KetererLamerson A Fters NORTHERN ARIZONA UNIVERSITY March 27, 2020 TO: Elizabeth D. Lamerson FROM: Michael E. Ketterer, Ph.D, Professor Emeritus, Chemistry and Biochemistry Michael Ketterer@nauedu SUBJECT: — Uranium concentrations and isotope compositions in air filters sections from the Lamerson Air Monitoring Network SUBMITTED BY: WhaleeuererLamerson Ai Filters Summary. A pro bono study has been completed of the uranium (U) quantities and isotope compositions of 46 air filter sections (n=4 blanks; n=42 exposed) from two Lamerson Monitoring Network high-volume ambient air monitors in Pike County, Ohio. The filters had been collected in May through October 2019. ‘The author (Michael E. Ketterer) is “blind” to the identities of the cut filter sections, all of which are identified herein by a three-digit code starting with the number zero. The author received custody of. the samples by US Mail in October 2019, and they have been handled/stored/maintained under his exclusive custody thereafter. The cut filter sections were digested with 2 M nitric acid in the presence of an added internal standard; quantities of U (nanograms per filter) Were measured by comparison to prepared standard solutions of known concentration. The technique of quadrupole inductively coupled plasma mass spectrometry (ICPMS) was used to perform all measurements. The isotopes 7U, 25U, 2%5U and ?*U were measured, and ion intensity information was used to determine the atom ratios 2U/2U and 5U/2U in all samples, with 2°U/28U being reported in selected samples. The U atom ratios are used in this report to compare the airborne isotope compositions to those expected for naturally occurring U. A cellulose substrate filter material was utilized; the analysis of blank filters was conducted, and these blank filter results were used to blank-correct the raw results obtained for the exposed filters. The irregularly cut filter sections’ individual areas were estimated using an algorithm based upon the average masses of relevant categories of filters (unexposed/circular, exposed/circular, unexposed/irregular, exposed/irregular). The analysis of blank filter sections (n=4) revealed an average of 0.073 nanograms (7.3 x 10 grams) of uranium, and a standard deviation of 0.070 ng. The average quantity of U present in the unexposed filter ‘was subtracted from the exposed filters’ results. Exposed filter sections contained U quantities ranging from 1.3 to 12.2 ng, which significantly exceeded the calculated 3-sigma detection limit of 0.2 ng U per filter section. ‘The data reveal the following: 1) The baseline levels of U in the cellulose filter media used in the Lamerson network were well-suited for good measurements of both U quantities and isotope ratios. 2) Non-naturally occurring, enriched U was consistently present in all 42 samples of ambient airborne particulate matter supplied from the Lamerson network. The 2%5U/2*U ratios exhibited by the unknown samples ranged between 0.00779 and 0.0115, which are systematically different from 235U/28U = 0.0072527 in Nature. 3) Samples also exhibited correlated elevations in 25"U/28°U. This is the expected situation when enriched U is present, as enriched U exhibits correlated elevations in ?U/2U that are correlated with the degree in elevation of ®5U/2#U. ‘The interpretation of elevated 24/239 as an indication of enriched U is complicated due to natural 70 - 2 disequilibria effects, which result in natural variance in ?U/8U in the surface environment.tere Lamers i Fiters 4) The presence of 2U, originating from PORTS-handled “recycled uranium” was detected in four specific samples (009, 024, 063, 065); 28U/288U ratios ranged from 0.000011 to 0.000016. The 2U isotope is a definitive indicator of PORTS origin, as *U has essentially zero natural and