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Reference M aterialsReference M aterialsProgram in CEN AMProgram in CEN AM
Rocio ArvizuRocio ArvizuResearch ChemistResearch Chemist
Centro Centro NacionalNacional de de MetrologíaMetrologíaMéxicoMéxico
Advance School in Metrology in ChemistryAdvance School in Metrology in ChemistryINMETRO INMETRO November 2003November 2003
CENAMCENAM
GENERAL DIRECTORGENERAL DIRECTORDir. Technologic ServicesDir. Technologic ServicesDir. AdministrationDir. Administration
Dir. Mechanical M.Dir. Mechanical M. Dir. M. of MaterialsDir. M. of Materials Dir. Physical M. Dir. Physical M. Dir. Electrical M. Dir. Electrical M.
Mass
Pressure and Force
Electromagnetism
Inorganic Mat Optic and Radiometry
Organic Mat.
Time and Frequency
Flow and Volume
Length
Ceramics Mat.
ThermometryAcoustic and Vibrations
kg
K
cd s
A
molm
Principal Activities in Metrology of MaterialsPrincipal Activities in Metrology of Materials
♦ To Develop and Maintain National StandardsPrimary MethodsCRM
Primary methodsUsing at least two independent methods
♦ To Contribute to the Development of NationalMeasurement System
Reference LaboratoriesPTs
♦ To Provide Metrological Services
Documents of Quality Assurance of CENAMDocuments of Quality Assurance of CENAMrelated with Traceabilityrelated with Traceability
♦ 100-AC-P.1.2.2 Vision of CENAM and 100-AC-P.1.2.4 Vision-Success Factors
“International and National high level scientific and technologicalorganization in the field of Metrology”
“Origin of traceability of measurements in Mexico”
♦ 100-AC-P.1.2.6 Development Plan 2000 – 2006“…maintain the national standards according to the new technology ofmeasurement in order to be the origin of traceability…”
“…all measurements are related with use of SI units and then comparable withmeasurements of the same quantity made in any place…”
TRACEABILITYTRACEABILITY
REFERENCE STANDARD
WORKING STANDARS
MEASUREMENTINSTRUMENT
FIELD LABORATORY
uncertainty
NATIONAL STANDARD
REFERENCE STANDARD
WORKING STANDARD
CENAM
NATIONAL STANDARDS
NMIs
BIPMCIPM-MRA (COMPARABILITY)
Recognized traceability to national standards of other countries
REFERENCE STANDARD
WORKING STANDARD
SECONDARYLABORATORY
Policy of TraceabilityPolicy of TraceabilityMetrology of MaterialsMetrology of Materials
♦ 600-AC-PL.006 Policies of Traceability in the Certification ofReference Materials
To establish the policy of traceability for values expressed in the certificates ofReference Materials.
To assure that all values as a result of any measurement will be traceable to the SIunits
Applicable to all chemical measurements, in order to make them harmonic withuncertainty estimation; according to following policies:
100-AC.P 2.3.10 Policy for uncertainty estimation,600-AC.PL.08 Declaration of uncertainty for certification of reference materials,600-AC.PL.14 Combination of Measurement results and uncertainties in reference materialcertification600-AC. PL.21 Acceptance criteria of the certified value and uncertainty.
It has been adopted the scheme of traceability proposed by W. Richter and G. Dubeand the recommendations issued by the CCQM of BIPM.
