European Accreditation
European Accreditation
European Accreditation
Publication
The Selection
and Use of
Reference Materials
PURPOSE
The aim of this paper is to provide a short, simple and user-friendly guide for laboratories,
and accreditation and certification bodies. It employs mainly ISO and VIM definitions and
provides references to other more comprehensive and expert texts. It is intended to provide
help for the inexperienced rather than the expert and necessarily simplifies some topics. It
includes discussion and clarification of some misunderstood issues. Although based on the
requirements of chemical measurement, it is intended to be also of use in other areas of
measurement.
Authorship
The publication has been prepared by the EEE-RM working group
Official language
The text may be translated into other languages as required. The English language version
remains the definitive version.
Copyright
The copyright of this text is held by EA. The text may not be copied for resale.
Further information
For further information about this publication, contact your national member of EA or the EA
Secretariat at secretariat@european-accreditation.org
Tansitionnal period:
CONTENTS
ABSTRACT ............................................................................................................................. 4
INTRODUCTION .................................................................................................................... 4
1 - TYPES OF REFERENCE MATERIALS........................................................................ 5
2 - CLASSIFICATION OF REFERENCE MATERIALS .................................................... 5
3 - TRACEABILITY OF REFERENCE MATERIALS ........................................................ 6
4 - THE AVAILABILITY AND SELECTION OF REFERENCE MATERIALS ................ 6
5 - USES OF REFERENCE MATERIALS .......................................................................... 7
5.1 Method Validation and Measurement Uncertainty ................................................. 7
5.2 Verification of the Correct Use of a Method ............................................................ 7
5.3 Calibration ..................................................................................................................... 8
5.4 Quality Control and Quality Assurance (QC&QA) .................................................. 8
6 - ASSESSMENT OF THE SUITABILITY OF REFERENCE MATERIALS ................ 8
6.1 Certificates and Supporting Reports ......................................................................... 9
6.2 - Assessment of the Suitability of Reference Materials ......................................... 9
7 - IN-HOUSE PREPARATION OF REFERENCE MATERIALS ................................. 10
8 - DEFINITIONS.................................................................................................................. 10
9 - KEY REFERENCE MATERIALS PUBLICATIONS ................................................... 10
10 - REFERENCES ............................................................................................................. 11
FIGURE 1: Overlap between functions associated with Measurement Traceability
and Analytical Quality ...................................................................................................... 13
FIGURE 2: Assessment of the suitability of a Reference Material ........................... 13
ABSTRACT
The aim of this paper is to provide a short, simple and user-friendly guide for laboratories,
and accreditation and certification bodies. It employs mainly ISO and VIM definitions and
provides references to other more comprehensive and expert texts. It is intended to provide
help for the inexperienced rather than the expert and necessarily simplifies some topics. It
includes discussion and clarification of some misunderstood issues. Although based on the
requirements of chemical measurement, it is intended to be also of use in other areas of
measurement.
INTRODUCTION
There are a number of authoritative and detailed texts on various aspects of reference
materials and these are listed at the end of this paper, together with some internationally
recognised (1-4) definitions. This paper aims to provide a simple guide on the use of
reference materials (RMs) within a wider quality programme. Reference materials are an
important tool in realising a number of aspects of measurement quality and are used for
method validation, calibration, estimation of measurement uncertainty, training and for
internal QC and external QA (proficiency testing) purposes.
In the wider sense, the validity of measurements can be assured when:
work is carried out to a clearly defined customer requirement
validated methods and equipment are used
qualified and competent staff undertake the work
comparability with measurements made in other laboratories is assured
(traceability and measurement uncertainty)
independent evidence of performance is available (proficiency testing)
well defined QC and QA procedures are employed, preferably involving third
party accreditation
Often a measurement operation serves more than one quality purpose and there can be
overlap of function as illustrated in Figure 1. Different types of reference materials are
required for different functions. For example, a certified reference material would be
desirable for method validation but a working level reference material would be adequate for
QC.
More detailed guidance on the QA of chemical measurements, including cover of reference
materials, calibration, QC and validation is provided in a joint CITAC Eurachem guide (5).
Other terminology, such as NIST Standard Reference Materials (SRMs) is also used and a
classification (class O - V) based on degree of traceability to SI has been proposed (8). Pan
(9) has also published a useful paper on this topic.
Primary method SI
Method of known bias SI/International standard
Independent method(s) Results of specified methods
Interlaboratory comparison Results of specified methods
Not all materials that are used as reference materials are described as such. Commercially
available chemicals of varying purity, commercial matrix materials and products from
research programs are often used as standards or reference materials. In the absence of
‘certification’ data provided by the supplier it is the responsibility of the user to assess the
information available and undertake further characterisation as appropriate. Guidance on
the preparation of reference materials is given in ISO Guides 31, 34 and 35 and guides on
the preparation of working level reference materials are also available (12,13).
