Certification of Mass Fractions of Polycyclic Aromatic Hydrocarbons, Organochlorines and ...

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IAEA/AQ/52
IAEA Analytical Quality in Nuclear Applications Series No. 52
Certification of Mass Fractions
of Polycyclic Aromatic
Hydrocarbons, Organochlorines
and Polybrominated Diphenyl
Ethers in IAEA-459
Marine Sediment Sample
INTERNATIONAL ATOMIC ENERGY AGENCY
VIENNA
ISSN 2074–7659
CERTIFICATION OF
MASS FRACTIONS OF POLYCYCLIC
AROMATIC HYDROCARBONS,
ORGANOCHLORINES AND
POLYBROMINATED DIPHENYL ETHERS
IN IAEA-459 MARINE SEDIMENT SAMPLE
The following States are Members of the International Atomic Energy Agency:
AFGHANISTAN GEORGIA OMAN
ALBANIA GERMANY PAKISTAN
ALGERIA GHANA PALAU
ANGOLA GREECE PANAMA
ANTIGUA AND BARBUDA GUATEMALA PAPUA NEW GUINEA
ARGENTINA GUYANA PARAGUAY
ARMENIA HAITI PERU
AUSTRALIA HOLY SEE PHILIPPINES
AUSTRIA HONDURAS POLAND
AZERBAIJAN HUNGARY PORTUGAL
BAHAMAS ICELAND QATAR
BAHRAIN INDIA REPUBLIC OF MOLDOVA
BANGLADESH INDONESIA ROMANIA
BARBADOS IRAN, ISLAMIC REPUBLIC OF RUSSIAN FEDERATION
BELARUS IRAQ RWANDA
BELGIUM IRELAND SAN MARINO
BELIZE ISRAEL SAUDI ARABIA
BENIN ITALY SENEGAL
BOLIVIA, PLURINATIONAL JAMAICA SERBIA
STATE OF JAPAN SEYCHELLES
BOSNIA AND HERZEGOVINA JORDAN SIERRA LEONE
BOTSWANA KAZAKHSTAN SINGAPORE
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BRUNEI DARUSSALAM KOREA, REPUBLIC OF SLOVENIA
BULGARIA KUWAIT SOUTH AFRICA
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BURUNDI LAO PEOPLE’S DEMOCRATIC SRI LANKA
CAMBODIA REPUBLIC SUDAN
CAMEROON LATVIA SWAZILAND
CANADA LEBANON SWEDEN
CENTRAL AFRICAN LESOTHO SWITZERLAND
REPUBLIC LIBERIA SYRIAN ARAB REPUBLIC
CHAD LIBYA TAJIKISTAN
CHILE LIECHTENSTEIN THAILAND
CHINA LITHUANIA THE FORMER YUGOSLAV
COLOMBIA LUXEMBOURG REPUBLIC OF MACEDONIA
CONGO MADAGASCAR TOGO
COSTA RICA MALAWI TRINIDAD AND TOBAGO
CÔTE D’IVOIRE MALAYSIA TUNISIA
CROATIA MALI TURKEY
CUBA MALTA TURKMENISTAN
CYPRUS MARSHALL ISLANDS UGANDA
CZECH REPUBLIC MAURITANIA UKRAINE
DEMOCRATIC REPUBLIC MAURITIUS UNITED ARAB EMIRATES
OF THE CONGO MEXICO UNITED KINGDOM OF
DENMARK MONACO GREAT BRITAIN AND
DJIBOUTI MONGOLIA NORTHERN IRELAND
DOMINICA MONTENEGRO UNITED REPUBLIC
DOMINICAN REPUBLIC MOROCCO OF TANZANIA
ECUADOR MOZAMBIQUE UNITED STATES OF AMERICA
EGYPT MYANMAR URUGUAY
EL SALVADOR NAMIBIA UZBEKISTAN
ERITREA NEPAL VANUATU
ESTONIA NETHERLANDS VENEZUELA, BOLIVARIAN
ETHIOPIA NEW ZEALAND REPUBLIC OF
FIJI NICARAGUA VIET NAM
FINLAND NIGER YEMEN
FRANCE NIGERIA ZAMBIA
GABON NORWAY ZIMBABWE
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IAEA/AQ/52
IAEA Analytical Quality in Nuclear Applications Series No. 52
CERTIFICATION OF
MASS FRACTIONS OF POLYCYCLIC
AROMATIC HYDROCARBONS,
ORGANOCHLORINES AND
POLYBROMINATED DIPHENYL ETHERS
IN IAEA-459 MARINE SEDIMENT SAMPLE
INTERNATIONAL ATOMIC ENERGY AGENCY
VIENNA, 2017
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For further information on this publication, please contact:
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CERTIFICATION OF MASS FRACTIONS OF POLYCYCLIC AROMATIC HYDROCARBONS, ORGANOCHLORINES
AND POLYBROMINATED DIPHENYL ETHERS IN IAEA-459 MARINE SEDIMENT SAMPLE
IAEA, VIENNA, 2017
IAEA/AQ/52
ISSN 2074–7659
© IAEA, 2017
Printed by the IAEA in Austria
October 2017
FOREWORD
One of the major programmes of the IAEA Environment Laboratories is to assist Member
States in the understanding, monitoring and protection of both terrestrial and marine
environments. To assess the impact of land and sea based pollution sources on marine coastal
environments, it is imperative to ensure the quality and comparability of the analytical data
generated by national and regional pollution monitoring programmes. Since the early 1970s,
the IAEA has assisted national laboratories and regional laboratory networks through the
production of certified reference materials, training in quality assurance and evaluation of
measurement performances by organizing worldwide and regional interlaboratory comparison
exercises and proficiency tests.