FIELD MEASUREMENTS
SI UNITS
Primary Methods
CRM
Primary Methods
RSM RL/ RM
Primary Methods
Metrology, 1997, 34W.Richter y G. Dube
Primary Methods
Practical ways to establish traceabilityPractical ways to establish traceability
Reference Materials
Simple Matrix Certified Reference Materials
Simple Matrix Certified Reference Materials
Transfer MethodsTransfer Methods
Transfer Methods Transfer Methods
PrimaryReference Materials
PrimaryReference Materials
Primary Methods
OTHER SI UNITSOTHER SI UNITSmolmolkgkg
Measurements Sample PreparationFieldField MeasurementsMeasurements
Complex Matrix Certified Reference Materials
Complex Matrix Certified Reference Materials
Sampling
Validation% of Recovery
Practical Realization of Traceability in Chemical Measurements
Unc
erta
inty
Unc
erta
inty
Potential Primary Methods in CENAMPotential Primary Methods in CENAM
Method Mathematical EquationGravimetry(Inorganic, Static GravimetricPrimary System)
Coulometry
Isotopic Dilution with MS
zFQn =
sB
Bsp
Bsp
pB
sp
sp
p
p
RRRR
RRRR
NN
Mm
n−−
⋅−−
⋅⋅=`
´
`
Mmn =
Traceability in GravimetryTraceability in Gravimetry
Amount of substancemol
Amount of substancemol
Quantity : MassUnit : kgUncertainty : 0.0023 mgPrototype Standard No. 21
Quantity : MassUnit : kgUncertainty : 0.0023 mgPrototype Standard No. 21
Quantity: amount of substance content of Naand Si
k = (40 and 400) mmol/kg
Relative Uncertainty: (0,6)%
Quantity: amount of substance content of Naand Si
k = (40 and 400) mmol/kg
Relative Uncertainty: (0,6)%
Ar(12C)Rel. atomic mass
12Cg mol-1
Ar(12C)Rel. atomic mass
12Cg mol-1
Quantity: MassUnit : kgUncertainty: 0,02 a 0,14 mg
Quantity: MassUnit : kgUncertainty: 0,02 a 0,14 mg
Ar = Rel. atomic mass (Na, Si)Unit: (22,989770 and 28,08559) gmol-1Uncertainty: (0,000002 and 0,0003) gmol-1
Ar = Rel. atomic mass (Na, Si)Unit: (22,989770 and 28,08559) gmol-1Uncertainty: (0,000002 and 0,0003) gmol-1
Mathematical equation of Gravimetry
Quantity: amount of substancecontent of Na and Si
Unit: mmol/kg
Mathematical equation of Gravimetry
Quantity: amount of substancecontent of Na and Si
Unit: mmol/kg
),(),( xSnxEn ba =
xmaxSnbxEk ),(),( =
TraTraceceabilityability in Gas in Gas MetrologyMetrology
kg (SI)(0 µg)
Atomic mass/mol(IUPAC)
PureGases
Purity Determination
National PatternPrototype No.21 (± 2 µg)
Gas Primary Mixtures
ISO 6143
Certified Gas Reference Mixtures
Transference Method
0,1 %
0,3 - 1 %
1 5 %
mol
FundamentalRatio
Frame of massesClass E2
ISO 6142
0
2
1
3
LEVEL
Gas Working Mixtures
CoulometricCoulometric TitrationTitration
VoltV
NS of electrical tension(continuous current)
seconds
NS of time
ohmΩ
NS of electric resistance(continuous current)
kilogramkg
NS mass
VoltageV
NanovóltmetroHP 34420A
times
Contador universalHP 53131A
resistanceΩ
Resistencia PatrónGuildline 9334/100
masskg
Balanza analíticaMettler AT260
intensity(I)A
Ampers
PRIMARY CRM
time(t)s
second
FaradayConstant (F)
CODATA(1998)
Potentiometer(pH)
Potentiostat (I)
mass(m)g
gram
zFtIn =Analite
End Point
Measuring systems developed in CENAMMeasuring systems developed in CENAM
SystemSystem Mathematical EquationMathematical Equation
pH Primary System
Conductivity PrimarySystem
pH Secondary System
Conductivity SecondarySystem
+
−= θθ
θ γγp
pF
RTmmm
FRTEE HClClHH
AgClAg2log
210ln
)(log10ln
2/
)( 12 RRg−
=κ2
4φπ ⋅∆⋅
=∆
=L
aLg
RKcelda=κ
Certification of CRMCertification of CRM
♦ 600-AC PL.20 Particular methods of certification in the area ofmaterials metrology
Primary MethodAt least two Independent Reference MethodsValue assignment by method-dependent measurementCollaboration studies with NMIsA combination of the above
Based on the ISO Guide 35:1989, Certification of reference materials –General and statistical principles. 1989