non-PORTS background. All Lamerson filter samples are expected to contain 2 based upon a 25U-234U238U two-component mixing model, which shows that the ambient air U is similar to the enriched U present in local PORTS-contaminated sediments in Little Beaver Creek and the Scioto River Chemical procedures. The sample shipment consisted of 42 exposed and four unexposed filter sections. Ms. Lamerson numbered the exposed filter sections with a three-digit code (003 through 083); the blank, unexposed filters were numbered 086, 088, 090 and 092. Samples were cut using a 43.7 mm diameter template, and the sample shipment contained circular as well as irregularly cut filter sections. The original exposed area was 7” x 9" (63 in?; 407 cm?) for the cellulose filters collected in the Lamerson Monitoring Network, and the cut, destructively analyzed section herein represents ~ 3 - 4 % of the total sample quantity. ‘Sample and blank filter halves were transferred to 125 ml. polypropylene “specimen cup”. ‘The masses of the halves were recorded to the nearest 0.0001 g. Ten mL. of 2 M HNOs (aq) was added to each sample, along with a Pu internal standard solution (0.00449 Bq, 30.8 picograms, prepared from NIST 434i solution). The samples were heated for 10.5 hours in a convection oven regulated to 60-65°C. The oven was unattended overnight, but located ina restricted access laboratory. The oven door was affixed with a tape bearing Michael Ketterer’s signature, which was found to be intact and not tampered with, upon return to the laboratory the following morning. Sample extracts were filtered using a cotton plug filter prepared in-house using a 7 ml. transfer pipet (Globe 138080). The filtered samples were collected in a 15 ml. polypropylene centrifuge tube. Observations indicated that all of the un-digested sample solids and filter fiber was removed through this filtration process In addition to the filter samples, natural U controls were prepared for purposes of validating the ICPMS-measured U ratios. These samples consisted of ~ 20 milligrams of dried/powdered soil that was digested and filtered in the same manner as the filter samples. The identities of these materials are as follows: * Wash 17-20: organic rich surface soil from Cascade foothills, Washington, USA; contains 2301} from weapons test fallout surface mineral soil from Mi * Vermillio nesota, USA; contains “from weapons test fallout * Harris Core: pre-1952 interval of a sediment core collected from a water storage reservoir in Kansas, USA; lacks anthropogenic (fallout) 2°U The filtered sample solutions (10 mL) were initially analyzed as-is; thereafter, selected sample solutions were subjected to a chemical separation to pre-concentrate and purify the uranium, ‘The purified U fractions were used for a second set of U measurements focusing on 2, 235 and 2%6U, The samples treated were as follows: exposed filters 009, 024, 063 065, 067, 077, and 081; unexposed filters 086, 088, 090, and 092. In these separations, theremaining portion (7-8 mL.) of the 2 M HNO: sample digest was mixed with 100 mg of UTEVA resin (ElChrom, Lisle, IL); the mixtures were shaken for 30 minutes on an orbital shaker. The resin was collected on a disposable column prepared with a 7 mL. transfer pipet equipped with a glass wool plug; the columns were rinsed twice with 3 mL of 2M HNOs; U was eluted using the following sequence: i) 0.5 ml. water; ii) 0.5 mL. of 0.05 M aqueous ammonium oxalate, and iii) 0.5 mL water. Mass spectrometry. Measurements were conducted at Northern Arizona University, using a Thermo X-2 quadrupole inductively coupled plasma mass spectrometer (ICPMS). The instrument was equipped with a fuoropolymer concentric nebulizer and an APEX Model HF (ESI Scientific) cyclonic spray chamber; the nebulizer operated in a