research seminar - washington state university€¦ · 1845 terminal drive, suite 201, richland, wa...

Radiochemical Analysis of Plutonium in Tissues from Former Nuclear Workers

Sergei Y. Tolmachev and George Tabatadze

United States Transuranium and Uranium Registries

College of Pharmacy, Washington State University

1845 Terminal Drive, Suite 201, Richland, WA 99354

www.ustur.wsu.edu

Research SeminarOregon State University, School of Nuclear Science and Engineering

November 27, 2017

“Learning from Plutonium and

Uranium Workers”

Outline

Research Seminar at Oregon State University, November 27, 2017

• U.S. Transuranium and Uranium Registries

• Radiochemistry at the USTUR

• Plutonium in human

U.S. Atomic Energy Commission Vision

• 1966 meeting “Plutonium Contamination in Man”

“to protect the interests of workers, employees, and the public

by …. the acquisition and provision of the latest and most

precise information about the effects of the transuranic

elements on man.”


National Plutonium Registry: Blue Ribbon Committee

Standing left to right: Carlos E. Newton, Jr., W. Daggett Norwood, H.D. Bruner, Philip A. Fuqua

Seated left to right: Thomas F. Mancuso, J.H. Sterner, Robley D. Evans, Herbert M. ParkerNot photographed: Clarence C. Lushbaugh, Lloyd M. Joshel


REGISTRIES MANAGEMENT ANALYTICAL SUPPORT

1968 National Plutonium Registry Rocky Flats Pacific Northwest

at Hanford Environmental Health Foundation Facility Laboratory

1970 United States Transuranium Registryat Hanford Environmental Health Foundation

1971 Los Alamos

National Laboratory

1978 United States Uranium Registryat Hanford Environmental Health Foundation

1987-90

1992 United States Transuranium and Uranium Registriesat College of Pharmacy, Washington State University

Genealogy of the USTUR


USTUR Mission

• Follow up occupationally exposed individuals

(nuclear workers) by studying the biokinetics

(uptake, translocation, retention, and excretion),

and dosimetry of actinides (uranium, plutonium,

americium)

• Refine internal radiation dose assessment

methods as the bases for reliable epidemiological

studies, risk projection, and credible standards for

radiological protection

• Assess adequacy of historical and current U.S.

regulatory controls and practices


USTUR Today

• Unique resource worldwide for the

comprehensive study of the biokinetics and

internal dosimetry of actinide elements in the

human body

• National Human Radiobiology Tissue Repository

• The USTUR has provided important scientific

information to ensure the adequacy of the safety

standards for these radioactive elements


• Inhalation

i. Americium Oxide (AmO2)

ii. Plutonium Oxide (PuO2)

iii. Plutonium Nitrate [Pu(NO3)4]

iv. Uranium Hexafluoride (UF6)

• Wound

i. Americium Nitrate [Am(NO3)3]

ii. Plutonium Nitrate [Pu(NO3)4]

iii. Plutonium Oxide (PuO2)

• Ca-EDTA/DTPA Chelation

i. Americium Oxide (AmO2)

ii. Plutonium Nitrate [Pu(NO3)4]

Primary Research: Biokinetic Modeling and Dosimetry of Actinides

Courtesy of W.J. Bair

Model development, validation, and parameterization


USTUR Registrants (I)

• Voluntary tissue donors (posthumous):

whole-(44) and partial-body (307) donations

• Former nuclear workers from DOE sites


USTUR Registrants (II)

• Documented radiation exposure and work history

• Acceptance criteria:

i. actinide internal deposition of ≥74 Bq (2 nCi)

ii. external dose to whole body ≥0.1 Sv (10 rem)