Reference Measurements Systems at CENAMReference Measurements Systems at CENAMCeramics DivisionX Ray fluorescence spectrometryParticle size and distributionPorosity and superface area measurement systemX Ray diffractionFourier transform Infrared spectrometryMicroprobe SystemScanning electro microscope with EDS and WDSSieving and Milling Laboratory
Inorganic DivisionGravimetric-potentiometric titrationUV-Vis spectrophotometryFlame atomic absorption spectrometry (FAAS)Hydride generation and Cold Vapor atomic absorption spectrometry (HG/CV-AAS)Graphite furnace atomic absorption spectrometry (GFAAS)Inductively coupled plasma optical emission spectrometry (ICP_OES)Inductively coupled plasma with high resolution mass spectrometry (ICP-HRMS)Measurements Systems of Nitrogen/Oxygen and Carbon/SulfurGravimetric Preparation Laboratory
Organic DivisionHigh performance liquid chromatography coupled to Diode Array Detector (HPLC)High performance liquid chromatography coupled to UV-Vis detectorHigh performance liquid chromatography coupled to refractive IndexHigh performance liquid chromatography coupled to electrochemical detectorHigh performance liquid chromatography coupled to florescence detector Gas chromatography coupled to quadrupole mass spectrometry (GC-MS)Gas chromatography coupled to high resolution mass spectrometryGas chromatography coupled to electron capture detectorGas chromatography coupled to photoionization detectorGas chromatography coupled to thermo conductivity detectorDifferential scanning calorimetryGravimetric Preparation Laboratory
Human ResourcesHuman Resources
48TOTAL
2Directorate
6Coordination of Reference Materials Program andQuality Control Assurance
2Instrumental
3Other Materials14
3Sediments, Soils, Ores, and Particulates13
1Fuels12
3Food11
3Biological Fluids and Materials10
1Advanced Materials9
1Metals and Metal Alloys8
1Electrolytic Conductivity7
1pH6
4Water5
6Gases4
4Organic Solutions3
4Inorganic Solutions2
3High Purity Chemicals1
StaffCategoryCat. No.
CRM Development StagesCRM Development Stages
Justification
Feasibility evaluation
Preparation or adquisition
of raw material
Homogeneity Tests
Chemical measurements
Statistical Analysis
Certification
Stability Tests
Experiment design
Yes
No
Yes
No
Communication with thecustomer
No
Experiment design
Corn Leaves RMCorn Leaves RM
CleaningNon ionic detergent
Drying60°C
Milling/sieving75 um
Homogenization
Microbiological ControlCobolt-60, 27.8 kGy
Recollection and selection of leavesMiddle life
Preparation of RM
ExampleExampleExperiment Design for CertificationExperiment Design for Certification
Objective: To assess the reproducibility between samples and Instrument response (days)
n bottles
Solutions
Day 2Calibration
Day 3Calibration
Day 1Calibration
Replicates Replicates Replicates
To measure nsamples randomOrder
To measure nsamples randomOrder
To measure nsamples randomOrder
Preparation of RMPreparation of RMReference Inorganic SolutionsReference Inorganic Solutions
Purity MeasurementHigh Purity Metals and Salts
ICP-HRMS Systems of measurement in Nitrogen/Oxygen and Carbon/Sulfur
Cleaning and Ampouling Process Gravimetric Preparation
Gravimetric Preparation
Certification process
Chemical MeasurementsChemical MeasurementsSpectrometric Standard Solution,1000 mg/LSpectrometric Standard Solution,1000 mg/L
Value AssignmentValue Assignment
983985987989991993995997999
10011003100510071009
GravimetricPreparation
ICP-OES FAAS Combination Assignment Valuewith TL
Con
cent
ratio
n, m
g/L
K , DMR-57b
11) mg/L±(996
996.3C =
Correction of measured value by transpiration loss for 2 years
11.1U =995.3C =
11.1 (u*K + %T1 year) =U =
0.995 0.9953 1 year the stability in concentration %T1 year =
1.99 0.2 % for 2 years =if %T2 years =
Transpiration loss (TL)
CRM
Policy relative to Uncertainty estimationPolicy relative to Uncertainty estimation
100-ACP100-ACP 2.3.10 Policy for uncertainty estimation2.3.10 Policy for uncertainty estimation
♦ To establish guidelines to report the uncertainty of measurement which isassociated to the CENAM measurements