self- aspirating mode with an uptake of ~ 150 yL/minute. Sample solutions were introduced manually (ie, no auto-sampler was used) and the washout was monitored manually in between samples while rinsing the sample introduction system with dilute HNOs (aq). The instrument was tuned using a solution of naturally occurring U, resulting in a 7U sensitivity of ~ 500,000 cps per 1 pg/L, along with background count rates (rinse solution at m/z 236) of < 1 cps. For the digested sample solutions, ion count data were collected at masss 234, 235, 236, 238 and 242 using a dwell time of 10 milliseconds and a measurement cycle consisting of 1000 sweeps/reading. A total of 3 to 5 readings were collected for each solution, Calibration standards of 0 and 0.5 pg/L U, both containing 30.8 pg *Pu/10 mL were prepared in 2 M aqueous HNOs. The unknown samples also contained 30.8 pg **Pu/10 mL. One 05 pg/L standard was prepared using U from a High Purity Standards stock solution; a second, independent 0.5 g/L. standard was formulated with a U stock obtained from Inorganic Ventures. ‘These U concentration standards were analyzed in the same manner as the unknown air filter extract and control sample solutions. The collective set of four analyses of the naturally occurring U control samples yielded the following UU isotope results: ppm sd tapi | Name | # meas) 234/238 | 234238 | 235u/238 sd 235238 i13 | Wash i720 [3 ae 77 0.00738 0.00005 aie | Harris Core [6 537 23 0.00724 0.00004 120 | Vermilion 4 73.0 ~ 0.00712 ‘0.00002 [4162 | Haris Core [5 si0 | 40 | 0.00730 | 0.00004 39.8 0.00726 = Note that “ppm 2U/238U" is equal to the 24U/28U ratio multipl by 10°, Asan example this column should be read as, the “¥U/2*U ratio for Lab ID 113 is 0.0000616. The measured 235U/23U average of 0.00726 and a standard deviation of 0.00011; this indicates ificant difference from the natural value of 0.0072527. Accordingly, no that there is no siXettererLamerson i Fiters mass bias correction was performed for any of the U ratios reported herein. Note that the 24/23 ratios agree relatively well with the expected value for 2U/25U at secular equilibrium (0.00005472 + 0. 00000011), albeit that some natural variation in 2%*U/288U due to 7U - *9U disequilibria is expected. Data from the ICPMS were saved as CSV and PDF files; these results were printed offline. The raw data were used to perform isotope ratio calculations offline, using the program Statgraphics. ‘Threshold for confirming the presence of non-naturally occurring U in unknown samples. A deviation in 2%5U/23U from the naturally occurring ratio (0.0072527) is used as the primary basis for ascertaining whether a sample contains any detectable contribution from an enriched or depleted uranium source. For an unknown air filter sample, the Null Hypothesis is that ®5U/2U is “not different” from Nature. The Null Hypothesis is accepted, unless 5U/29U exceeds a threshold value: CU/2U)acecnoia= (25U/2U) argo natu contts* 1 * (standard deviation of controls) For the four measured soil/sediment controls, (235U/25U).yrstae for enriched uranium = 0.00759, 0.00781, and 0.00826 for n = 3, 5, and 10, respectively. ‘The results for U ratios for the Lamerson Monitoring Network samples are given below. io Type | #meas| »urmy | to | mymy | DY Unknown [3 61.3 47 0.00822 | 0.00004 “Unknown 3 61.4 6.6 ‘0.00835 | 0.00001 ‘Unknown 3 60.0 10.6 0.00784 | 0.00008 Uninows | 3] HSE] 43] nies | omar Uniown | 3] a7] Sa amrOTF | w.00005 Unknown | 3] 828] Ba] 100787] 000007 12 ‘Unknown 3 67 | 0.00822 |~0.00019 fn cr a 3.4 | 0.00845 [0.00010 | 17 | Unknown | 3 49.0 38 | 0.00814 | 0.00010 30 | Unknown | 3 143 | 0.00828 | 0.00016 24) Unknown | 3 31 | ooi0ai | o.o00rt | 26 | Unknown | 3 38.1 46 | O.00801 | 0.00008 30 Unknown [3 329 23 | 0.00779 | 0.00002 [3a nknawn [3 Gi | 34 | 