September 2014 Update:  EPA has validated and published a rapid method for sodium
hydroxide/sodium peroxide fusion of radioisotope thermoelectric generator materials in water and air
filter matrices for analysis of plutonium-238 and plutonium-239. The method is summarized and
accessible through the link provided below.

Rapid Method for Sodium Hydroxide/Sodium Peroxide Fusion of Radioisotope
Thermoelectric Generator Materials in Water and Air Filter Matrices Prior to Plutonium
Analyses for Environmental Remediation Following Radiological Incidents
Analyte(s)
Plutonium-238
Plutonium-239
CASRN
13981-16-3
15117-48-3
Analysis Purpose: Qualitative analysis
Technique: Alpha Spectrophotometry

Method Developed for: Plutonium-238 and plutonium-239 in water and air filters
Method Selected for: SAM lists this method for qualitative analysis of concrete or brick building
materials

Description of Method: This method is a pre-treatment technique, to be used prior to use of the rapid
separation method "Rapid Radiochemical Method for Plutonium-238 and Plutonium 239/240 in Building
Materials for Environmental Remediation Following Radiological Incidents" (Reference  16.1 in the
method). The method is based on total dissolution of radioisotope thermoelectric generator (RTG)
materials in water or air filter samples; it may be adapted for application to brick and concrete sample
materials after destruction of organic matter, but must be validated by the laboratory prior to use. Air
filters are fused using rapid sodium hydroxide/sodium peroxide at 700 °C. For water samples, refractory
RTG particles are collected on a 0.45um filter using a vacuum.  RTG activity remaining in the aqueous
filtrate is preconcentrated using calcium phosphate precipitation. Solid fractions and filtrate fractions are
processed separately by fusing with sodium hydroxide/sodium peroxide prior to subsequent chemical
separation and alpha spectrometric analysis. The fusion method requires approximately one hour per
batch of twenty samples using multiple  furnaces. Pre-concentration steps are needed to eliminate the
alkaline fusion matrix and collect the radionuclides,  and require approximately two hours. Plutonium is
separated from the fusion matrix using a lanthanum/calcium fluoride matrix removal step in preparation
for separation and analysis using the rapid separation method cited above. Assuming a 68 m3 air volume,
the method is capable of meeting a required minimum detectable concentration (MDC) of 0.003 pCi/m3
or below for air filters. Assuming a 1L volume, the  method is capable of meeting a required MDC of
0.23 pCi/L for water samples (filtered solids, filtrate, or combined result).

Special Considerations:  Organic based materials, such as cellulose nitrate or cellulose acetate filters,
may react vigorously upon addition of peroxide or during charring  steps. Wet-ashing with nitric acid and
hydrogen peroxide is needed to destroy organic constituents prior to fusion. Samples with elevated
activity or samples that require multiple analyses may need to be split after dissolution. Analytical
parameters, such as the duration of the sample count and the aliquant size, should be modified to achieve
optimal throughput (see Section 4.3 of the method for examples).  All plutonium must be  reduced to
plutonium (+3  or +4) before isotopic exchange with the tracer can be achieved with reasonable certainty.
Additionally, only plutonium (+3 or +4) will precipitate in the lanthanum fluoride/calcium fluoride pre-
concentration step. Although peroxide may reduce plutonium+6 to +4, the valence must be controlled
with certainty (see Section 4.6 for valence control procedures).  Valence controls also ensure that
plutonium will be present in the plutonium +4 form prior to separation on TEVA™ resin. Although this
method was validated using plutonium-242 tracer, plutonium-236 tracer may be used assuming traceable
material can be obtained with sufficient purity.

U.S. Environmental Protection Agency                                              EPA/600/F-14/284
Office of Research and Development, Homeland Security Research Program                    September 2014

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Source:  U.S. EPA, National Air and Radiation Environmental Laboratory (NAREL).  April 2014. Rev
0 "Rapid Method for Sodium Hydroxide/Sodium Peroxide Fusion of Radioisotope Thermoelectric
Generator Materials in Water and Air Filter Matrices Prior to Plutonium Analyses for Environmental
Remediation Following Radiological Incidents," EPA 402-R14-003.
http://www2.epa.gov/radiation/rapid-radiochemical-methods-selected-radionuclides
U.S.  Environmental Protection Agency                                             EPA/600/F-14/284
Office of Research and Development, Homeland Security Research Program                   September 2014

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