published March 2018 WRPS Prepared for the US. Department of Energy Assistant Secretary for Environmental Management Contractor for the U.S. Department of Energy Of?ce of River Protection under Contract DE-A027-08RV14800 washingtonriver protectionsolurions P.0. Box 850 Richland, Washington 99352 0) Copyright License By acceptance of this article, the publisher andr?or recipient acknowledges the US. Government's right to retain a non exclusive, royalty-free license in and to any copyright covering this paper. 8 By Mary P. Curry at 4:38 pm, May 10, 201 Release Approval Date Approved for Public Release; Further Dissemination Unlimited Revision 0 LEGAL DISCLAIMER This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy. completeness, or any third party's use or the results of such use of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any speci?c commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof or its contractors or subcontractors. The views and opinions of authors expressed herein do not necessarily state or re?ect those of the United States Government or any agency thereof. This report has been reproduced from the best available copy. Printed in the United States of America R0 Plutonium Particle Examination by Scanning Electron Microscopy Analysis of Plutonium Finishing Plant Air Filters and Tech Smears J. S. Page Washington River Protection Solutions LLC Date Published March 201 8 A washington river protection solutions Prepared for the US. Department of Energy Of?ce of River Protection Contract No. R0 Table of Contents 1 Introduction .. 4 2 Method ..4 3 Analysis Results ..6 3.1 B3HLY5 (29) .. 6 3.2 B3HLY3 (28) .. 12 3.3 B3HLX5 (10) .. 15 4 References .. 19 List of Figures Figure 1. SEM Image of Several Particles and Their Measured Sizes as Found on Sample 818R000009 . 7 Figure 2. Results Summary of the Automated Runs on Sample .. 7 Figure 3. Image and Spectrum of a Large Plutonium Particle on Sample S18R000009 .. 8 Figure 4. Image and Spectrum of a Plutonium Particle Detected on Sample 818R000009 .. 8 Figure 5. Image and Spectrum of another Larger Plutonium Particle on Sample .. 8 Figure 6. Image and Spectrum of a Smaller Plutonium Particle on Sample ..9 Figure 7. Image and Spectrum of a Small Plutonium Particle on T0p of a Larger Soil Particle on Sample .. 9 Figure 8. Image and Spectrum of a Crushed Plutonium Particle on Sample 1 8R000009 .. 9 Figure 9. Elemental Mapping Results of a Large Plutonium Particle Showing the Location of Selected Elements in the Images .. 10 Figure 10. A Plutonium Particle with Elongated Morphology from the 261-Z-9 Crib .. 11 Figure 11. A to Plutonium Particle from the 261-Z-9 Crib .. 11 Figure 12. Image Showing Particles Typical in Sample SR18000011 with Several Measured for 13 Figure 13. Summary of the Automated Feature Analysis Run on Sample 81811000011 .. 13 Figure 14. Images of a Plutonium Particle on Sample S18R000011 Before and After it Rolled on the Surface .. 14 Figure 15. Image and Spectra of a Plutonium Particle on Sample .. 14 Figure 16. Typical Particles and Measured Sizes on Sample .. 16 Figure 17. Summary of the Automated Feature Analysis Results for Sample .. 16 Figure 18. Images and Spectra of Plutonium Particles Measured by the Automated Feature Analysis on Sample .. 17 Figure 19. Manual Analysis of a Plutonium Particle in Sample S18R000029 .. 18 List of Terms Acronyms and Abbreviations AF A automated feature analysis EDS energy dispersive spectrometry PAM portable alpha meter PFP Plutonium Finishing Plant SEM scanning electron microscopy Units disintegrations per minute keV kiloelectron volt um micrometer LAB-RPT-18-00003 R0 LAB-RPT-18-00003 R0 1 INTRODUCTION Under the direction from the Statement of Work titled, ?Managed Task Analysis of Air Filters by Scanning Electron Microscopy,? 