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Ozone Measurement Traceability with the<br />

<strong>NIST</strong> <strong>Standard</strong> <strong>Reference</strong> <strong>Photometer</strong><br />

James E. Norris<br />

Maryland Department of the Environment<br />

May 18, 2011<br />

<strong>NIST</strong> Analytical Chemistry Division<br />

1


• <strong>NIST</strong><br />

Outline<br />

• Measurement <strong>Standard</strong>s<br />

• Ozone <strong>Standard</strong>s<br />

• <strong>NIST</strong> <strong>Standard</strong> <strong>Reference</strong> <strong>Photometer</strong><br />

• U.S. Ozone Measurement Traceability<br />

• BIPM/<strong>NIST</strong> Collaboration<br />

• International Ozone Measurement Comparability<br />

• Summary<br />

<strong>NIST</strong> Analytical Chemistry Division<br />

2


National Institute of <strong>Standard</strong>s and<br />

Technology<br />

is a<br />

non-regulatory agency<br />

in the<br />

Technology Administration<br />

of the<br />

US Department of Commerce.<br />

Mission … to strengthen the U.S. economy and improve the quality<br />

of life by working with industry to develop and apply technology,<br />

measurements and standards.<br />

<strong>NIST</strong> Analytical Chemistry Division<br />

3


U.S. Federal Role in Metrology<br />

The Constitution of the United States<br />

Article 1, Section 8: The Congress shall have the power … to<br />

coin money, regulate the value thereof, and of foreign coin<br />

… and fix the standard of weights and measures … (1788)<br />

“Foreign traders had begun to voice concern that goods<br />

might not be assigned a proper quantitative value at<br />

American custom-houses and that, as a result, assessed<br />

duties might be unfair and uneven from port to port.”<br />

John Quincy Adams (1817)<br />

<strong>NIST</strong> Analytical Chemistry Division<br />

4


NBS Organic Act of 1901<br />

“It is therefore the unanimous opinion of<br />

your committee that no more essential aid<br />

could be given to<br />

• manufacturing<br />

• commerce<br />

• the makers of scientific apparatus<br />

• the scientific work of Government<br />

• schools, colleges, and universities<br />

than by the establishment of the<br />

institution proposed in this bill.”<br />

• Custody of the standards;<br />

• Comparison of the standards used in scientific investigations, engineering, manufacturing, commerce,<br />

and educational institutions with the standards adopted by or recognized by the Government;<br />

• Construction of standards, their multiples and subdivisions;<br />

• Testing and calibration of standard measuring apparatus;<br />

• Solution of standards problems; and,<br />

• Determination of physical constants and the properties of materials,<br />

when such measurements, standards and data are of great importance and are not to be<br />

obtained of sufficient accuracy elsewhere.<br />

<strong>NIST</strong> Analytical Chemistry Division<br />

5


Early Driver for <strong>Standard</strong>s<br />

1904<br />

• Out-of-town fire<br />

companies arriving at a<br />

Baltimore fire cannot<br />

couple their hoses to<br />

the hydrants. 1526<br />

buildings razed.<br />

1905<br />

• National Fire Protection<br />

Association adopted<br />

NBS-developed<br />

national hose coupling<br />

standard<br />

<strong>NIST</strong> Analytical Chemistry Division<br />

6


Birth of the “<strong>Standard</strong> Samples” Program<br />

1905<br />

<strong>Standard</strong> samples program begins<br />

with “standardized irons” in<br />

collaboration with the American<br />

Foundrymans Association<br />

1906<br />

At the request of the Association of<br />

American Steel Manufacturers, NBS<br />

began work on certification of 17<br />

types of steel<br />

• By 1951, there were 502 <strong>Standard</strong><br />

Samples, 98 of these were steels<br />

• Today there are more than 1400<br />

different SRMs<br />

• ~ 32,000 units sold annually<br />

<strong>NIST</strong> Analytical Chemistry Division<br />

7


Train Derailments<br />

… Poor Quality Control<br />

1912<br />

A report by the Interstate Commerce Commission revealed alarming statistics for<br />

railroad accidents; almost 42,000 over the past decade. NBS began a program to<br />

examine cracked rails and other failed parts through chemical, microscopic, and<br />