This publication describes the production of certified reference material IAEA-459, which is
produced following ISO Guides 34:2009 and 35:2006. This certified reference material is a
sediment sample with certified mass fractions of polycyclic aromatic hydrocarbons,
organochlorines and polybrominated diphenyl ethers. The assigned final values and their
associated uncertainties were derived from robust statistics on the results provided by selected
laboratories with demonstrated technical and quality competence, following the guidance
given in the ISO Guides. The material is used for quality control and assessment of method
performance for a number of organic analytes listed in the Stockholm Convention on
Persistent Organic Pollutants as well as other pollutants listed as priority substances included
in many environment monitoring programmes.
The IAEA is grateful to the Government of Monaco for its support and wishes to thank all
laboratories and participants who took part in the characterization study of this reference
material, in particular the Korea Institute of Ocean Science and Technology for the donation
of the raw material. The IAEA officers responsible for this publication were I. Tolosa,
R. Cassi and D. Huertas of the IAEA Environment Laboratories.
EDITORIAL NOTE
This publication has been prepared from the original material as submitted by the contributors and has not been edited by the editorial
staff of the IAEA. The views expressed remain the responsibility of the contributors and do not necessarily reflect those of the IAEA or
the governments of its Member States.
Neither the IAEA nor its Member States assume any responsibility for consequences which may arise from the use of this publication.
This publication does not address questions of responsibility, legal or otherwise, for acts or omissions on the part of any person.
The use of particular designations of countries or territories does not imply any judgement by the publisher, the IAEA, as to the legal
status of such countries or territories, of their authorities and institutions or of the delimitation of their boundaries.
The mention of names of specific companies or products (whether or not indicated as registered) does not imply any intention to
infringe proprietary rights, nor should it be construed as an endorsement or recommendation on the part of the IAEA.
The IAEA has no responsibility for the persistence or accuracy of URLs for external or third party Internet web sites referred to in this
publication and does not guarantee that any content on such web sites is, or will remain, accurate or appropriate.
CONTENTS

1. INTRODUCTION............................................................................................................................... 1
2. METHODOLOGY .............................................................................................................................. 2
2.1. COLLECTION AND PREPARATION OF THE MATERIAL ...........................................2
2.2. SELECTION OF LABORATORIES FOR THE CHARACTERIZATION STUDY ............2
2.3. HOMOGENEITY ASSESSMENT .....................................................................................2
2.4. STABILITY STUDY .........................................................................................................3
2.4.1. Short-term stability ..........................................................................................................3
2.5. CHARACTERIZATION ....................................................................................................4
2.6 . MOISTURE CONTENT....................................................................................................7
2.7 . ELEMENTAL COMPOSITION AND ISOTOPES VALUES ............................................7
3. RESULTS AND DISCUSSION ........................................................................................................ 7
3.1. RESULTS OF THE HOMOGENEITY STUDY .................................................................7
3.1.1. Between-unit homogeneity ..............................................................................................7
3.1.2. Within-unit homogeneity ............................................................................................... 10
3.2. RESULTS FOR STABILITY STUDY ............................................................................. 11
3.2.1. Short-term stability study............................................................................................... 11
3.2.2. Long-term stability study ............................................................................................... 11
3.3. DETERMINATION OF ASSIGNED VALUES AND UNCERTAINTIES ....................... 11
4. METROLOGICAL TRACEABILITY AND COMMUTABILITY ............................................. 23
5. CONCLUSIONS ............................................................................................................................... 23
APPENDIX I ................................................................................................................................................ 25
RESULTS FOR THE CERTIFIED MEASUREMENTS OF PAHS ....................................................... 25
APPENDIX II .............................................................................................................................................. 44
RESULTS FOR THE CERTIFIED MEASUREMENTS OF POLYCHORINATED BIPHENYLS
(PCBs) .......................................................................................................................................................... 44
APPENDIX III ............................................................................................................................................. 66
RESULTS FOR THE CERTIFIED MEASUREMENTS OF ORGANOCHLORINATED