♦ Applicable to all measurements results of the CENAM procedures
♦ Definitions ui, uc and U
♦ Percent of measurement results Y that can be contained in a reliable wayinside a confidence interval
♦ Every document in which CENAM declare a measurement value, must beaccompanied with a quantitative declaration of its uncertainty
ThreeThree policies and policies and OneOne procedure related to uncertainty procedure related to uncertaintyestimation in Metrology of Materials Areaestimation in Metrology of Materials Area
♦ Declaration of uncertainty for reference materials certification 600-AC.PL.08To Assess that the uncertainty estimation corresponding to chemical measurement carried out inthe Metrology Materials Area must include evaluation of uncertainty.Adopt the guide “Quantifying Uncertainty in Analytical Measurement, English edition, Firstedition 1995 “(1), as a mandatory reference document to assess the chemical measurements.
♦ Combination of Measurement results and uncertainties in reference materialcertification 600-AC.PL.14
Established to assess the consistence of the results issued through the reference materialscertificate with the combination of uncertainty procedure 600-AC.P-014, when it is necessary.It is adopted the document: “An Approach to Combining Results From Multiple MethodsMotivated by the ISO GUM” (1), as a mandatory guide reference when more than one method isaplyed
♦ Acceptance criteria of the certified value and its uncertainty 600-AC. PL.21Measurement methods of quantification must be on statistical control.
♦ General procedure 600-AC.P-113Guide to The expression of uncertainty in measurement, BIPM, IEC, IFCC, ISO, IUPAC, IUPAP,OIML, 1995
(1) JOURNAL OF RESEARCH OF THE NIST, V 105, No. 4, Jul-Ago 2000. U.S.A.
CRM Program Established at CENAMCRM Program Established at CENAMInformation collected by National Standards (NOM, NMX)Information collected by National Standards (NOM, NMX)
Number of testing laboratories accredited = 300
Number of tests = 967 Compulsory standards = 178Non compulsory standards = 789
Total = 968
Compulsory Standards
Total reviewed
Voluntary Standards Total reviewed
Environmental 94 Chemical 203 Food 28 Agricultural 138 Chemical 16 Food 141 Beverages 9 Plastic 67 Services 6 Environmental 53 Plastic 5 Petrochemical 51 Other manufactures 5 No ferrous metals 40 Iron and steel industry 4 Control and
measurement equipment 13
Petrochemical 2 Glass industry 11
Developed CRM by Metrology of MaterialsDeveloped CRM by Metrology of MaterialsNo. CRM
53
1621
9
16
32 33
25
8
05
10
15202530
3540
1994 1995 1996 1997 1998 1999 2000 2001 2002 2003Year
No. o
f CRM
29%
25%
8%
8%
7%6%5%4%3%
1%
1%
1%
2%Ino rganic So lut ions Organic So lut ions High Purity CompoundsSed iments , So ils and Part icules Food OtherspH Water FuelsAdvanced Materials Conduct ivity Metals and Metals AlloysBio log ical Fluids and Materials
69 gas mixtures, CRM forinternal use in order to support:PTsMRTC programCalibration servicesEvaluation of analyticalcompetence
168 CRM
ServicesServices offered by Metrology of Materials Areaoffered by Metrology of Materials Area
15Technical assistance in metrology inchemistry
23Training in the laboratories
511Training courses in catalogue & by request
6742Special analytical services
2845Gas analyzer calibration
13221462CRM Sales
No. services2003
Jun-Sep
No. services2002
Type of service
Reference Material sold by applicationReference Material sold by application
3 7%
2 4 %
14 %
14 %
6 %2 %2 %1%
S pe c t rome t r ic solut ions Ele c t roc he mic a l st a nda rs Food indust ry a pplic a t ion
Wa st e wa t e r a na lysis Che mic a l a nd pe t roc he mic a l a pplic a t ion Ge ne ra l a pplic a t ion
Envirome nt a l a na lysis Ce ra mic , c e me nt a nd gla ss
19 32 51181
297
630
1462 1322
0
200
400
600
800
1000
1200
1400
1600
1996 1997 1998 1999 2000 2001 2002 2003Year
No.