mechanical tests.<br />

<strong>NIST</strong> Analytical Chemistry Division<br />

8


• Technology Innovation Program<br />

• Manufacturing Extension Partnership<br />

• Baldrige National Quality Award<br />

• <strong>NIST</strong> Laboratories<br />

– ~1,400 technical staff including ~700 PhD<br />

scientists and engineers<br />

– 3 Nobel Laureates since 1997<br />

– MacArthur Fellowship winner in 2003<br />

– National Medal of Science winner in 1998<br />

– 14 National Academy Members<br />

– ~120 National Society Fellows and<br />

recipients of ~60 National or International<br />

Awards per year<br />

• One of three Federal Agencies singled out for<br />

significant budget growth under the American<br />

Competitiveness Initiative.<br />

<strong>NIST</strong> Today<br />

Chemists<br />

12%<br />

Engineers<br />

26%<br />

Physicists<br />

21%<br />

Comp.Sci./Prog.<br />

21%<br />

Other<br />

16%<br />

Math<br />

4%<br />

<strong>NIST</strong> Analytical Chemistry Division<br />

9


<strong>NIST</strong> still fulfills the NBS traditional function:<br />

the development & dissemination of primary standards<br />

pendulum clock<br />

1 s in 3 years<br />

(1904)<br />

silver voltameter<br />

current standard<br />

(1910)<br />

physical artifact<br />

(1889)<br />

second<br />

ampere<br />

kilogram<br />

<strong>NIST</strong> F1<br />

atomic clock<br />

1 s in 30 million<br />

years<br />

(1999)<br />

single<br />

electron<br />

counter<br />

(20xx)<br />

electronic<br />

kilogram<br />

(20xx)<br />

10<br />

<strong>NIST</strong> Analytical Chemistry Division


<strong>NIST</strong> Measurement <strong>Standard</strong>s<br />

•Physical<br />

• Mass<br />

• Force<br />

• Pressure<br />

• Temperature<br />

• Humidity<br />

• Chemical<br />

• Environmental<br />

• Food and Drug<br />

• Biological<br />

• Metals and Alloys<br />

11<br />

<strong>NIST</strong> Analytical Chemistry Division


<strong>NIST</strong> <strong>Standard</strong>s for Chemical Measurements<br />

Chemical standards constitute over 2/3 of ~1,400 <strong>NIST</strong> SRM types<br />