Primary Exposure


USTUR Donations


USTUR Operation

AutopsyTissue

CollectionRadiochemical

AnalysisBiokinetic Modeling

Drying and Ashing

Digestion and Dissolution

Radionuclide Separation

α-source Preparation

Actinide Measurements


Radiochemistry at USTUR


• Laboratory Facilities

• NHRTR

• Radiochemical Tissue Analysis

• Plutonium in Human

USTUR Laboratory Building

• Office

• Autopsy Lab

• Chemistry Lab

• Counting Room

• Drying/ashing room

• Sample storage area

6,500 sq. ft. facility


Autopsy Laboratory

MORTECH® Mortuary Refrigerator

MORTECH® Autopsy Station and Elevating Table


Tissue Ashing Room


VWR® 1685 HAFO Series Forced-Air Oven, Fisher Scientific® Isotempâ Muffle Furnace 550 Series, LINDBERG® Muffle Furnace Model 52641

Radiochemistry Laboratory


Counting Room


Sample Storage Area


National Human Radiobiology Tissue Repository

• Established in 1992

• Resources for radiation dosimetry and biological

effects studies

USTUR frozen-tissue collection:


Tissue Sample Analysis Protocol

Drying/Ashing

Digestion/Dissolution



Actinide Measurements(Alpha-Spec)


USTUR 106: Sample Drying and Ashing

• Drying: @ 100 ˚C for 4 days, max. 48 samples

• Ashing: @ 450 ˚C for 4 days (×2), max. 32 samples


USTUR 110: Sample Digestion

• Microwave Digestion

Soft tissue: HNO3 – HCl – HF, 9:3:4 (mL)

Bone: HNO3 – HCl, 10:3 (reverse aqua regia)

Controlled temperature: 220 ˚C

Monitored pressure: 40 bar

• Radiochemical tracers (NIST): 242Pu, 243Am, 232U

MARS-5 Microwave EasyPrep® Vessel


USTUR 350: Actinide Separation

• Vacuum-Assisted Extraction Chromatography

TEVA

DGA

TRU


USTUR 350: Actinide Separation (Pu)

9) Pu Elution: 20 mL0.1M HCl - 0.05M HF – 0.04M

Rongalite

5) Beaker rinse: 2 × 5 mL 3M HNO3

6) Separate cartridges 7) TEVA rinse: 30 mL 3M HNO3 8) Rinse: 20 mL 9M HCl (Th)

1) Sample in 40 mL 3M HN03 – 1M Al(NO3)3

2) Add 0.75 mL 1.5M Sulfamic Acid + 6 mL 0.75M Ascorbic Acid

3) Add 2.5 mL 3.5 M Sodium Nitrite

4) Sample loading (1 drop sec-1)

1 mL TEVA Resin

(50-100 µm)

1 mL TRU-Resin

(50-100 µm)

Alpha spectrometry

Electrodeposition

1 mL DGA-Resin

(50-100 µm)

Discard (4 – 8)

(6)


USTUR 350: Actinide Separation (Am)

10) Am to DGA: 15 mL 4M HCl11) Separate cartridges

Discard (10)

1 mL TRU-Resin

(50-100 µm)

1 mL DGA-Resin

(50-100 µm)

(11)

14) Am Elution: 10 mL 0.25M HCl

Alpha spectrometry

Electrodeposition

12) Rinse: 3 mL 1M HNO3

13) Rinse: 10 mL 0.1M HNO3 (U)

Discard (12,13)

1 mL DGA-Resin

(50-100 µm)

(14)

TRU – DGA cartridges from Step 6


USTUR 350: Actinide Separation (U)

TRU cartridge from Step 11

15) Rinse: 12 mL 2.0 M HCl – 0.2M HF (Th)16) U Elution: 15 mL 0.1M Ammonium Bioxalate

Alpha spectrometry

Electrodeposition Discard (15)

(16)


USTUR 520: Electrodeposition

• Phoenix® EP-12 Series electrodeposition unit

• Custom Electrolytic Cell

• Na2SO4 electrolyte solution

• 1 hr electrodeposition @ 0.75 A

• α-source: 5/8˝ stainless steel disk (planchet)


USTUR 600: Alpha-Spectrometry

• ORTEC: Ensemble (3) and Octête PC (3) systems

• Detector: ENS-U450 (48)

