SIST EN ISO 15366-2:2016

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 2: Samples containing plutonium and uranium in the nanogram range and below (ISO 15366-2:2014)

ISO 15366-2:2014 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 15366-2:2014 describes a slightly different separation technique from ISO 15366-1, based on the same chemistry, using smaller columns, different support material and special purification steps, applicable to samples containing plutonium and uranium amounts in the nanogram range and below. The detection limits were found to be 500 pg plutonium and 500 pg uranium.

Kernbrennstofftechnologie - Chemische Trennung und Reinigung von Uran und Plutonium in Salpetersäure-Lösungen für Isotopen- und Isotopenverdünnungsanalysen mittels Lösemittelextraktions-Chromatographie - Teil 2: Proben mit Plutonium und Uranium im Nanogrammbereich und weniger (ISO 15366-2:2014)

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 2: Échantillons ayant des teneurs en plutonium et en uranium de l'ordre du nanogramme et inférieures (ISO 15366-2:2015)

ISO 15366-2:2014 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]). La présente partie de l'ISO 15366 décrit une technique de séparation légèrement différente de celle de l'ISO 15366‑1, reposant sur la même chimie mais utilisant des colonnes plus petites, un matériau support différent et des étapes de purification spécifiques, applicable aux échantillons contenant des quantités de plutonium et d'uranium de l'ordre du nanogramme et inférieures. Les limites de détection se sont révélées être de 500 pg pour le plutonium et de 500 pg pour l'uranium. L'Annexe A décrit la préparation des colonnes et les matériaux de support de colonne.
Par rapport à l'ISO 15366‑1, les quantités d'uranium et de plutonium étant moindres, une purification supplémentaire sur une résine échangeuse d'anions est réalisée.

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 - 2. del: Vzorci s plutonijem in uranom v nanogramskih količinah in manj (ISO 15366-1:2014)

Standard ISO 15366-2:2014 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 15366-2:2014 opisuje nekoliko drugačno tehniko ločevanja kot standard ISO 15366-1, in sicer na podlagi enake kemije, z uporabo manjših stolpcev, drugačnega odpornega materiala in posebnih korakov čiščenja, ki se uporablja za vzorce, ki vsebujejo količine plutonija in urana v nanogramskem razponu ter nižjem. Ugotovljene meje zaznavanja so 500 pg za plutonij in 500 pg za uran.

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: 03-May-2016
• Due Date: 08-Jul-2016
• Completion Date: 17-May-2016
• Ref Project: EN ISO 15366-2:2016 - 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 2: Samples containing plutonium and uranium in the nanogram range and below (ISO 15366-2:2014)

Overview - EN ISO 15366-2:2016 (ISO 15366-2:2014)

EN ISO 15366-2:2016 is a CEN-adopted international standard for nuclear fuel technology that specifies chemical separation and purification procedures for uranium and plutonium in nitric acid solutions prior to isotopic and isotope-dilution analysis by techniques such as mass spectrometry or alpha spectrometry. It targets very low-level samples - plutonium and uranium in the nanogram range and below - and documents a solvent-extraction chromatography method using mini-columns coated with tri-n‑octylphosphine‑oxide (TOPO). The method’s detection limits were determined as ≈500 pg for both plutonium and uranium.

Key topics and technical requirements

• Scope and sample types: Dissolved solutions from irradiated light-water reactor fuel and high-activity liquid waste from spent fuel reprocessing plants.
• Separation principle: Extraction chromatography on disposable mini-columns with TOPO-coated supports (polyethylene or silica) in 3 mol·L−1 HNO3; selective retention of Pu(IV) and U(VI).
• Valency control: Use of iron(II) sulfate and sodium nitrite to adjust oxidation states prior to separation.
• Elution and purification:
  • Plutonium eluted after chemical reduction (e.g., ascorbic acid).
  • Uranium eluted with ammonium carbamate and further purified by anion exchange resin or fuming with concentrated HNO3.
• Column and support details: Mini-columns (disposable polypropylene) packed with polyethylene powder coated with TOPO; Annex A describes packing and conditioning.
• Quality and operational controls: Run blanks and control samples in parallel; work in clean conditions (laminar-flow fume hood or shielded glovebox); gravity flow rates should not exceed 0.4 mL·min−1.
• Reagents and apparatus: Suprapure-grade reagents (HNO3, HCl, TOPO in cyclohexane, ammonium carbamate, ascorbic acid, etc.), PTFE vials, shielded workspace and hotplates.

Practical applications and users

• Nuclear fuel and reprocessing laboratories performing isotopic analysis, isotope-dilution mass spectrometry and alpha spectrometry on ultra‑low-level uranium and plutonium samples.
• Radioanalytical and safeguards labs requiring validated separation methods for trace-level plutonium/uranium in spent fuel dissolution solutions and high-activity wastes.
• Environmental and forensic labs analyzing minute nuclear materials where robust separation and low detection limits (≈500 pg) are critical.

Related standards

• ISO 15366-1 - Part 1: procedures for higher amounts (microgram/milligram range).
• ISO 8299 - Guidance related to mass spectrometric isotopic analysis.
• ISO 11483 - Alpha spectrometry method references.

This standard is essential for practitioners implementing solvent extraction chromatography workflows for trace-level uranium and plutonium isotopic measurements, ensuring reproducible separation, low blank levels, and compatibility with downstream mass spectrometry or alpha spectrometry analysis.