• High Purity Neat Chemicals<br />

• Organic Solution <strong>Standard</strong>s<br />

• Inorganic Solution <strong>Standard</strong>s<br />

• Gas Mixture <strong>Standard</strong>s<br />

Complex Matrix <strong>Standard</strong>s<br />

• Advanced Materials<br />

• Biological Fluids/Tissues<br />

• Foods/Botanicals<br />

• Geologicals<br />

• Metals and Metal Alloys<br />

• Petroleum/Fossil Fuels<br />

• Sediments/Soils/Particulates<br />

• Cements<br />

• Molecular Spectrometry <strong>Standard</strong>s<br />

• Electrolytic Conductivity <strong>Standard</strong>s<br />

• pH / Ion Activity <strong>Standard</strong>s<br />

12<br />

<strong>NIST</strong> Analytical Chemistry Division


Hierarchy of Gas <strong>Standard</strong>s<br />

Primary <strong>Standard</strong>s<br />

<strong>Standard</strong> <strong>Reference</strong> Materials<br />

<strong>NIST</strong> Traceable <strong>Reference</strong> Material<br />

Research Gas Mixtures<br />

EPA Protocol Gases<br />

13<br />

<strong>NIST</strong> Analytical Chemistry Division


EPA Protocol Gas Audits<br />

• Compliance to EPA Traceability Protocol for Assay<br />

and Certification of Gaseous Calibration <strong>Standard</strong>s<br />

(EPA-600/R-97/121), September 1997.<br />

– Certificate of Analysis with vendor certified value.<br />

– Cylinder Labels.<br />

– Cylinder contents analyzed by <strong>NIST</strong>.<br />

– Vendor value within 2 % of <strong>NIST</strong> value to pass audit.<br />

14<br />

<strong>NIST</strong> Analytical Chemistry Division


Ozone Measurement Instruments<br />

• Wet Chemistry Titration<br />

• neutral buffered potassium iodide (NBKI)<br />

• boric acid potassium iodide (BAKI)<br />

• Chemiluminescence<br />

• reaction of O 3 with ethylene (C 2H 4)<br />

• Gas Phase Titration<br />

• reaction of O 3 with NO<br />

• UV Photometric<br />

• absorption at 253.7 nm<br />

15<br />

<strong>NIST</strong> Analytical Chemistry Division Division


C<br />

=<br />

UV Photometric Instruments<br />

Derivation of Beer-Lambert Law equation used<br />

for calculating ozone mole fractions<br />

−<br />

lnT<br />

α L<br />

×<br />

⎛<br />

⎜⎜<br />

⎝<br />

T ( sample)<br />

T ( std)<br />

C = ozone concentration<br />

T = transmittance (I/I 0 )<br />

α = ozone absorption coefficient (at STP)<br />

L = optical path-length<br />

T (sample) = sample gas temperature<br />

T (std) = standard temperature<br />

P (std) = standard pressure<br />

P (sample) = sample gas pressure<br />

×<br />

P(<br />

std)<br />

P(<br />

sample)<br />

⎞<br />

⎟⎟<br />

⎠<br />

16<br />

<strong>NIST</strong> Analytical Chemistry Division


<strong>NIST</strong> <strong>Standard</strong> <strong>Reference</strong> <strong>Photometer</strong> (SRP)<br />

U.S. EPA and <strong>NIST</strong> Collaboration (beginning 1981).<br />

UV Photometry (Absorption of 253.7 nm Hg Line).<br />

Custom Designed and Built Instrument.<br />

Measurement Range: 0 to 1000 nmol/mol (ppbv).<br />

Estimated Uncertainty: ± 1 ppbv (0 - 100 ppbv).<br />

± 1% (100 - 1000 ppbv).<br />

<strong>NIST</strong> Ozone <strong>Reference</strong> <strong>Standard</strong> - 1982 to Present.<br />

Ozone <strong>Reference</strong> <strong>Standard</strong> for many other Countries.<br />

BIPM Ozone <strong>Reference</strong> <strong>Standard</strong>.<br />

17<br />

<strong>NIST</strong> Analytical Chemistry Division


Arnold Bass and Jim Norris with SRP 2, circa 1984<br />

18<br />

<strong>NIST</strong> Analytical Chemistry Division Division


<strong>NIST</strong> SRP 47<br />

19<br />

<strong>NIST</strong> Analytical Chemistry Division


Schematic of SRP System<br />

20<br />

<strong>NIST</strong> Analytical Chemistry Division Division


Component (y)<br />

Optical Path<br />

Lopt<br />

Source Distribution<br />

Uncertainty u(y)<br />

<strong>Standard</strong><br />

Uncertainty<br />

Measurement<br />

Scale<br />

Rect. 0.0006 cm<br />

Repeatability Normal 0.01 cm<br />

Bias Rect 0.52 cm<br />

Pressure gauge Rect. 0.029 kPa<br />

Pressure P Difference<br />

between cells<br />

Rect. 0.017 kPa<br />

Temperature T<br />

Temperature<br />

probe<br />

Rect. 0.03 K<br />

Residual bias Rect. 0.058 K<br />

Scalers<br />

resolution<br />

Rect. 8×10 -6<br />

Ratio of<br />

intensities D<br />

Repeatability Triang. 1.1×10 -5<br />

Absorption<br />

Cross section σ<br />

Uncertainty Estimation for SRP<br />

Conventional<br />

value<br />

1.22×10 -19<br />

cm²/molecule<br />

Combined<br />

standard<br />

uncertainty<br />

u(y)<br />

0.52 cm<br />

Sensitivity<br />

coefficient<br />

∂x<br />

ci =<br />

∂y<br />

opt<br />

x<br />

0.034 kPa<br />

−<br />

P<br />

x<br />

0.07 K T<br />

1.4×10 -5<br />

2 −2<br />

2<br />

u ( x)<br />

= ( 0.<br />

28)<br />

+ ( 1.<br />

1⋅10<br />

x)<br />

nmol / mol<br />

2 −3<br />

2<br />

u ( x)<br />

= ( 0.<br />

28)<br />

+ ( 2.<br />

92⋅10<br />

x)<br />

nmol / mol<br />

contribution<br />

to u(x)<br />

ci ⋅ u(<br />

y)<br />

nmol/mol<br />

x<br />

− 2.89×10<br />

L<br />

-3 x<br />

x<br />

D ln(D)<br />

3.37×10 -4 x<br />

2.29×10 -4 x<br />

0.28<br />

1.22×10 -19 x<br />

− 1.06×10<br />

cm²/molecule σ<br />

-2 x<br />

summarised in one equation describing the uncertainty as a function of ozone mole fraction:<br />

without the absorption cross-section uncertainty (for UV photometer comparisons):<br />