• Software: AlphaVision 6.0.4

• Calibration: E&Z Analytics (1); USTUR (8)

• Sample count time: 150,000 s


USTUR Case Analysis Timeline

2 weeks

Actinide Measurements

2 weeks


1 week


2 – 3 Weeks

Digestion/Dissolution

2 weeks

Ashing

1 – 2 Weeks

Drying

~ 10 weeks


48 Tissue Samples

Tissue Analysis Throughput

Samples Analyzed

233

337

271

432

332

2013

2014

2015

2016

2017


Plutonium in Tissues of Occupationally Exposed Individuals


Deposition and Retention in Human Body


Liver (45%)

Skeleton (45%)

Soft tissues (10%)

Pu intake BloodstreamSystemic

deposition

Deposition and Retention in Human Body


• Respiratory tract (major)

• Systemic deposition (minor)

InhalationInsoluble material

Respiratory Tract +

Systemic

Route of Intake


239Pu Activity Concentration: Lung

Range 0.00055 – 7,225

Bq

kg

-1

Geometric Mean 1.43

95% CI for Mean 0.98 – 2.09

Median 1.28

95% CI for Median 0.52 – 2.61


239Pu Activity Concentration: LNTH

Range 0.0018 – 68,400

Bq

kg

-1

Geometric Mean 20.83

95% CI for Mean 13.83 – 31.38

Median 18.80

95% CI for Median 9.98 – 37.59


239Pu Activity Concentration: Liver

Range 0.00045 - 924

Bq

kg

-1

Geometric Mean 1.28

95% CI for Mean 0.92 – 1.78

Median 1.23

95% CI for Median 0.74 – 1.85


239Pu Activity Concentration: Skeleton

Range 0.0035 – 209

Bq

kg

-1

Geometric Mean 0.40

95% CI for Mean 0.30 – 0.53

Median 0.35

95% CI for Median 0.25 – 0.49


Summary: 239Pu Activity Concentration

Skeleton < Liver ≈ Lung << LNTH

1 4 54


239Pu Activity Concentration in Organs: USTUR vs Mayak PA


Hanford Site vs Mayak

Hanford

• 586-square-miles of shrub-steppe

desert in southeastern Washington

State

• In 1943, site was used to produce

plutonium for the bomb

• Continued operation during the

cold war

• Last reactor ceased operation in

1987

• Site clean up operation 1989 -

present


http://www.hanford.gov/page.cfm/HanfordHistory

Mayak

• The Mayak Production Association

• Built between 1945–48

• Secret Soviet Union atomic bomb

project

• Five nuclear reactors

• Plutonium for weapons

• Later reprocessing spent nuclear

fuel from nuclear reactors

• Mayak is still active as of 2017

https://en.wikipedia.org/wiki/Mayak

http://www.jccem.fsu.edu/Partners/MAYAK.cfm

http://www.hanford.gov/page.cfm/HanfordHistory

https://en.wikipedia.org/wiki/Mayak

http://www.jccem.fsu.edu/Partners/MAYAK.cfm

LNTH-to-Lung: 239Pu Concentration Ratio

LNTH : Lung > 19 ICRP Type S

Range 0.009 – 561

Geometric Mean 13.5

95% CI for Mean 10.9 – 16.5

Median 16.5

95% CI for Median 12.1 – 19.8


Skeleton-to-Liver: 239Pu Activity Ratio

1:1 (Systemic Model Assumption)

Range 0.03 – 125

Geometric Mean 1.63

95% CI for Mean 1.39 – 1.91

Median 1.41

95% CI for Median 1.17 – 1.63


USTUR: Take Home Message

• In-depth study of actinide biokinetics and

dosimetry

• Unique resource of data from former nuclear

workers

• Obtain, analyze, and preserve tissue samples for

future research

• Significant impact on national and international

radiation protection advisory bodies

• 50-y research funded by U.S. DOE


Questions?

[email protected]

www.ustur.wsu.edu


research seminar - washington state university€¦ · 1845 terminal drive, suite 201, richland, wa...

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