of C
RM
Sol
d
CRM CRM SoldSold
4 1998
H+ He 6 1999
Li Be B C N O F- Ne 9 2000
Na Mg Al Si P S Cl- Ar 3 2001
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 3 2002
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 1 2003
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 5 2004
Fr Ra Ac Ku Ha 5 2005
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 5 2006
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw 6 2007
In program: 47Total : 26 (2003)
CRM
Calibration Solutions and High Purity SaltsCalibration Solutions and High Purity SaltsNational Needs and DevelopmentNational Needs and Development
speciation High Purity SaltsReferenceSolutions
Cu Hg Cr+6 NaCl HClNi Se Cl - KCl H2SO4
Pb Sn F- K2Cr2O4
Zn P PO4- BFK
Al Sb NO3- Na2CO3
Ca As SO4= CaCO3
Cd Mn NO2- As2O3
Fe Ti Oxalato de NaK Bi Tris(hidroximetilaminometano)
Mg Li Acido OxálicoNa Mo EDTASi PtS TlAg VCr W
BBaGaInYCsCo
15 17 + 5 7 11 215 22 7 11 2
Salts Solutions11 41 + 511 46
National Needs: 53
Elemental
CoulombimetryReference Solutions
55 CRM
Organic CRMOrganic CRMNational NeedsNational Needs
•• Environmental (Gas, soil, water, sediments)Environmental (Gas, soil, water, sediments)•• Health and ClinicalHealth and Clinical•• High Purity organic compoundsHigh Purity organic compounds•• Biological MaterialsBiological Materials•• Food and beverageFood and beverage•• Petroleum ProductsPetroleum Products
DevelopmentDevelopment79 Certified reference materials for:
•• Nutritional constituents in food samples (vitamins like, A, C, E,Nutritional constituents in food samples (vitamins like, A, C, E, fatty acids, minerals) fatty acids, minerals)
•• PesticidesPesticides•• ketonesketones, , aldehydesaldehydes, alcohols mixtures for alcoholic industry, alcohols mixtures for alcoholic industry•• HydrocarbonsHydrocarbons•• Gas mixtures Gas mixtures (69)•• pHpH•• Electrolytic conductivityElectrolytic conductivity
Electrical Metrology
Physical Metrology
Materials Metrology
Mechanical Metrology
CENAMCENAM Services in Appendix C, BIPM KCDBServices in Appendix C, BIPM KCDB
Published in BIPM Annex C
ElectromagneticMeasurements
36
Temperature
20
Time and Frequency
---
Acoustics and Vibrations
16
Optics and Radiometry
13
CeramicMaterials
--- 8*
Length
13
Flow and volume
5
Force andpressure
22
Mass
45
TOTALMat. Met 31 + 43 = 74
213
* RM covered by Cycle III and IV
MetallicMaterials
38 + 8*Organic Materials
5 + 15*
There is NO one to one correspondence between BIPM servicesand our service catalogue
2
4
106
10
10
CCQM
SIM
Traceability can be established through national standardsand through those of other countries.
Due to the lack of CRMs most analytical laboratories employ chemicals with certificate of analysis which does not containsufficient information for demonstrating their traceability to national standards
At the same time there are few national standards which could give traceability to them.
Reference LaboratoriesReference Laboratories
CENAM´s annual sale of CRMS is now ca. 1500 units
Evaluation of traceability of Certificates of RMis over 5000.
