SIST EN ISO 15366-1:2016

Nuclear fuel technology - Chemical separation and purification of uranium and plutonium in nitric acid solutions for isotopic and isotopic dilution analysis by solvent extraction chromatography - Part 1: Samples containing plutonium in the microgram range and uranium in the milligram range (ISO 15366-1:2014)

ISO 15366-1:2014 describes procedures to chemically separate and purify uranium and plutonium in dissolved solutions of irradiated light water reactor fuels and in samples of high active liquid waste of spent fuel reprocessing plants, prior to their isotopic analysis by e.g. mass spectrometric method or alpha spectrometry. ISO 15366-1:2014 describes a technique for the separation of uranium and plutonium in spent fuel type samples based on chromatographic method. The procedure applies to samples containing 1 μg to 150 μg Pu (IV) and (VI) and 0,1 mg to 2 mg U (IV) and (VI) in up to 2 ml of 3 mol·l-1 nitric acid solution. It is applicable to mixtures of uranium and plutonium in which the U/Pu-ratio can range from 0 up to 200.

Kernbrennstofftechnologie - Chemische Trennung und Reinigung von Uran und Plutonium in Salpetersäure-Lösungen für Isotopen- und Isotopenverdünnungsanalysen mittels Lösemittelextraktions-Chromatographie - Teil 1: Proben mit Plutonium im Mikrogrammbereich und Uranium im Milligrammbereich (ISO 15366-1:2014)

Technologie du combustible nucléaire - Séparation et purification chimiques de l'uranium et du plutonium dans les solutions d'acide nitrique par extraction chromatographique par solvant pour les mesures isotopiques et les analyses par dilution isotopique - Partie 1: Échantillons ayant des teneurs en plutonium de l'ordre du microgramme et en uranium de l'ordre du milligramme (ISO 15366-1:2014)

ISO 15366-1:2014 spécifie des modes opératoires pour séparer et purifier chimiquement l'uranium et le plutonium contenus dans les solutions de dissolution de combustibles irradiés dans les réacteurs à eau légère ainsi que dans des échantillons d'effluents liquides hautement radioactifs provenant d'usines de retraitement des combustibles irradiés, en vue de leur analyse isotopique par la méthode de spectrométrie de masse (voir ISO 8299[1]) ou par la méthode de spectrométrie alpha (voir ISO 11483[2]).
ISO 15366-1:2014 décrit une technique de séparation de l'uranium et du plutonium dans des échantillons de type combustibles irradiés reposant sur une méthode chromatographique. Le mode opératoire s'applique à des échantillons contenant de 1 μg à 150 μg de Pu(IV) et (VI) et de 0,1 mg à 2 mg d'U(IV) et (VI) dans 2 ml maximum de solution d'acide nitrique à 3 mol·l−1. Il est applicable aux mélanges d'uranium et de plutonium dont le rapport U/Pu peut aller de 0 à 200.

Tehnologija jedrskih goriv - Kemično ločevanje in čiščenje urana in plutonija v raztopinah dušikove kisline za analizo izotopov in razredčenih izotopov s kromatografijo z ekstrakcjo s topilom - 1. del: Vzorci s plutonijem v mikrogramskih količinah in uranom v miligramskih količinah (ISO 15366-1:2014)

Standard ISO 15366-1:2014 opisuje postopke za kemično ločevanje in čiščenje urana in plutonija v raztopinah ožarčenih lahkovodnih reaktorskih goriv ter v vzorcih visokoradioaktivnih tekočih odpadkov iz obratov za predelavo izrabljenega goriva pred izotopsko analizo npr. z masno spektrometrično metodo ali alfa spektrometrijo. Standard ISO 15366-1:2014 opisuje tehniko ločevanja urana in plutonija v vzorcih vrst izrabljenega goriva na podlagi kromatografske metode. Postopek se uporablja za vzorce, ki vsebujejo od 1 μg do 150 μg Pu (IV) in (VI) ter od 0,1 mg do 2 mg U (IV) in (VI) v največ 2 ml 3 mol·l-1 raztopini dušikove kisline. Uporablja se za mešanice urana in plutonija z razmerjem U/Pu v razponu od 0 do 200.