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 2: Samples containing plutonium and uranium in the nanogram
range and below (ISO 15366-2:2014)
Kernbrennstofftechnologie - Chemische Trennung und Reinigung von Uran und
Plutonium in Salpetersäure-Lösungen für Isotopen- und Isotopenverdünnungsanalysen
mittels Lösemittelextraktions-Chromatographie - Teil 2: Proben mit Plutonium und
Uranium im Nanogrammbereich und weniger (ISO 15366-2:2014)
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 2:
Échantillons ayant des teneurs en plutonium et en uranium de l'ordre du nanogramme et
inférieures (ISO 15366-2:2015)
Ta slovenski standard je istoveten z: EN ISO 15366-2:2016
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 15366-2
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 2: Samples
containing plutonium and uranium in the nanogram range
and below (ISO 15366-2:2014)
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 2:
Partie 2: Échantillons ayant des teneurs en plutonium Proben mit Plutonium und Uranium im
et en uranium de l'ordre du nanogramme et inférieures Nanogrammbereich und weniger (ISO 15366-2:2014)
(ISO 15366-2:2014)
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 15366-2:2016 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
European foreword
The text of ISO 15366-2:2014 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 15366-2:2016 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 15366-2:2014 has been approved by CEN as EN ISO 15366-2:2016 without any
modification.
INTERNATIONAL ISO
STANDARD 15366-2
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 2:
Samples containing plutonium and
uranium in the nanogram range and
below
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 2: Échantillons ayant des teneurs en plutonium et en uranium
de l’ordre du nanogramme et inférieures
Reference number
ISO 15366-2:2014(E)
©
ISO 2014
ISO 15366-2:2014(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 15366-2:2014(E)
Contents Page
Foreword .iv
1 Scope . 1
2 Principle of the method . 1
3 Apparatus . 2
4 Reagents . 2
5 Procedure (see Figure 1). 3
6 Characteristics of the separation . 5
7 Quality control . 5
8 Interferences . 6
Annex A (normative) Packing and conditioning of the chromatographic mini-columns as used in
the ISO 15366-2 procedure, loaded with an inert polyethylene support coated with tri-n-
octyl-phosphine-oxide (TOPO) . 7
Bibliography .10
ISO 15366-2:2014(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, Subcommittee SC 5, Nuclear
Fuel Technology.
This first edition, together with the first edition of ISO 15366-1, 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 15366-2:2014(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 2:
Samples containing plutonium and uranium in the
nanogram range and below
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
[1] [2]
(see ISO 8299 ) or alpha spectrometry (see ISO 11483 ). This part of ISO 15366 describes a slightly
different separation technique from ISO 15366-1, based on the same chemistry, using smaller columns,
different support material and special purification steps, applicable to samples containing plutonium
and uranium amounts in the nanogram range and below. The detection limits were found to be 500 pg
plutonium and 500 pg uranium. Annex A describes the preparation of the columns and the column
support materials.
In comparison with ISO 15366-1, as uranium and plutonium amounts are lowest, additional purification
on an anion exchange resin is performed.
2 Principle of the method
The chemical separation of small plutonium and uranium amounts (>500 pg) is also based on a column
[3][4]
extraction chromatography using tri-n-octylphosphine-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 mini-columns loaded with a polyethylene or silica gel powder coated
−1
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.
[5]
Plutonium is eluted after reduction to the trivalent state with ascorbic acid ; uranium is eluted by
an ammonium carbamate solution and finally purified from ammonium salts by an ion exchange
[6] −1
separation or fuming by 14 mol·l nitric acid.
In order to ensure a favourable kinetics of chemical reactions the (gravity) column flow rates should not
−1
exceed 0,4 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 or 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.
The whole process is carried out under clean conditions preferably in a laminar flow fume hood.
ISO 15366-2:2014(E)
3 Apparatus
3.1 Biological shielding, e.g. shielded glove box or fume cupboard, preferably a laminar flow fume
cupboard.
3.2 Disposable polypropylene columns and frits (see Figure A.1). Type: micro-column. 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.). It is recommended to leach all equipment, which will be in
contact with samples, eluates or eluents with nitric acid (4.1) and distilled water before use. After drying,
store it in plastic bags in a clean area.
3.5 PTFE vials, of dimensions: volume 15 ml, diameter 28 mm, height 37 mm. With screw caps and
metal jackets.
These vials may be used at least 10 times, after a careful cleaning with hot nitric acid, followed by a
rinsing with demineralized or de-ionized water.
4 Reagents
Use only reagents of recognized suprapure grade or equivalent. All aqueous solutions shall be prepared
with distilled 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·l .
−1
4.3 Ammonium carbamate [CAS No. 1111-78-0] solution, c(NH CO NH ) = 0,7 mol·l .
4 2 2
1)
4.4 Polyethylene powder GUR X 117/PE-UHMW Ultra-high-molecular grain size 25 µm to 95 µm,
pore size ≤5 µm (see A.2.5).
−5 −1 −3 −1
4.5 L(+)-Ascorbic acid solution c(C H O ) = 10 mol·l or c(C H O ) = 10 mol·l in formic acid
6 8 6 6 8 6
solution (4.2)
−1
4.6 Tri-n-octylphosphine-oxide, c(TOPO) = 0,2 mol·l solution in cyclohexane.
WARNING — This reagent is flammable and should always be handled in a well-ventilated place
and never in the vicinity of a naked flame.
−1 −1
4.7 Iron(II) sulfate solution, c(FeSO ) = 0,1 mol·l or c(FeSO ) = 0,8 mol·l in water. To be prepared
4 4
freshly for each working session.
−1 −1
4.8 Sodium nitrite solution, c(NaNO ) = 1 mol·l or c(NaNO ) = 5 mol·l in water. To be prepared
2 2
freshly for each working session.
4.9 Aqua regia, mixture 3:1 (per volume) of concentrated hydrochloric acid and concentrated nitric
acid.
1) Silic
...