(Certified) Reference

Materials

Ioannis Papadakis
Index
 definitions - documentation
 types of (C)RMs
 production of (C)RMs
 selection and use of (C)RMs
 CRMs and traceability
 suppliers/producers of (C)RMs
ISO Guides
 ISO 30 (1992) terms and definitions used in
connection with RMs
 ISO 31 (2000) certificates of RMs
 ISO 32 (1997) calibration in analytical
chemistry and use of CRMs
 ISO 33 (2000) uses of CRMs
 ISO 34 (2000) general requirements for the
competence of RM producers
 ISO 35 (1989) certification of RMs
Reference Material
Definition
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
Reference Material (RM)
 a reference material may be in the form
of a pure or mixed gas, liquid or solid
 examples are water for the calibration of
viscometers, sapphire as a heat-
capacity calibrant in calorimetry, and
solutions used for calibration in
chemical analysis
Certified Reference Material
Definition
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
Certified Reference Material
(CRM)
 all CRMs lie within the definition of
“measurement standards” or “etalons”
 CRMs are generally prepared in
batches for which the property values
are determined within stated uncertainty
limits by measurements on samples
representative of the whole batch
Classification of RMs
 physical character
 gases, liquids or solids
 supplied property
 pure chemical species, physico-chemical property
 preparation method
 synthetic mixtures, natural materials
 metrological qualification
 primary RM, secondary RM
 intended use
 calibration of instruments, validation of analytical methods
Reference Materials in Analytical Chemistry - A Guide for Selection and Use, edited
by A Zschunke, Springer, 2000
CRM Production
According to ISO-35
 producing a CRM is:
 the integrated process of correct preparation,
homogeneity and stability demonstration, and
accurate and traceable characterisation,
 whereby all components of uncertainty of “the
sample on the desk of the user” should be
properly accounted for according to the ISO-
GUM (Guide for the expression of uncertainty in
measurement)
CRM Production
Non-trivial Job!
 it requires ...
 skills and installation to process the
material in a suitable form, especially for
matrix CRMs
(e.g. making 2000 containers of orange juice sample for
heavy metals content measurement, with demonstrated
homogeneity and stability)
 demonstrated measurement capability, to
produce reference value
CRM Production
Production Process
 select the material
 prepare the units (e.g. bottles)
 labelling
 measure homogeneity
 measure stability
 assignment of reference values
 distribution/marketing
Select the Material

 depends on the needs of the

analytical community
 measurement that needs to be
supported
 depends on availability of material
Prepare the Units
 select appropriate container
(size, shape, material, properties …)
 prepare the units (e.g. vials) under the
appropriate conditions
 each unit should contain the
appropriate amount of material
 prepare appropriate number of units
Measure Homogeneity

 fast measurement method

 small sample quantity
 good reproducibility
 within containers
 between containers
Measure Stability

 fast measurement method

 small sample quantity
 good reproducibility
 different storing temperatures
 different times
Assignment of Reference Value

 by measurement (CRM)
 by designation (RM)
Assignment of Reference Value
by Measurement
 one method in one lab
(e.g. a primary method)
 one method in several labs
 several methods in several labs
Traceability of the Assigned
Value
 needs to be stated
 … and demonstrated
 information available in
certification report
Uncertainty of the Assigned
Value (UCRM )
UCRM uncertainty of the average concentration of
1 unit (of the n prepared) after storage for time
T and after transport
UCRM [%]=k*(u2assign +u2bb +u2lts +u2sts )1/2

uassign uncertainty value assignment measurement

ubb uncertainty bottle to bottle variation
ults uncertainty long term stability
usts uncertainty short term stability (transport)
Labelling

 equally important
 clear and concise
Distribution / Marketing

 certification report
 appropriate price
 appropriate delivery
 appropriate storage
 reach scientific community
In General High Quality CRMs
Should…
 state traceability of certified value
(e.g. traceability to S.I., or to values obtained with method XYZ)
 state an ISO-GUM uncertainty of certified
value
 demonstrate traceability & uncertainty
of certified value
(e.g. in a certification report; experimental evidence of
demonstrated capability from participation to international
comparisons)
 preferably be produced according to the
guidelines of ISO-35
Use of CRMs
 (ideally) supplier should give advice
 storage temperature
 influence of moisture on long term
stability (e.g. biological activity)
 influence of contamination
 possibility to divide in different portions
after opening
Use of CRMs

how can CRMs help my measurements?

 calibration (?)
 validation (?)
 measurement control (?)
Calibration

response

concentration

use as a matrix matched calibrant

(direct or via working standards)
to ensure traceability of results
to an external reference (the CRM)
Validation certified concentration

Concentration

check the measurement results

in terms of validity:
is there any method specific bias ?
is there any systematic error ?
Measurement Control

10

12
13
14
15
16
17
18
11
2
3
4
5
6
7
8
9
1
 Abuse of CRM (Upper) Control line

-3s
 Instead : use in- (Upper) Warning line

-2s
house materials or

-1s
quality control

0
materials
(i.e. of proven homogeneity

1s
and stability; sometimes

2s
named in-house RMs or (Lower) Warning line
laboratory RMs) 3s (Lower) Control line
Use of CRMs

how can CRMs help my measurements?

X YES
 calibration (?)
X YES
 validation (?)
X NO
 measurement control (?)
How CRMs are Used in Terms of
Traceability?
n
a tio S.I.
r
lib
c a
to calibrate own value 1
analytical instrument

value 2

my result
How CRMs are Used in Terms of
Traceability?
on
a ti S.I.
li d
v a
value 1 to validate own
analytical method

value 2

my result value CRM

Selection of CRMs
 availability (problem with matrix CRMs)
 concentration range of certified property
 uncertainty of certified property
 traceability of certified property
 what is your uncertainty requirement
 contribution of CRM uncertainty on your
measurement uncertainty
 demonstrated competence of CRM producer
 CRM matrix
 cost
CRM Producers
 general
 COMAR database: http://www.bam.de
 individual suppliers
 IRMM: http://www.irmm.jrc.be
 BAM: http://www.bam.de
 LGC: http://www.lgc.co.uk
 NIST: http://www.nist.gov
 others...
General Statement

I use a CRM, therefore my

measurement result is
automatically correct
Things to Remember

 very important component

 production is not trivial
 selection and use is not easy
 CRMs do not automatically
ensure quality outcome
 THANK YOU
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