General Information

• Status: Published
• Public Enquiry End Date: 29-Nov-2015
• Publication Date: 16-May-2016
• ICS: 27.120.30 - Fissile materials and nuclear fuel technology
• ICS: 71.040.50 - Physicochemical methods of analysis
• Technical Committee: I13 - Imaginarni 13
• Current Stage: 6060 - National Implementation/Publication (Adopted Project)
• Start Date: 06-May-2016
• Due Date: 11-Jul-2016
• Completion Date: 17-May-2016
• Ref Project: EN ISO 15366-1:2016 - Nuclear fuel technology - Chemical separation and purification of uranium and plutonium in nitric acid solutions for isotopic and isotopic dilution analysis by solvent extraction chromatography - Part 1: Samples containing plutonium in the microgram range and uranium in the milligram range (ISO 15366-1:2014)

Overview

EN ISO 15366-1:2016 (ISO 15366-1:2014) specifies a validated radiochemical procedure for the chemical separation and purification of uranium and plutonium from nitric acid solutions using solvent extraction chromatography. It is designed for samples from irradiated light‑water reactor fuel dissolutions and high‑activity liquid wastes from reprocessing plants, prior to isotopic analysis (e.g., mass spectrometry or alpha spectrometry).

Key scope points:

• Applies to samples containing 1 μg to 150 μg Pu (IV/V/VI) and 0.1 mg to 2 mg U (IV/VI) in up to 2 ml of 3 mol·L⁻¹ HNO3.
• Applicable for mixtures with U/Pu ratios from 0 up to 200.
• Endorsed by CEN as a European standard (EN ISO 15366-1:2016).

Key topics and technical requirements

• Separation principle: Column extraction chromatography using tri‑n‑octylphosphine oxide (TOPO) coated on an inert silica support to selectively extract Pu(IV) and U(VI) from 3 mol·L⁻¹ nitric acid.
• Valency control: Redox valency adjustment is performed (iron(II) sulfate and sodium nitrite) to ensure plutonium is in the tetravalent state before separation; subsequent controlled reduction and elution steps recover separated fractions.
• Elution chemistry:
  • Plutonium is eluted after reduction (e.g., with ascorbic acid) and can be measured by alpha spectrometry as a check on recovery and to complement mass spectrometric results.
  • Uranium is eluted using ammonium carbamate solution.
• Apparatus and consumables: Disposable polypropylene or glass columns with specified bed volume and frit porosity; silica gel particle size and TOPO loading detailed in Annex A.
• Analytical controls: Parallel blanks and certified control samples are required to monitor cross‑contamination, recovery efficiency and correct isotopic equilibration.
• Operational limits: Gravity column flow rates recommended not to exceed 0.1 mL·min⁻¹ to ensure favourable kinetics.
• Reagents and safety: Use analytical grade reagents and deionized water; note flammability of TOPO in cyclohexane and handling restrictions for radioactive materials.

Applications and users

This standard is directly applicable to:

• Nuclear fuel technology and spent fuel reprocessing laboratories.
• Radiochemistry and isotopic analysis facilities performing uranium/plutonium assay by mass spectrometry or alpha spectrometry.
• Nuclear safeguards, environmental monitoring, and R&D groups needing reliable U/Pu separation for isotopic dilution and isotopic composition measurement.

Related standards

• ISO 15366-2 (Part 2): procedure for nanogram and sub‑nanogram level samples.
• ISO 8299 and ISO 11483: referenced for isotopic measurement methods (mass spectrometry and alpha spectrometry).

Keywords: EN ISO 15366-1:2016, ISO 15366-1:2014, nuclear fuel technology, uranium plutonium separation, solvent extraction chromatography, TOPO, nitric acid solutions, isotopic analysis, mass spectrometry, alpha spectrometry.

Standards Content (Sample)

