Entwicklung von CRM unter Doppel-Akkreditierung Fachveranstaltung am 26. Juni 2013 Sigma-Aldrich Buchs, Switzerland Dr. Michael Weber Director, Marketing and R&D Analytical Standards and Reagents
Outline Why chemical metrology is different Accreditation vs. certification Tailor-made products for AAS, ICP and IC -TraceCERT Standards (CRM) - Custom Standards Platform Challenges in CRM production
About Zanzibar Values Reference: P.W. Petley The fundamental physical constants and the frontier of measurement, Hilger, p.8-9, (1988)
Chemical Metrology is different! TRACEABILITY of measurement result (here = amount of Peperoni) Balances do not care about the nature of the fuit «apples and oranges» Analytical intruments do! «balance has to be calibrated for oranges / apples first»
Realization of Traceability in Chemistry What about the chemical standard kilogram = the standard mole? In chemistry there is no standard mole! NMIs to provide primary chemical rerefernce materials MANY different of them are needed (apples vs. oranges problem ) EMPA Cadmium (vacuum distilled) BAM Copper Primary-A High-purity Silver (Sigma-Aldrich)
Accreditation vs. Certification Certification: Confirmation that you do something according to certain guidelines Examples: ISO 9001 management ISO 14001 environment & safety Effect: Application: May influence your product or service quality A calcium standard is certified to be 1001 mg/l in concentration with 0.4% uncertainty Accreditation: Formal attestation of a technical competence to do something within a defined scope and quality Examples: ISO/IEC 17025 testing and calibration ISO Guide 34 CRM production Effect: Application: Defines product or service quality A laboratory is accredited as a testing lab to measure calcium by IC at conc levels of 1-10 000 ppm with an uncertainty of >0.2%
ISO 9000 17025 ISO Guide 34 Increasing technical competence and complexity ISO 9001 ISO / IEC 17025 ISO Guide 34 Our company is properly managed This does not automatically mean that the product is good! You can make bad products in a properly managed company... Our company is properly managed + we can measure Our company is properly managed + we can measure + we guarantee CRM homogeneity and stability
Double Accreditation = Gold Standard ISO/IEC 17025: General requirements for the competence of testing and calibration labs ISO Guide 34:General requirements for the competence of Reference Material producers For CRM producers the double accr. is the highest achievable level of (certified) reliability Every accreditation is strictly limited to the defined scope (analyte, matrix, concentration) no one has overall accreditation Only very few companies have double accreditation
Challenges in CRM Production Highest purity starting materials are crucial (ppb level impurities) Special equipment is needed contamination free / PFA or FEP materials / clean room filling Availability of comprehensive analytical expertise Development of adequate containers & packaging 1.010 Transpiration through HD-PE bottles (Fluka 50 ml) Increase of Concentration relative to 1.000 gl -1 1.008 1.006 1.004 1.002 1.000 30 C measured (mean of 9 bottles) extrapolated 23 C 30 C 23 C 0 360 1 720 2 1080 3 Years Bottle stored without Al-bag Bottle stored in Al-bag
The 4 1=0 Rule in Analytical Chemistry purity / impurity accuracy / concentration Specification and analytical testing understand application instrument availability Packaging (Bottle, cap, bag) nothing to go in (leach out) nothing to go out (transpiration of soutions) Documentation certificate application note Very often all the four categories of requirements must be fulfilled If not, the product value is zero