21<br />

<strong>NIST</strong> Analytical Chemistry Division Division


<strong>NIST</strong> SRPs<br />

(United States Network)<br />

SRP # Agency Location<br />

0 <strong>NIST</strong> (Traveling <strong>Standard</strong>) Gaithersburg, MD<br />

1 EPA Office of Research and Development Research Triangle Park, NC<br />

2 <strong>NIST</strong> (National <strong>Standard</strong>) Gaithersburg, MD<br />

3 EPA Region 2 Laboratory Edison, NJ<br />

4 California Air Resources Board Sacramento, CA<br />

5 EPA Region 6 Laboratory Houston, TX<br />

6 EPA Region 5 Laboratory Chicago, IL<br />

7 EPA Office of Air Quality and Planning Stds. Research Triangle Park, NC<br />

8 EPA Region 8 Laboratory Golden, CO<br />

9 EPA Region 1 Laboratory North Chelmsford, MA<br />

10 EPA Region 4 Laboratory Athens, GA<br />

13 EPA Region 7 Laboratory Kansas City, KS<br />

36 EPA Region 9 Laboratory Richmond, CA<br />

22<br />

<strong>NIST</strong> Analytical Chemistry Division Division


International <strong>NIST</strong> SRPs<br />

SRP # Location Organization<br />

11 Stockholm, Sweden ITM<br />

12 Toronto, Canada Ontario MOE<br />

14,18 Bern, Switzerland METAS<br />

15,23 Dubendorf, Switzerland EMPA<br />

16 Ottawa, Canada Environment Canada<br />

17 Prague, Czech Republic CHMI<br />

19 Braunschweig, Germany PTB<br />

20 London, United Kingdom NPL<br />

21 Sydney, Australia NSW-EPA<br />

22, 44 Madrid, Spain ISCIII<br />

24, 40 Paris, France LNE<br />

25 Lisbon, Portugal IA<br />

26 Vienna, Austria UBA-Austria<br />

27,28,31,32,33 Sevres, France BIPM<br />

29 Langen, Germany UBA-Germany<br />

30 Kaohsiung, Taiwan, R.O.C. Taiwan EPA<br />

34 Hong Kong, S.A.R., China Hong Kong EPD<br />

35 Tsukuba, Japan NIES<br />

37 Helsinki, Finland FMI<br />

38 St. Petersburg, Russia VNIIM<br />

39 Mexico City, Mexico INE-CENICA<br />

41 Beijing, China NIM<br />

42 Ispra, Italy EC-JRC<br />

43 New Delhi, India NPLI<br />

45 Santiago, Chile CENMA<br />

46 Singapore NMC<br />

23<br />

<strong>NIST</strong> Analytical Chemistry Division Division


<strong>NIST</strong> SRP Network<br />

(Worldwide)<br />

24<br />

<strong>NIST</strong> Analytical Chemistry Division Division


SRP Original Comparison vs. SRP 2<br />

(Slopes)<br />

Slope<br />

1.010<br />

1.008<br />

1.006<br />

1.004<br />

1.002<br />

1.000<br />

0.998<br />

0.996<br />

0.994<br />

0.992<br />

0.990<br />

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50<br />

SRP Number<br />

Average Slope: 0.99890<br />

<strong>Standard</strong> Deviation: 0.00167<br />

Delta (Max – Min): 0.72%<br />

25<br />

<strong>NIST</strong> Analytical Chemistry Division


SRP Original Comparison vs. SRP 2<br />

(Intercepts)<br />

Intercept (nmol/mol)<br />

1.6<br />

1.2<br />

0.8<br />

0.4<br />

0.0<br />

-0.4<br />

-0.8<br />

-1.2<br />

-1.6<br />

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50<br />

SRP Number<br />

Average Intercept: - 0.079<br />

<strong>Standard</strong> Deviation: 0.282<br />

Delta (Max – Min): 1.715 nmol/mol<br />

26<br />

<strong>NIST</strong> Analytical Chemistry Division


U.S. Ozone Monitoring Sites<br />

Courtesy: USEPA Website<br />

27<br />

<strong>NIST</strong> Analytical Chemistry Division


Ozone Traceability in the United States<br />

<strong>NIST</strong><br />

SRP 2, 0<br />

U.S. EPA OAQPS<br />