SLOVENSKI STANDARD
01-junij-2016
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Nuclear fuel technology - Chemical separation and purification of uranium and plutonium
in nitric acid solutions for isotopic and isotopic dilution analysis by solvent extraction
chromatography - Part 1: Samples containing plutonium in the microgram range and
uranium in the milligram range (ISO 15366-1:2014)
Kernbrennstofftechnologie - Chemische Trennung und Reinigung von Uran und
Plutonium in Salpetersäure-Lösungen für Isotopen- und Isotopenverdünnungsanalysen
mittels Lösemittelextraktions-Chromatographie - Teil 1: Proben mit Plutonium im
Mikrogrammbereich und Uranium im Milligrammbereich (ISO 15366-1:2014)
Technologie du combustible nucléaire - Séparation et purification chimiques de l'uranium
et du plutonium dans les solutions d'acide nitrique par extraction chromatographique par
solvant pour les mesures isotopiques et les analyses par dilution isotopique - Partie 1:
Échantillons ayant des teneurs en plutonium de l'ordre du microgramme et en uranium
de l'ordre du milligramme (ISO 15366-1:2014)
Ta slovenski standard je istoveten z: EN ISO 15366-1:2016
ICS:
27.120.30 Cepljivi materiali in jedrska Fissile materials and nuclear
gorivna tehnologija fuel technology
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN ISO 15366-1
EUROPEAN STANDARD
NORME EUROPÉENNE
April 2016
EUROPÄISCHE NORM
ICS 27.120.30
English Version
Nuclear fuel technology - Chemical separation and
purification of uranium and plutonium in nitric acid
solutions for isotopic and isotopic dilution analysis by
solvent extraction chromatography - Part 1: Samples
containing plutonium in the microgram range and
uranium in the milligram range (ISO 15366-1:2014)
Technologie du combustible nucléaire - Séparation et Kernbrennstofftechnologie - Chemische Trennung und
purification chimiques de l'uranium et du plutonium Reinigung von Uran und Plutonium in Salpetersäure-
dans les solutions d'acide nitrique par extraction Lösungen für Isotopen- und
chromatographique par solvant pour les mesures Isotopenverdünnungsanalysen mittels
isotopiques et les analyses par dilution isotopique - Lösemittelextraktions-Chromatographie - Teil 1:
Partie 1: Échantillons ayant des teneurs en plutonium Proben mit Plutonium im Mikrogrammbereich und
de l'ordre du microgramme et en uranium de l'ordre Uranium im Milligrammbereich (ISO 15366-1:2014)
du milligramme (ISO 15366-1:2014)
This European Standard was approved by CEN on 21 February 2016.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN
member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and
United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2016 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 15366-1:2016 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
European foreword
The text of ISO 15366-1:2014 has been prepared by Technical Committee ISO/TC 85 “Nuclear energy,
nuclear technologies, and radiological protection” of the International Organization for Standardization
(ISO) and has been taken over as EN ISO 15366-1:2016 by Technical Committee CEN/TC 430 “Nuclear
energy, nuclear technologies, and radiological protection” the secretariat of which is held by AFNOR.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by October 2016, and conflicting national standards shall
be withdrawn at the latest by October 2016.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent
rights.
According to the CEN-CENELEC Internal Regulations, the national standards organizations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria,
Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta,
Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and the United Kingdom.
Endorsement notice
The text of ISO 15366-1:2014 has been approved by CEN as EN ISO 15366-1:2016 without any
modification.
INTERNATIONAL ISO
STANDARD 15366-1
First edition
2014-07-01
Nuclear fuel technology — Chemical
separation and purification of
uranium and plutonium in nitric acid
solutions for isotopic and isotopic
dilution analysis by solvent extraction
chromatography —
Part 1:
Samples containing plutonium in the
microgram range and uranium in the
milligram range
Technologie du combustible nucléaire — Séparation et purification
chimiques de l’uranium et du plutonium dans les solutions d’acide
nitrique par extraction chromatographique par solvant pour les
mesures isotopiques et les analyses par dilution isotopique —
Partie 1: Échantillons ayant des teneurs en plutonium de l’ordre du
microgramme et en uranium de l’ordre du milligramme
Reference number
ISO 15366-1:2014(E)
©
ISO 2014
ISO 15366-1:2014(E)
© ISO 2014
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail [e-mail]
Web www.iso.org
Published in Switzerland
ii © ISO 2014 – All rights reserved

ISO 15366-1:2014(E)
Contents Page
Foreword .iv
1 Scope . 1
2 Principle of the method . 1
3 Apparatus . 1
4 Reagents . 2
5 Procedure (see Figure 1). 2
6 Characteristics of the separation . 4
7 Quality control . 5
8 Interferences . 5
Annex A (normative) Packing and conditioning of the chromatographic columns as used in
the ISO 15366 1 procedure, loaded with an inert silica support coated with tri-n-octyl-
phosphine-oxide (TOPO) . 7
Bibliography .10
ISO 15366-1:2014(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2. www.iso.org/directives
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received. www.iso.org/patents
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical Barriers
to Trade (TBT) see the following URL: Foreword - Supplementary information
The committee responsible for this document is ISO/TC 85, Nuclear energy, nuclear technologies, and
radiological protection, Subcommittee SC 5, Nuclear fuel cycle.
This first edition, together with the first edition of ISO 15366-2, cancels and replaces the first edition of
ISO 15366:1999, which has been technically revised.
ISO 15366 consists of the following parts, under the general title Chemical separation and purification of
uranium and plutonium in nitric acid solutions for isotopic and isotopic dilution analysis by solvent extraction
chromatography —
— Part 1: Sample containing plutonium in the microgram range and uranium in the milligram range
— Part 2: Sample containing plutonium and uranium amounts in the nanogram range and below
iv © ISO 2014 – All rights reserved

