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
Technical Committee
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
03-May-2016
Due Date
08-Jul-2016
Completion Date
17-May-2016

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SLOVENSKI STANDARD
SIST EN ISO 15366-2:2016
01-junij-2016
7HKQRORJLMDMHGUVNLKJRULY.HPLþQRORþHYDQMHLQþLãþHQMHXUDQDLQSOXWRQLMDY
UD]WRSLQDKGXãLNRYHNLVOLQH]DDQDOL]RL]RWRSRYLQUD]UHGþHQLKL]RWRSRYV
NURPDWRJUDILMR]HNVWUDNFMRVWRSLORPGHO9]RUFLVSOXWRQLMHPLQXUDQRPY
QDQRJUDPVNLKNROLþLQDKLQPDQM ,62

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
SIST EN ISO 15366-2:2016 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
SIST EN ISO 15366-2:2016
---------------------- Page: 2 ----------------------
SIST EN ISO 15366-2:2016
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.
---------------------- Page: 3 ----------------------
SIST EN ISO 15366-2:2016
EN ISO 15366-2:2016 (E)
Contents Page

European foreword ....................................................................................................................................................... 3

---------------------- Page: 4 ----------------------
SIST EN ISO 15366-2:2016
EN ISO 15366-2:2016 (E)
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.
---------------------- Page: 5 ----------------------
SIST EN ISO 15366-2:2016
---------------------- Page: 6 ----------------------
SIST EN ISO 15366-2:2016
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
---------------------- Page: 7 ----------------------
SIST EN ISO 15366-2:2016
ISO 15366-2:2014(E)
COPYRIGHT PROTECTED DOCUMENT
© 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 copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2014 – All rights reserved
---------------------- Page: 8 ----------------------
SIST EN ISO 15366-2:2016
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 2014 – All rights reserved iii
---------------------- Page: 9 ----------------------
SIST EN ISO 15366-2:2016
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
---------------------- Page: 10 ----------------------
SIST EN ISO 15366-2:2016
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

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

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 2014 – All rights reserved 1
---------------------- Page: 11 ----------------------
SIST EN ISO 15366-2:2016
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 .

4.2 Formic acid solution, c(HCOOH) = 1 mol·l .
4.3 Ammonium carbamate [CAS No. 1111-78-0] solution, c(NH CO NH ) = 0,7 mol·l .
4 2 2

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)
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
...

SLOVENSKI STANDARD
kSIST FprEN ISO 15366-2:2015
01-november-2015
7HKQRORJLMDMHGUVNLKJRULY.HPLþQRORþHYDQMHLQþLãþHQMHXUDQDLQSOXWRQLMDY
UD]WRSLQDKGXãLNRYHNLVOLQH]DDQDOL]RL]RWRSRYLQUD]UHGþHQLKL]RWRSRYV
NURPDWRJUDILMR]HNVWUDNFMRVWRSLORPGHO9]RUFLVSOXWRQLMHPLQXUDQRPY
QDQRJUDPVNLKNROLþLQDKLQPDQM ,62

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: FprEN ISO 15366-2
ICS:
27.120.30 Fisijski materiali Fissile materials
kSIST FprEN ISO 15366-2:2015 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
kSIST FprEN ISO 15366-2:2015
---------------------- Page: 2 ----------------------
kSIST FprEN ISO 15366-2:2015
EUROPEAN STANDARD
FINAL DRAFT
FprEN ISO 15366-2
NORME EUROPÉENNE
EUROPÄISCHE NORM
August 2015
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 dans les Reinigung von Uran und Plutonium in Salpetersäure-

solutions d'acide nitrique par extraction chromatographique Lösungen für Isotopen- und Isotopenverdünnungsanalysen

par solvant pour les mesures isotopiques et les analyses mittels Lösemittelextraktions-Chromatographie - Teil 2:

par dilution isotopique - Partie 2: Échantillons ayant des Proben mit Plutonium und Uranium im Nanogrammbereich

teneurs en plutonium et en uranium de l'ordre du und weniger (ISO 15366-2:2014)
nanogramme et inférieures (ISO 15366-2:2015)

This draft European Standard is submitted to CEN members for unique acceptance procedure. It has been drawn up by the Technical

Committee CEN/TC 430.

If this draft becomes a European Standard, 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.

This draft European Standard was established by CEN 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.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are aware and to

provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without notice and

shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels

© 2015 CEN All rights of exploitation in any form and by any means reserved Ref. No. FprEN ISO 15366-2:2015 E

worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
kSIST FprEN ISO 15366-2:2015
FprEN ISO 15366-2:2015 (E)
Contents Page

European foreword .............................................................................................................................................3

---------------------- Page: 4 ----------------------
kSIST FprEN ISO 15366-2:2015
FprEN ISO 15366-2:2015 (E)
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 FprEN ISO 15366-2:2015 by Technical Committee CEN/TC 430 “Nuclear energy,

nuclear technologies, and radiological protection” the secretariat of which is held by AFNOR.

This document is currently submitted to the Unique Acceptance Procedure.
Endorsement notice

The text of ISO 15366-2:2014 has been approved by CEN as FprEN ISO 15366-2:2015 without any

modification.
---------------------- Page: 5 ----------------------
kSIST FprEN ISO 15366-2:2015
---------------------- Page: 6 ----------------------
kSIST FprEN ISO 15366-2:2015
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
---------------------- Page: 7 ----------------------
kSIST FprEN ISO 15366-2:2015
ISO 15366-2:2014(E)
COPYRIGHT PROTECTED DOCUMENT
© 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 copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2014 – All rights reserved
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kSIST FprEN ISO 15366-2:2015
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

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kSIST FprEN ISO 15366-2:2015
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

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kSIST FprEN ISO 15366-2:2015
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

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

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.

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kSIST FprEN ISO 15366-2:2015
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 .

4.2 Formic acid solution, c(HCOOH) = 1 mol·l .
4.3 Ammonium carbamate [CAS No. 1111-78-0] solution, c(NH CO NH ) = 0,7 mol·l .
4 2 2

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)
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) Silica gel may also be used. See ISO 15366-1.
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kSIST FprEN ISO 15366-2:2015
ISO 15366-2:2014(E)

4.10 Concentrated hydrochloric acid and hydrochloric acid solution c(HCl) = 6 mol·l

4.11 Anion exchange resin AG MP1, slurry in distilled water. Fill th
...

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