0.00902 | a.00025 36 “Unknown 3 CBI 10.6 | 0.00795 | 0.00008etree Lamerson A iter 38 | Unknowa [3 a] 63] o.00804 | 0.00020 33 | Unknown | —3 70 50 | o00868 | 0.0005 30 | Unknown ws | 245 | 0.00804 | 0.00070 a | Unknow a | tao] 0.00834 | 0.00030 3 | Unknown | 3 Tad 27 | 0.00873 | 0.00008 44__| Unknown | 3 Bs | 0.00896 | 0.00008 45 | Unknown | 3 666 a | 0.00819 | 6.00003 47 | Unknown | 3 | 567) aa] 0.00789 | —O.00016 50 | Unknown | 3 716 | 4a | 0.00819 | 0.0007 [St | akon | 3 60.0 aa | d.00838 | o.00016 33 | Unknown | 3 56.1 58 | 0.00886 | 0.00001 | [38 | Unknown |S Bi 57 | 0.00786 | 0.00009 [86 | daknown | 3 ora 70 | 00515 | 0.00009 [37 / onknowa | 5 2] 63 | 0.00887 | 0.00006 a eps oS | 62 | 000825) o.0007 | Unknown | 3 7a6 | 118] e.0086s | 0.00009 3 | Unknown |S 28 | a7 | e.0087s | 0.00005 | Unknown |S Tet | 15.0 | 0.00829 | 0.00005 @5 | Unknown [5] 665 50 | 0.00873 | 0.00008 7 | Unknown |S 905 | 97 | o.oi032 | o.000r4 7a | Gnknown | 5 [aia | 0.00833 .00008 75] Unknown | 3 sos | 4.0 | o.008i0 | 0.00003 76 | Unknown | 3 os 0.00778. | 0.00079 77 | Unienown | 3 778 69 | ooiisi | 0.00005 3) | Unknown | 3 oa | 118 | 000782 | o.000IT sr | Unknown | 3 72 36 | 0.01058 | 0.00004 3 | Unknown | 3 ee 0.00791 | 0.00052 : Nat 7 I 13 | control | 3 61.6 77 | 0.00739 | 0.00005r [natu 6 537 2.9 | 0.00724 | 0.00004 natu | ep] 120 control 4 73.0 2.0 | 0.00712 | 0.00002 | Nat U Nat al 1162 | Ucontor | 5 51.0 4.0 | 0.00730 | 0.00004 l ‘Avg | 0.00726 Calculation of filter basis weight, sample loading, and scale-up to U quantities Present on the entire filter. The collection of samples consisted of intact, circular sections (d = 4.37 cm; r = 2.185 cm) as well as jagged, irregularly shaped sections approximating a 4.37 cm diameter circular section. The following procedures were used to address calculating the area of the analyzed filter section, and to scale the mass of U found in the analyzed section to the entire filter: {i) Two blank/unexposed filters had perfect circular shapes: 090, 092. These filters had masses of 0.1341 and 0.1348 g (average = 0.1345 g). Two exposed filters had perfect circular shapes: 030, 080. ‘These filters had masses of 0.1407 and 0.1415 g (average = 0.1411 g). These results project that an exposed filter section contains an average of 0.0066 grams of particulate material fora perfectly circular section. ii) The area of an unexposed circular 4.37 cm diameter section (r = 2.185 cm) is 15.0 cm ‘The basis weight of the unexposed filter material is 0.1345 g / 15.0 cm? = 0.00897 g/cm? iii) The circular sections have an air particulate matter loading of 0.0066 g / 15.0 cm? = 0.00044 g/em?, Itis assumed that the irregular filters have the same loading and the same approximate area iv) The net mass of filter material (gross mass of filter section - 0.0066 g) is calculated for each irregularly shaped filter. The exposed area in cm? analyzed is calculated: (Net mass of filter substrate, grams) / (1 cm? substrate / 0.00897 g substrate) v) The exposed area of the entire filter is 7" x 9", with area 63 in? (407 cm’). The fraction of entire filter area that has been analyzed herein is obtained: Fractional area analyzed = (calculated n? of exposed area) / 407 cm? vi) The mass of U found in the entire 7” x9" filter is calculated: Mass of U in 7” x 9” exposed filter = mass of U in analyzed section / fractional area analyzed Using this algorithm, the results for masses of U found in the analyzed filter sections, and that present in the entire exposed 7” x 9" filter, are shown below. It is noted that the quantity present in the entire 7” x 9" exposed area may be used to calculate airborne Uconcentrations in units such as micrograms per cubic meter, using the monitors’ results for the total sampled air volumes. [Sample | ng Uin | sd | Gross | Tare | Gn” | Fractional | ng Uin | “Code | section | ngu | mass | mass | exposed | area’ | entire iter 3 | 937 [oas | o.1360 | o.1zea | iaas | owas 7 | 4 | eis | 00s | oda | oda] 15.76 | ooze | 6 [sar | one | oaz96 | oaza0 | a7 | — 00387 oe 7 | 303 | os | oraas [0.1379 | i537 | ome ca 9 | as [0.04 | oes | 0309) 1560 | —o.0388 20 i [90s o0a [ores | 0.1392 | iss2 | —o0aa2 Br |e [0.03 | o.tias | o.x0R | 12.08 | —om296 6 Te |S | 010 | o.iaae | oazer | i290} —on3sa | 168 | aa 046 | oat | omnes | i280} — omnis er 20 | 3a7 [08 | 0.1389 | ozs | tear | O38 wo WH | 666 [ois | o:iiea | onze | 1258 | — 0.0308 as 2% | S27 Pour | oases | asia | a70a | ocean | 125 30 | 402 | 08 | O:ia0R | O32 | 7896 | —O.036E 103 m 0.07 | 0.370 | Oas08 | ise — Ose 7 36 | 78 foto | 0.340 | oar | 14.20 | asa | —az0 38 | 368 | 0.02 | ox07i | 0.1005 | in.20 | o0276 1a ae ert | 007 | o1a47 | o.xzer | raze | —o0a8T Br a0 | aar fone | oizaa | eine] asa3 | ome 1 a} 234 | 0.00 | o.t082 | 0.0996 | 11-10 | ozs a a] S70 [one [0.1480 | 0.1364 | i543) 0.0379 | 150 | ome oie [ores | oasi7 | 1468 | —o.036r aE | sas [00s | 0.1496 | 01430] 1594 | —o.0aeR 152 a | 697 | v2 | oxaio | ose | ~1a.98-| 0.0369 189 30 438 Pour ores porsv | isa. | 00s? | a6 si | a0 one | 0.1329 | 0.1265 et, 33 | 686 | 011 | 0122 | 01156 | 1289 | o0R7 26 35 | i204 | 0.15 | 0.1468 | 0.1402 | i563 | 00385 sey 36} 299 | 0.03 | oai77| ost | 12:39 | 0.0305 837927 [820 | Oa] Oise | aS] omRI 32 | 7a0| O09 | Onis | wate | 12.12 | —oa298 | 258] @ | 4as [oar | osi7 | over | Tee] — 0398 i [izes [aaa | oar | Oaas | ines] — 0.0366 a a | sar [a6 oass7 | 1736] 00a ce iis | 0a? ‘ora ] 1250] ome 6 oa) as ‘oT | ist] 0H 18 a) aa] oe aa isa] aaa] | sa} ona | 03580 | 1773 |—oaas | Tas Te} eat] oar | ona | waa | a7} — 00H ier Wem) ora | oa | aaa | isso | —ona6 | 167 wo | aaa oe | oar | oasas | tae | — ORG oo ai | 490 | eae | oasia | ones | aeaa | — oma we | 670 | os | ras | ones | 1820] cose | 19 | Enriched U in Lamerson Monitoring Network Filters. It is apparent that all 42 exposed filter sections exhibit *%5U/238U ratios that exceed thresholds for detection of enriched uranium, The basis for this statement is that ®5U/2U ratios measured in all of the unknown filters exceed the (average + 3*SD) threshold 285U/28U value of 0.00759. Moreover, a majority (24 of 42) of the filters exhibited ?"U/2'*U > 0.00826, the (average + 10°SD) threshold. On this basis, to a reasonable degree of scientific certainty, itis concluded that all of the air filters collected in 2019 at the Lamerson Monitoring Network exhibit influence from enriched uranium sources. It is evident that the ambient airshed near the PORTS facility is being affected by historic and/or contemporary enriched uranium emissions from PORTS; the facility is the single explanatory source. graphical depiction of the comparison between the 3*SD range measured for the natural U controls vs. the values of the Lamerson Monitoring Network samples is shown in Figure 1 below. ‘The unequivocal presence of © was also confirmed in four selected filters (009, 024, 063, 065); 2U/23#U ratios ranged from 0.000011 to 0.000016. In contrast, naturally occurring, U has a2U/20U of ~ 107 or less; nuclear weapons tests added small amounts of U to this natural background (Ketterer et al, 2013). The presence of 2U in PORTS-handled U is well documented (Moody, 1995; Ketterer and Szechenyi, 2019), and results from the blending of significant quantities of Pu production reactor-originating “recycled U" into the plant feed. It is also known that depleted U, which exhibits 25U/25*U < 0.0072527, contains %6U (Bu et al, 2017). As depleted U contains 2, itis possible that leaks from cylinders of depleted uranium hexafluoride (DUFs) also represent potential sources of the °°U found inKetererLamerson A ites the air filters. Nevertheless, the