30 samples were received at the 222-S Laboratory for scanning electron microscopy with energy dispersive spectrometry analysis, client sample request 222S20180187. Fifteen of these samples were blanks and were used as a reference to obtain information on the clean media. The analysis results, consisting of images and elemental analysis of particles observed and particle sizes for all 15 ?eld samples and 3 of the blank samples, were reported in R1, ?Scanning Electron Microscopy Energy Dispersive Spectrometry Analysis of Plutonium Finishing Plant Air Filter and Tech Smears.? Most of the detected particulate was typical Hanford soil material and demolition debris with trace unique particles such as plutonium, barium sulfate, lead, and cerium?rich phases. Most of the ?eld samples had reported alpha radiation levels of less than one hundred to several hundred decays per minute, but four of the samples had alpha levels over 10,000 dpm. All plutonium particles detected and reported were found on three of these four high-level samples. This report focuses solely on the plutonium particles detected in this analysis, as requested by the customer, see Attachment A. The results of the three samples where plutonium particles were found by SEM are presented for each sample individually, but the discussion of the plutonium phase and its characteristics is can'ied throughout as the plutonium particles were similar across all three samples, suggesting the same origination. In addition, the plutonium particles found on these recent samples are compared to plutonium particles from the 216-Z-9 trench to provide more information on the source of origination. 2 METHOD The samples were received on January 18, 2018. All the samples were adhered to 2-inch metal planchets and were contained in cardboard holders. They were photographed and then analyzed by no additional preparation steps were performed prior to analysis. Each sample was loaded individually into the SEM instrument by placing the entire planchet onto the sample stage. The specimens were analyzed according to the laboratory technical procedure, 161?103, ?222?8 Laboratory Technology Procedure for the ASPEX Explorer Scanning Electron Microscope,? and the analysis was documented in the SEM laboratory notebook, Instrument Notebook.? The analysis was done at a 25 keV accelerating voltage using the variable pressure mode (0.1 Torr), which allowed the samples to be analyzed without carbon coating. The backscatter electron detector was used for the entire sample set, and the EDS acquisition time was 30 seconds in manual mode. In addition, the samples were analyzed using the automated feature analysis (AFA) routine on the SEM to speci?cally look for plutonium-rich particles. This routine automatically progressed through a de?ned sample area in a continuous step?wise fashion, across the sample surface, measuring particles containing high mass elements. The tabulated particles were then manually evaluated to determine which contained plutonium, and these particles were reimaged manually. PFP Plutonium Finishing Plant LAB-RPT-18-00003 R0 The alpha counts were also measured on all the samples at the 222-8 Laboratory by radiological personnel using a portable alpha meter (PAM) model 2360. Total counts were recorded for one minute and a disintegrations per minute value was calculated (measured alpha activity). These results are shown for each sample along with the reported alpha counts in the body of this report. The reported alpha activity was provided by PFP personnel and acquired on their radiological instruments. R0 3 ANALYSIS RESULTS 3.1 B3HLY5 (29) S18R000009 Reported Alpha Activity: 15,830 Measured Alpha Activity: 7432 Sample was a tech smear taken from a location on a vehicle. Visually, the smear was nearly covered with a brown residue. The SEM analysis showed the smear to be heavily loaded soil mineral particles with a large range in size from sub- micrometer to up to ~200 um (Figure The AFA run was set up with a de?ned area on the tech smear that visually exhibited the most particulate, with the brightness and S18R000009 contrast of the backseatter detector adjusted to eliminate lower 2 mass elements. Due to the heavy particulate load of this sample, two separate AF A runs were combined that totaled ~14 hours of analysis and resulted in over 8000 detected and measured