Absolute lack of capabilityLack of strategy of priority CRMsLack of mechanism to produce CRMs
MRTC program to work together with RM producersAnd Reference Laboratories
Reference LaboratoriesReference LaboratoriesCENAM ProposalCENAM Proposal
Reference LaboratoriesReference LaboratoriesCENAM ProposalCENAM Proposal
CENAMCENAM NMINMI
HEALTH R L ENVIROMENTAL R L AGRICULTURE R L AGRICULTURE R L
LAB.LAB. 1 LAB. 3LAB. 3 LAB. 5LAB. 5 LAB. 6LAB. 6 LAB. nLAB. n
Analytical Laboratories, Private Research Institutes, Universities, GovernmentResearch Institutes, etc.
LAB.LAB. 2 LAB.LAB. 4 LAB.LAB. 7
MetrologicalMetrological ActivitiesActivities ofof ReferenceReference LaboratoriesLaboratories
♦ Maintain traceability to SI
♦ Disseminate accuracy to the National Standards toward thetesting laboratories by means of:
Preparation Capabilities of candidates RMMeasurement Capabilities
♦ Guarantee: harmonize and reliable chemical measurements,which will be carried out in the country.
CRMCRM networknetwork andand PT PT providersproviders: : proposedproposed schemeschemewithwith ReferenceReference LaboratoriesLaboratories (a-e) (a-e)
NORAMET
NRC NIST
CENAM
5.2 Water, Contaminated Water
3. Organic Sol.
SIMSIM
4.2 Gas, environmental 10.4 Botanic M.,Tissues
11.1, 11.2 Food, Nutritional and Contaminants
ab c d
e
CENAM &Reference Labs
NORAMET/SIM CRM network
PTsPTs (Waste Water Laboratories) (Waste Water Laboratories)
Hg
0
50
100
150
200
250
300
1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004Year
% R
SD
As
0
5
10
15
20
25
1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004
Year
% R
SD
Cd
0
5
10
15
20
25
1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004Year
% R
SD
PTsPTs (Waste Water Laboratories) (Waste Water Laboratories)
Cr VI
0
5
10
15
20
25
1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004
Year
% R
SD
CN
05
10152025
303540
4550
1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004
Year
% RS
D
Fig. 1a Mean values and standard deviation for Glucose concentration in sample 1
Certified value ± U ± 3U
CERTIFIED VALUE: 88.7 mg/dLUncertainty (U): ± 1.68 mg/dL
70.0
80.0
90.0
100.0
110.0
7390
2315
4817
5429
2710
3811
7375
9359
5437
6344
2556
7663
1740
9900
8063
7636
7266
1524
5528
6527
8127
2161
7242
2890
4617
4953
6865
4891
3337
6840
6986
6234
8224
3554
2667
9983
7786
8004
1952
2991
2884
4483
3207
3683
LABORATORY CODE
CO
NC
ENTR
ATI
ON
(m
g/dL
)
*Colorimetric (QH) Dried Chemestry (QS) O2 Electrod (O2Z)Not reported (NR)METHOD:
Impact on health and trade
EU Directive on IVD: CEN/TC 140ISO/TC 212 for IVD test systems
PTsPTs (Clinical Laboratories) (Clinical Laboratories)
InternationalInternational CollaborationCollaboration in in ChemicalChemical MetrologyMetrology ProgramProgram
Within SIM since 1995 CENAM collaboration with:Jamaica, Chile, Costa Rica,Ecuador, Argentina
Bilateral since training and development in:NIST 1992PTB 1996BAM 2001KRISS 2002NMIJ 2003
All fields Primary methods, uncertaintyGas metrology, IDMS, Soils CRMIDMS (organics)Planning
CONCLUSIONSCONCLUSIONS
Traceable measurements are fundamental for reliability of regulatory actions.
Traceability could be achieved by establishing reference points of the chain of comparison:
Reference MethodsReference Materials/devicesReference measuring instruments
Practical ways in establishing traceability is to conform anorganization of responsible member entities with specifictasks in metrology, corresponding to reference point
Centro Nacional de Metrologíae-mail: [email protected] [email protected]
[email protected] site: http://www.cenam.mx
November, 2003
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