PESTICIDES................................................................................................................................................ 66
APPENDIX IV ............................................................................................................................................. 72
RESULTS FOR THE CERTIFIED MEASUREMENTS OF POLYBROMINATED DIPHENYL
ETHERS (PBDEs) ....................................................................................................................................... 72
APPENDIX V .............................................................................................................................................. 77
RESULTS FOR THE INFORMATION MEASUREMENTS OF POLYCYCLIC AROMATIC
HYDROCARBONS (PAHs) ...................................................................................................................... 77
APPENDIX VI ........................................................................................................................................... 101
RESULTS FOR THE INFORMATION MEASUREMENTS OF POLYCHLORINATED
BIPHENYLS (PCBs)................................................................................................................................. 101
APPENDIX VII ......................................................................................................................................... 111
RESULTS FOR THE INFORMATION MEASUREMENTS OF ORGANOCHLORINATED
PESTICIDES.............................................................................................................................................. 111
APPENDIX VIII ........................................................................................................................................ 120
RESULTS FOR THE INFORMATION MEASUREMENTS OF POLYBROMINATED DIPHENYL
ETHERS (PBDEs) ..................................................................................................................................... 120
APPENDIX IX ........................................................................................................................................... 125
RESULTS FOR THE INFORMATION MEASUREMENTS OF ALIPHATIC HYDROCARBON 125
APPENDIX X ................................................................................................................................ 126
SYSTEMATIC NUMBERING OF PCB CONGENERS ....................................................................... 126
APPENDIX XI ........................................................................................................................................... 127
SYSTEMATIC NUMBERING OF PBDES CONGENERS .................................................................. 127
REFERENCES........................................................................................................................................... 128
LIST OF PARTICIPATING LABORATORIES .................................................................................... 129
CONTRIBUTORS TO DRAFTING AND REVIEW ............................................................................. 133
1. INTRODUCTION
The Marine Environmental Studies Laboratory (MESL) of IAEA-EL provides assistance to
Member States’ laboratories to enhance the quality of the analytical measurement results, in
trace elements and organic contaminants in the marine environmental samples. This is
achieved through the production of certified reference materials, organization of
interlaboratory comparisons and proficiency tests, and by conducting training courses on the
analysis of contaminants in marine samples. This activity is undertaken in the framework of
the EL’s subprogramme 2.4.1 “Reference Products for Science and Trade” and the Project
2.4.1.1 “Provision of Reference Products and Assurance of Laboratory Performance”.
Certified Reference Materials (CRMs) are valuable tools for analytical method development
and validation to improve the measurements and quality control in analytical laboratories.
More specifically, marine matrix CRMs are needed to ensure the reliability of the analytical
measurements and ensure the use of high quality data as the basis for decision making in
national or regional marine pollution monitoring programmes. Furthermore, since the
Stockholm Convention (SC) on persistent organic pollutants (POPs) was adopted 15 years
ago, a great number of different analytical methodologies have been extensively developed
and there is great need of CRMs for these contaminants. While there are several CRMs
certified for organic contaminants, there is still a noticeable lack of matrix CRMs, in
particular for POPs in marine sediments, where the concentrations levels are in the low range
of µg kg-1. To meet this need, MESL has developed a sediment CRM for the determination of
a great number of organic analytes listed as Persistent Organic Pollutants (POPs) by the
Stockholm Convention as well as other POPs listed as priority substances (PSs), such as
polycyclic aromatic hydrocarbons included in many environment monitoring programmes.
This report describes and provides information on the sample preparation methodology
followed and on the assignment of property values with their associated uncertainties for a
number of persistent organic contaminants in a marine sediment sample. Certification of the
mass fractions was made for major POPs, including polycyclic aromatic hydrocarbons
(PAHs), polychlorinated biphenyls (PCBs), chlorinated pesticides and polybrominated
diphenyl ethers (PBDEs). Results on aliphatic hydrocarbons and other minor POPs are also
provided as information values.
The CRM IAEA-459 was produced to satisfy the needs of laboratories to strengthen data
quality assurance in the analysis of POPs and other priority substances in marine samples

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