particles . .. that were classi?ed as ?defined? in a rule ?le supplied by the vendor (Figure 2). The majority of these particles were iron-rich phases. GROUP: 2018018? F: PFP Tech Smears suPuD: 3311135 The resulting AFA data was manually evaluated by looking at all the collected EDS spectrum of detected particles with a reported potassium level above 5% (potassium was used to mark the presence of plutonium in the EDS spectrum due to the good X-ray overlap of its K-lines with the plutonium M?lines since plutonium X?ray information was not supplied in the instrument?s rule This data analysis indicated that six particles displayed an EDS spectrum that matched plutonium. These six particles were then found manually on the sample using the reported coordinates from the AF A run, and several images and EDS spectra were acquired confn'ming the presence of plutonium (Figures 3 through 8). The size measurement of these particles showed that the two larger plutonium particles were ~100 um and ~50 um across while the smaller particles were around 5 to 10 pm in size. One of the particles appears to have been crushed during sampling (Figure 8), suggesting this plutonium phase is friable. It is of interest to note that the EDS analysis shows silicon is associated with all six plutonium particles. It has also been reported that silicon was part of an unwanted material derived from processes at the Plutonium Reclamation Facility where it was observed with plutonium and an organic material to form a crud that would cause dif?culties in the facility?s reclamation processes, PNNL-25888, ?Literature Review: Crud Formation at the Liquid/ Liquid Interface during TBP-based Solvent?Extraction Process.? 1 The elemental composition of the larger plutonium particle was further explored by performing an EDS mapping which produced pseudo?images based upon the detected X-rays of selected elements (Figure 9). The results indicate that the phosphorous observed in the EDS spectra of 2 is a trademark of Columbia Energy and Environmental Services, Richland, Washington. 6 R0 the plutonium particles is solely associated with the plutonium and is not found in the other background particulate (mineral particles). Figure 1. SEM Image of Several Particles and Their Measured Sizes as Found on Sample 818R000009 Figure 2. Results Summary of the Automated Runs on Sample . Starting 02-13-2018PFP.afa Particle count bv class: All Particles Detected and Measured Results in c:\AFAData\48 Rule Name Count Beginning of Analysis Iron-Titanium 2943 Starting Run_1 with field 1 at Iron mm 2936 2:56:16 PM on 2/13/2018. Garnet 423 Initial emission: uA Misc. Silicates 252 .I .. [2:56:16 Other 166 Barium Sulfate 71 i Result summary: Barium Rich 60 Data Filename Stainless Steel 57 Cerium Rich 44 Beam Energy 25 kV Titanium 29 . Distance 16.2 mm Zircon 26 Spot 30% Lead Rich 8 Detector BSED Strontium-bearing 3 Contrast 100% Brightness -33.9% Stub Client name CHZM Hill Detail 15,830 Description PFP Smear Area 123.721 mm2 LAB-RPT-18-00003 R0 Figure 3. Image and Spectrum of a Large Plutonium Particle on Sample SISR000009 0.000 71000- 0000- 5.000- If) 5 4.000 0 3.000 2000- 1.0001'0 1'1 1'2 1'3 1'4' 15 Figure 5. Image and Spectrum of another Larger Plutonium Particle on Sample S18R000009 Pu 10.000- 8,000? 5000- 0 '19 4,000? I 2,000- 9111115LAB-RPT-18-00003 R0 Figure 6. Image and Spectrum of a Smaller Plutonium Particle on Sample S18R000009 Pu . 4:33 pm Figure 7. Image and Spectrum of a Small Plutonium Particle on Top of a Larger Soil Particle on Sample LAB-RPT-18-00003 R0 Figure 9. Elemental Mapping Results of a Large Plutonium Particle Showing the Location of Selected Elements in the Images Backseatter Detector Oxygen Aluminum Silicon 3-. 