INTERNATIONAL STANDARD ISO 15366-1:2014(E)
Nuclear fuel technology — Chemical separation and
purification of uranium and plutonium in nitric acid
solutions for isotopic and isotopic dilution analysis by
solvent extraction chromatography —
Part 1:
Samples containing plutonium in the microgram range and
uranium in the milligram range
1 Scope
This part of ISO 15366 describes procedures to chemically separate and purify uranium and plutonium
in dissolved solutions of irradiated light water reactor fuels and in samples of high active liquid waste
of spent fuel reprocessing plants, prior to their isotopic analysis by e.g. mass spectrometric method (see
[1] [2]
ISO 8299 ) or alpha spectrometry (see ISO 11483 ).
This part of ISO 15366, describes a technique for the separation of uranium and plutonium in spent fuel
type samples based on chromatographic method. The procedure applies to samples containing 1 μg to
−1
150 μg Pu (IV) and (VI) and 0,1 mg to 2 mg U (IV) and (VI) in up to 2 ml of 3 mol·l nitric acid solution. It
is applicable to mixtures of uranium and plutonium in which the U/Pu-ratio can range from 0 up to 200.
2 Principle of the method
The chemical separation is based on a column extraction chromatography using tri-n-octylphosphine-
[3][4]
oxide (TOPO) as extractant. The necessary valency adjustment prior to the separation is done with
iron(II) sulfate and sodium nitrite. The extraction process is performed in disposable columns loaded
[5] −1
with a silica gel powder coated with the TOPO. Plutonium(IV) and uranium(VI) in 3 mol·l nitric
acid medium are selectively extracted into the TOPO while americium, the fission products and other
interfering elements are not retained. Plutonium is eluted after reduction to the trivalent state with
[6]
ascorbic acid ; uranium is eluted by an ammonium carbamate solution. Besides the measurement
by mass spectrometry, the plutonium fractions are also measured by alpha spectrometry for the
determination of the isotopic abundance of Pu (mass spectrometry might be biased by residual
amounts of uranium in the plutonium fraction) and for checking the recovery of plutonium.
In order to ensure favourable kinetics of the chemical reactions, the (gravity) column flow rates should
−1
not exceed 0,1 ml·min .
Parallel measurement of blank and/or control sample is recommended to verify the analysis.
Blanks are run in parallel with the samples to verify the absence of significant external cross-
contamination and cross-contamination between samples.
Control samples prepared from certified or analysed materials are also prepared and separated along
with the sample to verify that suitable valency adjustment, isotopic equilibration and separation
efficiency are achieved.
3 Apparatus
3.1 Biological shielding, e.g. shielded glove box or fume cupboard.
ISO 15366-1:2014(E)
3.2 Disposable polypropylene or glass columns, of length 90 mm, funnel reservoir 9,5 ml, support
bed volume 1,4 ml, height of bed 26 mm, inner diameter of bed reservoir 8,4 mm. Frits of polyethylene
or glass 20 µm respectively 70 µm porosity (See Figure A.1). Suitable polypropylene columns with
polyethylene frits are available commercially and well adapted to robotized operation. The packing and
conditioning of the columns are described in Annex A. The chromatographic columns shall be disposed of
in the radioactive waste after use.
3.3 Two hot plates.
3.4 Standard laboratory equipment (flasks and beakers, pipettes, glassware, stands and supports for
columns, sample vials, fraction tubes, etc.).
3.5 Glass vials.
4 Reagents
Use only reagents of recognized analytical grade. All aqueous solutions shall be prepared with distilled
or de-ionized water (resistivity 1 MΩ·m to 10 MΩ·m).
−1 −1
4.1 Concentrated nitric acid and nitric acid solutions, c(HNO ) = 6 mol·l and 3 mol·l .
−1
4.2 Formic acid solution, c(HCOOH) = 1 mol
...