SRP 7<br />

U.S. EPA Regional Laboratories<br />

SRP 1,3,4,5,6,8,9,10,13,36<br />

State and Local Air Monitoring Laboratories<br />

Commercial Ozone Instrumentation<br />

Ambient Air Monitoring Stations<br />

Commercial Ozone Instrumentation<br />

28<br />

<strong>NIST</strong> Analytical Chemistry Division Division


U.S. EPA - SRP Network Traceability<br />

US-EPA<br />

<strong>NIST</strong><br />

Annually<br />

by <strong>NIST</strong><br />

US-EPA<br />

Annually<br />

by EPA<br />

SRP 1<br />

SRP 3<br />

SRP 4<br />

SRP 5<br />

SRP 2 or SRP 0 SRP 7 SRP 6<br />

SRP 8<br />

SRP 9<br />

Periodic Upgrades<br />

SRP 10<br />

SRP 13<br />

SRP 36<br />

Agreement within 1% (Slope), 1 ppbv (Intercept) required!<br />

29<br />

<strong>NIST</strong> Analytical Chemistry Division


<strong>NIST</strong> SRP Electronics Upgrade Project<br />

(1999-2000)<br />

• SRP 0-22 built with original electronics.<br />

• all have been upgraded.<br />

• Driven by obsolete electronic components.<br />

• Several circuit chips were no longer produced.<br />

• Consisted of completed electronics system redesign.<br />

• new Electronics module and Detector module.<br />

• Improved V/f conversion rate (increased signal).<br />

• Increased from 1V in-10KHz out to 1V in-30KHz out.<br />

• Included new dual external manifold.<br />

• Balanced pressure difference; improved intercepts.<br />

• Included new version 4.0 control software.<br />

• Windows based VB code.<br />

30<br />

<strong>NIST</strong> Analytical Chemistry Division Division


Average Slope<br />

1.03<br />

1.02<br />

1.01<br />

1.00<br />

0.99<br />

0.98<br />

0.97<br />

U.S. EPA SRPs vs. <strong>NIST</strong> SRP 2<br />

before and after electronics upgrade<br />

0 2 4 6 8 10 12 14<br />

Before Upgrade<br />

After Upgrade<br />

SRP Number<br />

31<br />

<strong>NIST</strong> Analytical Chemistry Division Division


Average Intercept<br />

2.00<br />

1.50<br />

1.00<br />

0.50<br />

0.00<br />

-0.50<br />

-1.00<br />

-1.50<br />

-2.00<br />

U.S. EPA SRPs vs. <strong>NIST</strong> SRP 2<br />

before and after electronics upgrade<br />

0 2 4 6 8 10 12 14<br />

Before Upgrade<br />

After Upgrade<br />

SRP Number<br />

32<br />

<strong>NIST</strong> Analytical Chemistry Division Division


International SRP Network Traceability<br />

as of 2002<br />

Canada<br />

SRP 12 (MOE)<br />

SRP 16 (EC)<br />

<strong>NIST</strong> SRP 2 or SRP 0<br />

SRP 21 (NSW-EPA)<br />

SRP 30 (TEPA)<br />

1 - 2 years<br />

2 - ? years<br />

Asia- Pacific<br />

2 - ? years<br />

Europe<br />

SRP 11 (ITM - Sweden)<br />

SRP 14, 18 (METAS - Switzerland)<br />

SRP 15, 23 (EMPA - Switzerland)<br />

SRP 17 (CHMI - Czech Republic)<br />

SRP 19 (PTB - Germany)<br />

SRP 20 (NPL - United Kingdom)<br />

SRP 22 (ISCIII - Spain)<br />

SRP 24 (LNE – France)<br />

SRP 25 (IA – Portugal)<br />

SRP 26 (UBA – Austria)<br />

SRP 29 (UBA-Germany)<br />

33<br />

<strong>NIST</strong> Analytical Chemistry Division


Bureau International des Poids et Mesures<br />

(International Bureau of Weights and Measures)<br />

The task of the BIPM is to ensure world-wide uniformity of<br />

measurements and their traceability to the International System<br />

of Units (SI).<br />

It does this with the authority of the Convention of the Metre, a diplomatic<br />