Information about reference materials is available from a number of sources. The COMAR
Database, contains information on more than 10,000 RMs/CRMS which can be accessed
directly or through institutes which provide an advisory service. Further information can be
obtained from the COMAR Central Secretariat (comar@BAM.de). Advisory services assist
users identify the type of material required for their task and identify a supplier. A database
covering reference materials currently under development has been prepared by CITAC and
ISO REMCO (14). A number of suppliers provide a comprehensive range of materials
including materials produced by other organisations and aim to provide a one-stop-shop for
users. A first internet database for a selection of RMs has recently appeared and is likely to
be followed by others (http://www.iaea.org/programmes/nahunet/e4/nmrm/index.htm)
A more detailed description of the use of RMs is available in ISO Guides 32 and 33
5.3 Calibration
Normally a pure substance RM is used for calibration of the measurement stage of a
method. Other components of the test method, such as sample digestion, separation and
derivatisation are, of course, not covered and loss of analyte, contamination and
interferences and their associated uncertainties must be addressed as part of the validation
of the method. The uncertainty associated with RM purity will contribute to the total
uncertainty of the measurement. For example, an RM certified as 99.9% pure, with an
expanded uncertainty U (k=2) of 0.1% will contribute an uncertainty component of 0.1% to
the overall measurement uncertainty budget. In the case of trace analysis, this level of
uncertainty will rarely be important but for assay work, it can be expected to be significant.
Some other methods, such as XRF analysis, use matrix RMs for calibration of the complete
analytical process. In addition to a close matrix match, the analyte form must be the same in
the samples and RMs, and the analytical concentrations of the RMs must span that of the
samples (12).
ISO Guide 32 and reference 7 provide additional useful information.
8 - DEFINITIONS
Calibration (1): Set of operations that establish, under specified conditions, the relationship
between the values of quantities indicated by a measurement instrument or measuring
system or values represented by a material measure or a reference material, and the
corresponding values realised by standards.
Certified Reference Material (1): Reference material, accompanied by a certificate, one or
more of whose property values are certified by a procedure which establishes traceability to
an accurate realisation of the unit in which the property values are expressed, and for which
each certified value is accompanied by an uncertainty at a stated level of confidence.
Primary method (2): A primary method is a method having the highest metrological
qualities, whose operation can be completely described, and understood and for which a
complete uncertainty statement can be written down in terms of SI units. A primary direct
method measures the value of an unknown without reference to a standard of the same
quantity. A primary ratio method measures the ratio of an unknown to a standard of the
same quantity; its operation must be completely described by a measurement equation. The
methods identified as having the potential to be primary methods are: isotope dilution mass
spectrometry: gravimetry, covering gravimetric mixtures and “gravimetric analysis”;
titrimetry; coulometry; determination of freezing point depression; differential scanning
calorimetry and nuclear magnetic resonance spectroscopy. Other methods such as
chromatography, which has extensive applications in organic chemical analysis, have also
been proposed.
Reference material (RM) (1): Material or substance one or more of whose property values
are sufficiently homogeneous and well established to be used for the calibration of an
apparatus, the assessment of a measurement method, or for assigning values to materials.
Traceability (1): Property of a result of a measurement or the value of a standard whereby
it can be related to stated references, usually national or international standards, through an
unbroken chain of comparisons all having stated uncertainties.
Uncertainty of measurement (1): Parameter associated with the result of a measurement
that characterises the dispersion of the values that could reasonably be attributed to the
measurand.
Validation (3): Confirmation by examination and provision of objective evidence that the
particular requirements of a specified intended use are fulfilled. Method validation has not
been formally defined but a Guide on the topic is available (4)
10 - REFERENCES
1. International vocabulary of basic and general terms in metrology (VIM), second
edition, 1993, ISO/BIPM/IEC/IFCC/IUPAC/IUPAP/IOML, Published by ISO
2. Minutes of 4th CCQM meeting, Feb 1998, Paris
10. ILAC Guidelines for the Competence of Reference Material Producers, ILAC
G12, 2000 (see www.ILAC.org)
11. A Marschal, Traceability and Calibration in Analytical Chemistry - Principles and
Applications to Real Life in Connection with ISO 9000, EN 45000 And ISO Guide
25, Eurolab Symposium, Firenze, April 1994
12. B Brookman and R Walker, Guidelines for the In-House Production of Reference
Materials, March 1997, LGC Report, UK
13. J M Christensen, Guidelines for Preparation and Certification of Reference
Materials for Chemical Analysis in Occupational Health, NORDREF, 1998 (ISBN:
87-7904-010-1)
14. S D Rasberry and C L Monti, Worldwide Production of CRMs: 1996 Status
Report, NIST Report Feb 1996
15. S L R Ellison and A Williams, Measurement Uncertainty: The Key to the Use of
Recovery Factors, pp 30-37, The Use of Recovery Factors in Trace Analysis, Ed
M Parkany, RSC, 1996
16. ISO/IEC 17025 General requirements for the competence of testing and
calibration laboratories (ISO/IEC 17025:1999)
Prepared by Bernard King on behalf of and with assistance from the EEE-RM
working group.
Validation Traceable
calibration
Measurement Uncertainty/
Traceability
QC/QA
Valid measurement
No
Reported RM charac-teristics fully match analytical
requirement Limitations but RM is
best available and
meets minimum
requirements
Yes
Yes
No
Notes to Fig. 2:
Note 1: The analytical requirements specification should include details concerning the
measurand, concentration, traceability, measurement uncertainty, etc
June 2002