Certified Reference Materials -

A Path to Traceable Chemical

Measurements

Paul Armishaw
5 May 2016
 What I plan to talk about

• Why traceability
– so measurements can be compared
• Traceable to what?
– SI units
– other reference
• CRMs
– realization of a quantity
– means of achieving traceability
• ISO Guide 34
– The quality standard for reference material producers
• ISO Guide 31
– good practice for the content of CRM certificates
 Metrological Comparability of Measurement Results

“Metrological • Why do laboratories make measurements

comparability
– to make comparisons
of measurement
results:
• changing with time?
comparability of • different to some other item?
measurement • complies with a standard?
results, for
quantities
• So the measurement result is not interpreted in isolation
of a given kind, • it has meaning when compared to other results
that are • Comparable measurement results
metrologically • must be traceable to a common reference
traceable
to the same
reference”

VIM
Example of comparing results

0.22

0.21
Dieldrin (mg/kg)

0.20

0.19

0.18

0.17
Method 1 Method 2
Source: <insert source here>

The persistent insecticide dieldrin, measured in beef fat using two methods.
Extraneous Residue Limit is 0.2 mg/kg.
Making a Comparison is Not Enough

Mid-day cannon

Expensive watches
Metrological Traceability

“property of a
measurement
Metrological traceability means
result whereby the measurements can be meaningfully
result can be compared.
related to a
reference through Even when….
a documented
unbroken chain of – made at different times
calibrations, each
contributing to the – at different places
measurement
uncertainty” – by different people
– using different equipment
VIM
Traceable to What?

“Measurement • SI units
standard:
– mole, kilogram, metre, ampere, second, kelvin,
realization of the
definition of a
candela
given quantity, • Other references
with stated – Standard method for operationally defined
quantity value and measurands
associated
measurement • eg total petroleum hydrocarbons
uncertainty, used
as a reference” NOTE 2: A measurement standard is frequently used as a
reference in establishing measured quantity values and
VIM associated measurement uncertainties for other quantities
of the same kind, thereby establishing metrological
traceability through calibration of other measurement
standards, measuring instruments, or measuring systems.
Reference Materials and Certified Reference
Material
“Reference material:
material, sufficiently homogeneous and stable with respect
to one or more specified properties, which has been
established to be fit for its intended use in a measurement
procedure.”
ISO Guide 30

“Certified reference material:

reference material (RM) characterized by a metrologically
valid procedure for one or more specified properties,
accompanied by an RM certificate that provides the value
of the specified property, its associated uncertainty, and a
statement of metrological traceability.”
ISO Guide 30
Reference materials carry information:
That is what the user pays for

NIST SRM 2387

Ash 3.10
Calories 629
Carbohydrates 25.0
Dietary Fiber-Total 5.57
Fat (extracted) 51.6
Protein 22.2
Solids 99.2
Acrylamide X
Aflatoxins X
Elements X
Fatty Acids X
Tocopherols X
Vitamins X
Sum of Fatty 49.8
Acids (as triglycerides)
Amino Acids X

http://www.eater.com/2015/2/13/8033591/761-jar-
of-peanut-butter-for-sale https://www-s.nist.gov/srmors/view_detail.cfm?srm=2387
Quality standards for reference material producers

• ISO guide 34: General requirements for the competence of reference

material producers
• ISO Guide 35: Reference materials – General and statistical principles for
certification
• ISO Guide 31: Reference materials – Contents of certificates, labels and
accompanying documentation
• ISO Guide 30: Terms and definitions used in connection with reference
materials
• ISO Guide 32: Uses of certified reference materials
ISO Guide 34

• Specifies general requirements for reference

material producers to demonstrate competency
• Guidelines for development and implementation
of management system – quality, administrative
and technical
– based on ISO 9000 series
– similar to ISO 17025
• Specifies the quality assurance (QA)
requirements for the RM production
• Specifies requirements for production of
reference materials and certified reference
materials
What is needed in a certified reference material

“measurement • Certified property value

standard: – metrologically traceable
realization of the
• Stable
definition of a
given quantity, – during storage
with stated – during transport
quantity value and • Homogeneous
associated – between units
measurement
– within units
uncertainty, used
• minimum sub-sample specified
as a reference”
• In a useful form
– pure solid, solution, fresh, freeze dried, etc
VIM – ‘how far does the light shine?”
Guide 35: Detailed guidance for preparing and
certifying reference materials