treaty between fifty-one nations, and it operates through a series of<br />

Consultative Committees, whose members are the national metrology<br />

laboratories of the Member States of the Convention, and through its own<br />

Laboratory work.<br />

The BIPM carries out measurement-related research. It takes part in, and<br />

organizes, international comparisons of national measurement standards,<br />

and it carries out calibrations for Member States.<br />

Source – BIPM website<br />

34<br />

<strong>NIST</strong> Analytical Chemistry Division


Consultative Committees under the International<br />

Committee for Weights and Measures (CIPM)<br />

CCAUV: Consultative Committee for Acoustics, Ultrasound and Vibration<br />

CCEM: Consultative Committee for Electricity and Magnetism<br />

CCL: Consultative Committee for Length<br />

CCM: Consultative Committee for Mass and Related Quantities<br />

CCPR: Consultative Committee for Photometry and Radiometry<br />

CCQM: Consultative Committee for Amount of Substance<br />

(Metrology in Chemistry)<br />

CCRI: Consultative Committee for Ionizing Radiation<br />

CCT: Consultative Committee for Thermometry<br />

CCTF: Consultative Committee for Time and Frequency<br />

CCU: Consultative Committee for Units<br />

Source – BIPM website<br />

35<br />

<strong>NIST</strong> Analytical Chemistry Division Division


Consultative Committee for Amount of Substance<br />

(CCQM)<br />

• Established by the CIPM in 1993<br />

• 35 member and observer organizations<br />

• Yearly meetings of CCQM plenary, attended by some 60 representatives<br />

• 7 working groups, meeting twice a year and attended by some 150 experts<br />

from NMI’s and other expert institutes<br />

Working Groups<br />

– Gas Analysis; chair: Dr. M. Milton (NPL, UK)<br />

– Organic Analysis; chair: Dr. W. May (<strong>NIST</strong>, USA)<br />

– Inorganic Analysis; chair: Dr M. Sargent (LGC, UK)<br />

– Electrochemical Analysis; chair: Dr. M. Máriássy (SMU, SK)<br />

– Bioanalysis; chair: Mrs H. Parkes, (LGC, UK)<br />

– Surface Analysis; chair; Dr. W. Unger BAM, DE)<br />

– Key Comparisons and CMC quality review; chair: Dr L. Mackay (NMIA, AU)<br />

Working Groups are responsible for selecting and overseeing the operation of<br />