pervasive enriched *5U/2U signatures more strongly implicate PORTS-related enriched U as being the explanatory contamination source. A mixing plot of °U/2"U vs. 25U/38U is shown in Figure 2; also included therein are data points from enriched U contaminated sediments from the proximity of PORTS (results from Ketterer and Szechenyi, 2019). ‘The plot indicates that the enriched U is similar in its isotope composition to legacy PORTS emissions, although further studies should be pursued to investigate whether depleted U emissions from leaking DUFs cylinders may be present. Acknowledgments This project has been prepared as a pro bono, independent, scholarly work of the author. Although the analytical work has been conducted at the laboratories of Northern Arizona University’s Department of Chemistry and Biochemistry, this work isthe initiative and product ofthe author alone; any resuls/opinions expressed represent those of the authors, and do not reflect opinions of the University, the Arizona Board of Regents, or the State of Arizona. The author is grateful to the Chemistry and Biochemistry Department for laboratory access, stimulating discussions, and collegiality. I particularly wish to express appreciation to Prof. Jani C. Ingram, and her research group, for their generosity in sharing laboratory space and ICPMS instrumentation while the work was conducted. 1 also thank James Biddle, Radiation Safety Officer, for ‘making our work possible under the authority of the University’s Radioactive Materials License, Issued by the State of Arizona, in order to utilize “Pu tracer in the measurements. Finally, | owe utmost thanks and ‘respect to Elizabeth Lamerson and her fellow citizens of southern Ohio forthe collaboration. Literature Cited Bu, W, Zheng, J; Ketterer, ME; Hu, S; Uchida, S; Wang, X, “Development and application of mass spectrometric techniques for ultratrace determination of 2) in environmental samples ~ A review, Analytica Chimica Acta 2017, 995, 1-20. Ketterer, M.E; Groves, A.D. Strick, BJ; Asplund, CS. Jones, VJ, “Deposition of 4U from atmospheric nuclear testing in Washington state (USA) and the Pechora region (Russian Arcti)", Journal of Environmental Radioactivity 2013, 118, 143-149, Ketterer, M.E: Szechenyi, SC, “Investigation of anthropogenic uranium, neptunium, and plutonium in ‘environmental samples near Piketon, Ohio”, technical report released April 27, 2019, Moody, KJ, “Forensic Radiochemistry of PUBLIC Site Inspection Samples’, Lawrence Liver Laboratory 1995, UCRLAID-119658. ore Nath 100.01200 0.01100 0.01000 Lamerson Monitoring nu Peal Network 0.00900 0.00800 0.00700 0.00600 Figure 1. Comparison of 25U/28U results for the Lamerson Air Monitoring Network filter sections (blue points) vs. the measured range for natural U controls (red points and shaded region). The uncertainties (one standard deviation of experimental measurements) are shown when in excess of the symbol dimensions. ul236 /238y 0.00010 0.00009 0.00008 0.00007 0.00006 0.00005 0.00004 0.00003 0.00002 0.00001 0.00000 0.005 0.010 0.015 0.020 0.025 0.030 2354 /238 Figure 2. Mixing plot of 2°U/2#U vs. ®5U/28U for natural U (green), sediments from the PORTS facility proximity (blue points), and Lamerson Air Monitoring Network filter ‘sections (red points). The mixing line for all points is shown in red.Attachment, Blind Sample Key Completed with Data from March 27, 2020 Report Blind Sample Key Data Added on March 31, 2020 By Elizabeth D. Lamerson,———— a = = ss = = pEDESAE : = rsa = a = = — = aomsama = Sea = — = EEE = SssonISS = aS a SaaS = = Sea = —— = — = esas = — Es —— = aaron = — sa — = Four peony 13/4 ih oun sang wera om th pet (A ample. Two ofthe ae om ch pare sme were et to bean biol at Norn ean testy NAL). 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