• Assigning property values

– single primary method
– several independent reference methods
– interlaboratory study
– method specific approach
• Homogeneity testing
• Stability testing
– long-term storage
– short term transport
• Evaluating uncertainty
Assigning property values:
several independent reference methods
• Pure substance reference materials
– Organic purity
• gas chromatography – flame ionisation detector
• liquid chromatograph
• quantitative NMR
– Confirmation of identify
• microanalysis
• mass spectrometry
• infrared spectroscopy
• NMR
– Inorganic impurities/solvents
• thermogravimetric analysis
• direct scanning calorimetry
• Karl Fischer (water)
Assigning property values:
several independent reference methods
• Matrix reference materials
– isotope dilution mass spectrometry techniques
– extensive cleanup two dimensional HPLC
– LC/MS
– GC/MS
– high resolution GC/MS
– high resolution ICP MS
– ICP MS/MS
– look for different ions and transitions
• Method defined measurand
– total recoverable hydrocarbons in soil
Stability testing

2.5

2.0 y = -0.0001x + 2.2689

Folic acid (mg/kg)

1.5

1.0

0.5

0.0
0 20 40 60 80 100 120 140 160 180
Time (weeks)

Long-term stability testing of folic acid in wheat flour CRM

Isochronous Stability testing

Accelerated stability Long-term stability

1, 3, 5, 7 and 14 days at at -20oC
40oC

+40oC -20oC

-80oC
Samples removed Samples removed
Reference
from oven after 1, from freezer after
3, 5, 7 and 14 days 1, 2, 3, 4, 5 and 6
months

Stored at -80oC until Stored at -80oC until

analysis analysis

Samples and reference

sample analysed in a
single batch using same
calibration standard
Homogeneity testing

0.7
Ethanol (g/kg)

0.6

0.5
5 11 105 132 158 187 215 228 251 339

Bottle No

Homogeneity testing ethanol in water solution for breathalyser calibration.

ANOVA to separate within-bottle and between-bottle variance.
Uncertainty in the property value of the CRM

 The combined standard uncertainty in the property value to include

uncertainty due to characterisation, inhomogeneity, long and short
term stability:
uCRM = √u2char + u2bb + u2lts +u2sts

 Degrees of freedom calculated from the Welch-Satterthwaite

equation (ISO GUM)

where

 k95(coverage factor) = t95 (veff)

ISO Guide 31: Certificates of Reference Materials

• Title of document
• Name of material
• Reference material code and batch no.
• Description of the CRM
• Intended use
• Instruction for use and storage
• Safety information
• Property value, MU, certification method
• Date of certification
• Traceability and period of validity
• Other relevant information
97% pure

9% water
 Certification of a Reference Material in Accordance with
Regulation 48 of the National Measurement Regulations 1999 (Cth)
in Accordance with the National Measurement Act 1960 (Cth)
Name or description of reference material: Aqueous ethanol solution.

Permanent distinguishing marks: Bottles labelled with batch number ETOH 16-03.

Date on which property values of reference material were established: 17 March 2016.

Date of certification: 29 March 2016.

Date of expiry of certificate: 17 March 2017.

Certified property value of reference material: 4.87 g of ethanol per kg of solution.

Uncertainty of property value: ± 0.07 g of ethanol per kg of solution (k=2.0).

This uncertainty is calculated in accordance with the principles of the JCGM 100: 2008 -Evaluation of
measurement data - Guide to the expression of uncertainty in measurement, with an interval estimated to have a
level of confidence of greater than 95 % at the time of certification.

Storage of the reference material at 4 - 10 °C is recommended.

Signature: Date: 29 March 2016

Name of Signatory: Paul Armishaw

Being a person with powers delegated by the Chief Metrologist acting under Section 18D of the
National Measurement Acts 1960 (Cth) in respect of regulation 48 of the National Measurement
Regulations 1999 (Cth), I hereby certify that the above reference material is certified in accordance with
the regulations.
Acknowledgements

• Organisers for the kind invitation to speak.

• NMI Colleagues in the CRV team – whose data I have plundered
Department of Industry, Innovation and Science | National Measurement Institute
National Measurement Institute
105 Delhi Rd, Riverside Corporate Park, NORTH RYDE NSW 2113
Telephone +61 2 9449 0111
info@measurement.gov.au