GERMAN FEDERAL INSTITUTE

FOR RISK ASSESSMENT

IRMS – Reference Material and

Quality Control
Dr. Melanie Gimpel
Classification of Reference Material

1) Primary (or calibration) materials

2) Secondary (or reference) materials

3) Inter-laboratory comparison materials

4) In-house (or laboratory) standards

Element Ratio Isotope delta scale

Hydrogen VSMOW
2H/1H (Standard Mean Ocean Water)
Carbon VPDB
13C/12C (Pee Dee Belemnite)
Nitrogen Atmospheric Nitrogen
15N/14N
(Air N2)
Oxygen
18O/16O VSMOW

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 2
Primary (Calibration) Material I

• Define the δ-scales versus which natural variations in isotopic compositions

are expressed
• The IAEA has defined these scales by reference to natural or virtual materials
identified by the “V“ prefix
• Kept and distributed
by the IAEA (International Atomic Energy Agency),
NIST (National Institute of Standards and Technology)
and USGS (United States Geological Survey)
• Primary standards are only available in small quantities
• Some original primary standards have become exhausted and have been
replaced by similar materials
• Isotopic laboratories calibrate their own working standards using reference
material

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 3
Primary (Calibration) Material VSMOW δ-scale

 VSMOW2:
• VSMOW: exhausted; was prepared by blending distilled ocean water (latitude 0°/
longitude 180°) with small amount of other waters existed
• VSMOW 2: prepared in 1999 by blending three selected fresh water samples, obtained
from Lakes in Italy, Israel and Egypt to produce an isotopic composition close to the
definition of SMOW (Craig, 1961)
• δ2H value was adjusted isotopically by a modified platinum catalytic exchange reaction
 SLAP2:
• Lower end of the scale: Standard Light Antarctic Precipitation (SLAP), depleted in
heavy isotopes with respect to VSMOW2
• was prepared in 2006 from four selected Antarctic snow/ice samples obtained from the
U.S. National Science Foundation’s South Pole station (coordinated by T.B. Coplen),
from an ice core of the Vostok drilling site (J.M. Petit), from the Dome F drilling site (O.
Abe) and from the Dome C drilling site (O. Abe).
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Primary (Calibration) Material VSMOW δ-scale II

Table: δ2H and δ18O values for the relative difference in hydrogen and oxygen stable
amount ratio for the international measurement standards
(source: IAEA Reference Sheet RS_VSMOW2_SLAP2_rev1/2017-07-11)

VSMOW VSMOW2
SMOW VSMOW
SLAP SLAP2

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Primary (Calibration) Material VPDB δ-scale I

VPDB δ-scale

• PDB: calcium carbonate from a Cretaceous belemnite

from the PeeDee formation in South Carolina (USA),
exhausted

• Considerably enriched in 13C with respect to organic

carbon compounds source: www.wikipedia.org

• VPDB: after exhausting of PDB values were assigned to TS-limestone (NBS 19)
and a hypothetical VPDB was created
• Now the calcite (CaCO3) IAEA 603 is the primary reference material for the PDB-
Scale with a δ13C of +2.46 ‰

NBS 19 IAEA 603

PDB VPDB
R=0,0112372 R=0,0111802 LSVEC LSVEC

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 6
Secondary (Reference) Material
• Natural or synthetic compounds which have been carefully calibrated versus
primary calibration material
• δ-values agreed and adopted internationally but have associated uncertainties

Description Nature δ13C ‰ SD

IAEA-CH-3 Cellulose -24.724 0.041
IAEA-CH-6 Sucrose -10.449 0.033
IAEA-CH-7 Polyethylene -32.151 0.050
IAEA-600 Caffeine -27.771 0.043
USGS-24 Graphite -16.049 0.035
USGS-40 L-Glutamic acid -26.389 0.042
USGS-41 L-Glutamic acid +37.626 0.049
NBS-22 Oil -30.031 0.043
LSVEC Lithium carbonate -46.6 0.2
BCR 656 Ethanol -26.91 0.07
https://nucleus.iaea.org/rpst/ReferenceProducts/ReferenceMaterials/Stable_Isotopes/2H13C15Nand18O/index.htm

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 7
Inter-laboratory Comparison Material

1) Primary (or calibration) materials

2) Secondary (or reference) materials

3) Inter-laboratory comparison materials

4) In-house (or laboratory) standards

• Materials circulated in inter-laboratory comparison exercises

• δ-values are assigned as the consensus mean of results from
participating laboratories, following appropriate statistical
treatments
• Participation in Proficiency Testing Schemes (PTS)

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 8
Inhouse/ Laboratory Standards