TraceCERT Standards for IC, ICP and AAS TraceCERT stands for traceable, certified Reference Materials Multiple-traceable to different references NIST, BAM, EMPA etc.) Single element and ion standards (anions, cations) at the 1000 ppm level + several multielemental Highest accuracy, 3-4 page certificate Special packaging with up to 4 years expiry www.sigma-aldrich.com/inorganiccrm Produced in double accredited laboratory fulfilling and ISO/IEC 17025 and ISO Guide 34
Custom Standards Platform For elements (periodic table) and ions (anions/ cations), 1-5000 ppm All custom mixes certified under double accreditation All custom mixes are produced as TraceCERT quality grade www.sigma-aldrich.com/csp
Testmischung als Multielement-CRM für High-Resolution Continuum Source AAS Element Konz. (mg/l) Ag 2 Cd 1 Co 150 Cr 15 Fe 1200 Mn 5 Ni 30 Pb 5000 Sn 120 Zn 1 Matrix: 5% HNO 3 und 0.05%HF Herausforderungen für Produktion Spuren in Hauptkomponenten (Wasser, Säuren) Einflüsse aus der Umgebung (Reinraum LF-Bench) Hoch/tiefe Konzentrationen im Mix erfordert sehr saubere Startmaterialien
Einfluss von Spurenverunreinigungen auf die zertifizierten Konzentrationen Verunreinigung in μg/l im Mix Startmaterial Analyt Ag Cd Co Cr Fe Mn Ni Pb Sn Zn gefunden Ag Metall Ag kleiner als 0.002 0.002 0.002 0.010 0.002 0.010 0.020 0.010 0.002 gefunden Cd Metall Cd kleiner als 0.0005 0.0001 0.0005 0.0005 0.0001 0.001 0.0001 0.0001 0.001 gefunden 0.105 1.500 27.000 0.060 Co Metall Co kleiner als 0.015 0.015 0.075 0.015 0.075 gefunden Cr(NO 3) 3 x 9 H 2O Cr kleiner als 0.3 0.015 0.015 0.15 0.03 0.075 0.15 0.075 0.015 gefunden 16.8 20.4 Fe Metall Fe kleiner als 0.120 0.120 0.600 6.000 0.120 0.120 0.120 gefunden 0.001 0.0885 0.527 0.0485 0.0125 0.0015 0.1895 Mn Metall Mn kleiner als 0.0005 0.001 gefunden 0.075 0.060 Ni Metall Ni kleiner als 0.003 0.003 0.15 0.015 0.015 0.003 0.015 gefunden 8.000 Pb(NO 3) 2 Pb kleiner als 0.500 0.500 0.500 0.500 0.500 0.500 0.500 0.500 gefunden 0.840 18.000 Sn Metall Sn kleiner als 0.120 0.120 0.120 0.600 0.600 0.120 0.120 gefunden 0.002 0.001 0.019 Zn Metall Zn kleiner als 0.0001 0.0005 0.001 0.0005 0.0005 0.0001 Daten aus Spurenanalytik verwenden für: Korrektur des Gehaltes im Mix zusätzliche Unsicherheitsbeiträge Problematik: Verunreinigung im Startmaterial kleiner als Nachweisgrenze können nicht dazugerechnet werden Ag Cd Co Cr Fe Mn Ni Pb Sn Zn Sollkonzentration im Mix 2 1 150 15 1200 5 30 5000 120 1 Summe Verunreinigung gefunden 0.008 0.000 0.017 0.000 0.002 0.000 0.048 0.018 0.000 0.000 Korrektur 0.4% 0.00% 0.01% 0.00% 0.00% 0.00% 0.16% 0.00% 0.00% 0.02% Summe Verunreinigung kleiner als 0.001 0.001 0.001 0.002 0.001 0.007 0.001 0.000 0.001 0.001 Unsicherheitsbeitrag 0.03% 0.08% 0.00% 0.01% 0.00% 0.13% 0.00% 0.00% 0.00% 0.08%
Challenges in Industrial RM Production Rigorous safety policy (zero tolerance for incidents) Rigorous compliance issues hazardous, tox, drugs Storage and transportation Global supply chain is a real challenge Implementation of quality guidelines is a must but costly (accreditation)
The Devil is in the Details Ok, we did not spend so much time for uncertainty estimation..... but who will notice? Langer/Baaske mass of starting material (m SM ) weighing value buoyancy correction buoyancy correction weighing value mass of batch solution (m Batch ) purity starting material (P SM ) determined impurities non detected impurities homogeneity solvent quality dilution and homogenisation (Hom) determination of density ( ) bottle leaching transpiration storing bahaviour (Store) certified concentration (c cert ) Bottom-up uncertainty calculation for a TraceCERT calibration CRM solution