9 .1 Plutonium A previous report characterized plutonium?bearing particles from the crib located near PFP (LAB-RPT-12-00006, ?Characterization of Plutonium-Bearing Waste in the High-Level Waste Storage Tanks 18, and 241-AZ-101 and the Plutonium Finishing Plant Crib?). That document reports the observed plutonium particles from the crib had a size range of 5 to 26 um and consisted of either a plutonium oxide phase or an undetermined plutonium-rich phase (Figures 10 and 1 1). There was evidence of trace to only moderate levels of phosphate and silicon in the plutonium particles from the crib, compared to the higher levels detected in all the plutonium particles on the PFP smear sample. This suggests likely different plutonium sources between the crib and smear samples. 10 R0 Figure 10. A Plutonium Particle with Elongated Morphology from the 261-Z-9 Crib Figure 11. A to Plutonium Particle from the Crib ll LAB-RPT-18-00003 R0 3.2 B3HLY3 (28) 818R000011 Reported Alpha Activity: 13,600 Measured Alpha Activity: 3766 Similar to sample sample was a tech smear taken from a location on a vehicle. Visually, the smear had a slight, dark discoloration across the surface. The SEM analysis - r' - showed mineral particles embedded in the ?bers ranging in size mwi?tmw from sub-micrometer up to ~30 um (Figure 12). An AFA run was Ema? .. performed to search for plutonium particles. The run was set up with a de?ned area on the tech smear that visually exhibited the S13R000011 most particulate, with the brightness and contrast of the snow: 20180?? backscatter detector adjusted to eliminate lower mass elements. p; PFP ?ch 3mm The 65-hour automated run resulted in over 150 detected and sumumnua measured particles which were classi?ed as ?de?ned? in a rule ?le supplied by the vendor (Figure 13). The majority of these particles were classi?ed as iron-rich mineral phases. The resulting AFA data was manually evaluated by looking at all the collected EDS spectrum of detected particles with a reported potassium level above 5% (potassium was used to mark the presence of plutonium). This data analysis indicated that only one particle had an EDS spectrum that matched plutonium. This particle was then found manually on the sample using the reported coordinates from the AP A run, and several images and EDS spectra were taken. During the manual analysis, the plutonium particle rolled on the sample. Figure 14 shows two images of the same particle before and after a roll. The dark material on the particle in the left image was not analyzed by EDS because the particle rolled before this could be performed, but it appears to be a carbon-rich material adhered to the surface. Figure 15 contains the results of the EDS analysis at three different locations on the particle. Spot #2 shows a mineral phase on or adhered to the surface, and spots #1 and #3 are from a bare location on the particle. Both of these bare locations indicate that the phase is a plutonium oxide with trace phosphorous and silicon in or on the particle. The elemental content of this plutonium particle is more consistent with the 26l?Z-9 crib plutonium particles. 12 R0 Figure 12. Image Showing Particles Typical in Sample SR18000011 with Several Measured for Size Figure 13. Summary of the Automated Feature Analysis Run on Sample All Particles Detected and Measured 13 Starting 02-12-2018PFP.afa Results in Beginning of Analysis Starting Run__1 with field 1 at 2:41:49 PM on 2/12/2018. Initial emission: l=33.500 [2:41:49 Result summary: Data Filename Beam Energy 25 kV Working Distance 14.6 mm Spot 30% Detector BSED Contrast 100% Brightness -34.4% Stub Client name CHZM Hill Detail 13,600 Description PFP Smear Area 534.210 Particle count by class: Rule Name Iron-Titanium Iron Rich Barium Rich Stainless Steel Cerium Rich Other Brass Lead Rich Barium Sulfate Misc. Silicates Zinc Misc. salts Count 44 47 15 12 NNw-b-th'ILH-a R0 Figure 14. Images of a Plutonium Particle on Sample S18R000011 Before and After it Rolled on the Surface Figure 15. Image and Spectra of a Plutonium Particle on Sample PU Fe Pu Mg I 2 mo- ILP {I'14.000 '3 12000 10003? 3 3000 0 Y. 5000 4000 0 2000 em Fe . .- . "0123450700101112131:15 EU 14 R0 3.3 B3HLX5 (10) Reported Alpha Activity: 11,570 Measured Alpha Activity: 469 Sample was a tech smear with a darkened smudge across the surface. The SEM analysis showed mostly mineral matter on, and embedded in, the ?bers of the sample. The majority 76: of these particles were mineral phases sub-micrometer to ~20 pm in a? @0900 Size With some larger particles scattered throughout (Figure 16). 