Characteristics of Standard Material

• Stable, isotopically homogeneous
• Easy to weigh out ( tin capsules) or to inject
• Similar isotopic ratio to the samples
• Similar composition and characteristics to the samples
• Easy to store and to handle, not hazardous
• Non-hygroscopic (for hydrogen and oxygen)
• Low priced

Examples
• 13C/12C in wine  wine
• 13C/12C in solids  fructose
• 13C/12C and 15N/14N in caseine  caseine
• 18O/16O in wine water  wine, light and heavy water
Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 9
Preparation of „light“ and „heavy“ water as inhouse standard I

• Fractionation of deionised water

 Light Water: δ 18O = -14,6 ‰ vs. VSMOW

 Heavy Water: δ 18O = +15,6 ‰ vs. VSMOW

• Equipment/ tools:

 Round bottom flasks 1 l

 Distiller
 Heating mantles
 Boiling chips

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 10
 Preparation of „light“ and heavy water - procedure

Distille 750 g Water (deionised) (δ 18O ~ 7 ‰)

approx. 8 hours until 80-160 g

30-50 ml Condensate after is left
approx. 90 min

Repeat procedure and collect

Repeat this procedure until all residue fractions
you have about 800 ml

Repeat procedure with

collected fractions until ~
Light water * 100ml left, test

*perform an IRMS measurement to

ensure that δ 18O  -15 ‰
Heavy Water **
Add approx. 3 mg NaN3 for conservation **perform an IRMS measurement to
Store in the refrigerator, shelf life 5 years ensure that δ 18O  +15 ‰

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 11
Quality Control Charts I

• Example EA liquid 13C/12C, Wine

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 12
Quality Control Charts II

• Example EA liquid 13C/12C, Wine

-27,9
18.04.2018

20.04.2018

24.04.2018

07.05.2018

08.05.2018

09.05.2018
-28

-28,1

-28,2 Upper control limit (UCL)

-28,3 Upper warning limit
-28,4
Center line
-28,5

-28,6
Lower warning limit
-28,7 Lower control limit (LCL)
-28,8
Werte Mittelwert ober KG obere WG

• Definition of thresholds: from the official method or from previous period

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 13
Quality Control Charts III – Control / Warning situations
• 1 value beyond the control limit or
• 3 values beyond the warning limit

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 14
Quality Control Charts III – Control / Warning situations

• 7 successive values increasing or decreasing

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 15
Quality Control Charts III – Control / Warning situations

• 7 successive values at the same side of the center line

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 16
Proficiency Test (PTS) I
Food Analysis using Isotopic Techniques (FIT) –PTS
• Implemented by Eurofins Scientific in 1994
• Since 1999 FIT-PTS was expanded to laboratories around the world (> 50)
performing stable isotope measurements on food
• 3 rounds per year (7 samples each round)
• Techniques: IRMS and SNIF-NMR

(1) Samples Participants (3) Lab code

(7) Anonymous Report (2) Results

Eurofins JRC Ispra
(4) Anonymous Data

(5) Statistical Report (6) Validation/Comments

• Dr. Claude Guillou (JRC Ispra, EU)
Expert Committee • Dr. Eric Jamin (Eurofins Analytics France)
• Dr. Carsten Fauhl-Hassek (BfR, Germany)
• Dr. Andrew Damant (FSA, UK)

https://www.eurofins.com/food-and-feed-testing/food-testing-services/authenticity/fit-pts/

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 17
Proficiency Test (PTS) II - Samples

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 18
Proficiency Test (PTS) III - Results

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 19
Proficiency Test (PTS) IV

• Statistical Analysis: evaluation of data is performed according to the

ISO/IUPAC/AOAC International Harmonised Protocol for Proficiency Testing
of analytical laboratories
• Results are expressed as z-scores:

= ( − )/

: reported result from the participating laboratory

: the assigned or "true value for the analyte being determined,
here: taken as the robust mean of all reported results
: target value for the standard deviation,
in this exercise the target SD values are derived from recently reported
collaborative trial results AOAC, CEN, … or from the robust standard deviation
of all reported values

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 20
Food Analysis using Isotopic Techniques (FIT) – PTS V
Z-score

Melanie Gimpel, Stable Isotopes Analysis of Wine – Referencing and Quality Control page 21
GERMAN FEDERAL INSTITUTE
FOR RISK ASSESSMENT

Thank you for your attention

Melanie Gimpel

German Federal Institute for Risk Assessment

Max-Dohrn-Str. 8-10  10589 Berlin, GERMANY
Phone +49 30 - 184 12 - 0  Fax +49 30 - 184 12 - 47 41
[email protected]  www.bfr.bund.de/en