0 An AFA run was performed to search for plutonium particles. The eaaQ?b-w. run was set up with a de?ned area on the tech smear that exhibited the most particulate, with the brightness and contrast of the backseatter detector adjusted to eliminate lower mass elements. The 8-hour automated run resulted in over 3600 detected and measured particles which were classi?ed as ?de?ned? in a rule ?le supplied by the vendor (Figure 17). The resulting data was manually evaluated by focusing on all detected particles with a reported potassium level above 5% (potassium was used to mark the presence of plutonium). This data analysis showed that a total of two plutonium particles were found (Figure 18). Manual analysis of these two plutonium particles was attempted by returning to the reported particle locations on the sample, but only one of the two particles was found manually. The images and EDS spectrum in Figure 19 Show this particle. Many of the detected elements in the spectrum are probably associated with neighboring particles due to the relatively small size of the plutonium particle, but the phosphorous seems to be associated with the plutonium as it was seen in both particles in the AFA run. 15 8-00003 R0 Figure 16. Typical Particles and Measured Sizes on Sample Figure 17. Summary of the Automated Feature Analysis Results for Sample All Particles Detected and Measured Starting 02-06-2018PFP.afa Particle count by ciass: . Results in Rule Name Count :11: Beginning of Analysis Other 958 Starting Run_1 with field 1 at 3:03:15 Iron Rich 890 . 9, pM on 2/5/2013. Misc Metal 544 . 5. lnitialemission: Iron-Titanium 231 Barium Rich 95 if; if. -. Stainless Steel 53 5135' ?a Lead Rich 44 . . . 5- "it. Result summary: Misc. Silicates 12 I: "an . .I-y Data Filename Strontium-bearing 20 - . Cerium Rich 7 .4 j- Liar!" Beam Energy: 25 kV Titanium 6 t. . 9541, Working Distance 15.9 mm Manganese 5 . I Spot 30% Garnet 5 . . i Detector: BSED Titanium 4 - :2 5' Contrast 100% Stainless Steel 3 3?3 I Barium Sulfate 3 7- Stub 7" . 1? Client name CH2M Hill . Detail=11,570dpm - Description PFP Smear Area 263.416 16 R0 Figure 18. Images and Spectra of Plutonium Particles Measured by the Automated Feature Analysis on Sample SISR000029 Spectrum 440 330 720 110keV SizeArea 2.2 um2 Specttum 550? 440 330 220 110 SizeArea 11.3 um2 17 LAB-RPT-18-00003 R0 Figure 19. Manual Analysis of a Plutonium Particle in Sample 1.37 pm 2.?5 pm 2,511} Si Pu Pu 2,000- 3 1,500- I: 1,000- co Fe 500LAB-RPT- 8 -00003 R0 4 References Laboratory Technology Procedure for the ASPEX Explorer Scanning Electron Microscope,? as revised, Washington River Protection Solutions LLC, Richland, Washington. Instrument Notebook,? Laboratory Notebook, 222-S Laboratory, Washington River Protection Solutions LLC, Richland, Washington. 2018, ?Scanning Electron Microscopy Energy Dispersive Spectrometry Analysis of Plutonium Finishing Plant Air Filter and Tech Smears,? Rev. 1, Washington River Protection Solutions LLC, Richland, Washington. 2013, f?Characterization of Plutonium-Bearing Waste in the High-Level Waste Storage Tanks 241-TX-118, and 1 01 and the Plutonium Finishing Plant Z-9 Crib,? Washington River Protection Solutions LLC, Richland, Washington. 2016, ?Literature Review: Crud Formation at the Liquid/Liquid interface during TBP-based Solvent-Extraction Process,? Paci?c Northwest National Laboratory, Richland, Washington. 19 LAB-RPT-18-00003 R0 Attachment A PROBLEM AND DISCREPANCY REPORT Number: Rev. Number: 0 222-3 222320180187 SAMPLE EVENT INFORMATION SAF F18-017 SAMPLING INFORMATION NUMBER OF SAMPLES: 30 SAMPLE MATRIX: OTHER SOLID ISSUE BACKGROUND CLASS: Miscellaneous Issues TYPE: Other DESCRIPTION: The narrative discussion for the samples listed above should be restricted to alpha and plutonium observations only. RESOLUTION PROPOSED RESOLUTION: Please correct the issue and resubmit the hard copy and data package. FINAL RESOLUTION: SUBMITTED BY: HEY, BF, 20