key comparisons that address chemical measurement-related issues important<br />

for international trade, environmental health, and safety-related decision<br />

making.<br />

36<br />

<strong>NIST</strong> Analytical Chemistry Division Division


CCQM Key Comparison Database<br />

Example (gases)<br />

CCQM-K1.a<br />

Carbon monoxide (CO) in Nitrogen (N2)<br />

1994 - 1995, Approved for equivalence<br />

Results available<br />

CCQM-K1.b<br />

Carbon dioxide (CO2) in Nitrogen (N2)<br />

1993 - 1994, Approved for equivalence<br />

Results available<br />

CCQM-K1.c<br />

Nitrogen monoxide (NO) in Nitrogen (N2)<br />

1995 - 1996, Approved for equivalence<br />

Results available<br />

CCQM-K1.d<br />

Sulfur dioxide (SO2) in Nitrogen (N2)<br />

1996 - 1997, Approved for equivalence<br />

Results available<br />

CCQM-K1.e<br />

Natural gas type I<br />

1996 - 1997, Approved for equivalence<br />

Results available<br />

CCQM-K1.f<br />

Natural gas type II<br />

1996 - 1997, Approved for equivalence<br />

Results available<br />

CCQM-K1.g<br />

Natural gas type III<br />

1996 - 1997, Approved for equivalence<br />

Results available<br />

CCQM-K3<br />

Automotive emission gases<br />

1998 - 1999, Approved for equivalence<br />

Results available<br />

Source – BIPM website<br />

37<br />

<strong>NIST</strong> Analytical Chemistry Division Division


Automotive Emission Gases<br />

38<br />

<strong>NIST</strong> Analytical Chemistry Division Division


BIPM – <strong>NIST</strong> Collaboration<br />

• Delivery of SRP 27 and SRP 28.<br />

• Detailed Training during assembly of SRP 31 and SRP 32.<br />

• SRP 33 assembled at BIPM using BIPM machined parts.<br />

• Detailed Review of SRP – publication available (Metrologia).<br />

• Temperature Measurement Bias: - 0.4% estimate.<br />

• Optical Path-length Bias: + 0.5% estimate.<br />

• SRP Bias Upgrade Project – publication in progress.<br />

• Develop International Ozone Traceability System through CCQM.<br />

• CCQM – P28 - Ozone Ambient Level Pilot Study – publication available.<br />

• BIPM.QM-K1, CCQM Key Comparison 2007-2008, 2009-2010, etc.<br />

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<strong>NIST</strong> Analytical Chemistry Division Division


<strong>NIST</strong> SRP Bias Upgrade<br />

(2008-2010)<br />

• Temperature and Optical Path-length Biases.<br />

• Determined by extensive SRP review by BIPM/<strong>NIST</strong>.<br />

• Development of new light source block design.<br />

• Thermal Isolation of Heated Source Block.<br />

• Improved Collimation of Light Beam.<br />

• Development of new absorption cells.<br />

• Optically sealed windows at 3° angle – fixed length.<br />

• Fused Quartz Inlet/Outlet Ports – No Teflon or O-rings.<br />

• Path-length measurement by Coordinate Measurement Machine.<br />

• Measurement Quantification from each Bias Correction.<br />

• Independent Measurements after each Bias Upgrade.<br />

• Manuscript in review process.<br />

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<strong>NIST</strong> Analytical Chemistry Division Division


Derivation of Beer-Lambert Law equation used<br />

for calculating ozone mole fractions with the SRP<br />

C<br />

=<br />

−<br />

lnT<br />

α L<br />

×<br />

⎛<br />

⎜⎜<br />

⎝<br />

T ( sample)<br />

T ( std)<br />

×<br />

P(<br />

std)<br />

P(<br />

sample)<br />

Optical Path-length Bias<br />

· Multiple internal reflections in absorption cells from cell windows<br />

and optical filter.<br />

· Path-length (L) is underestimated, C is overestimated.<br />

Temperature Gradient Bias<br />

· Sample and reference gases heated thru thermal transfer of<br />

heat from source lamp block.<br />

· Sample Temperature [T(sample)] is underestimated, C is<br />

underestimated.<br />

⎞<br />

⎟⎟<br />

⎠<br />

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<strong>NIST</strong> Analytical Chemistry Division Division


<strong>NIST</strong> SRP Bias Upgrade Project<br />

SRP Bias Upgrade (performed in steps).<br />

1. Initial measurements.<br />

2. New cells installed – set of measurements.<br />

3. New source/optics block & shutter cover installed – final set of measurements.<br />

• 22 of 38 SRPs upgraded so far, including SRP 2.<br />

• 7 directly vs. SRP 2 at <strong>NIST</strong>.<br />

• 10 using SRP 0 as transfer.<br />

• SRP 32 vs. SRP 27 (data not corrected to SRP 0 or SRP 2).<br />

• 4 SRPs upgraded by BIPM.<br />

• data not officially available.<br />

• 10 new SRPs built new with bias upgrade included.<br />

• Average shift in slope from new cells (optical bias): -0.67%.<br />

• Average shift in slope from new source (temp. grad. bias): +0.37%.<br />

• Average net change in slope from bias upgrade: -0.30%.<br />

• No noticeable change in the intercepts.<br />

• Overall agreement in all SRPs before bias upgrade: 0.72%.<br />

• Overall agreement in all bias upgraded SRPs: 0.33%.<br />

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<strong>NIST</strong> Analytical Chemistry Division Division


Most Recent Comparison vs. SRP 2<br />

(Slopes)<br />

Slope<br />

1.010<br />

1.008<br />

1.006<br />

1.004<br />

1.002<br />

1.000<br />

0.998<br />

0.996<br />

0.994<br />

0.992<br />

0.990<br />

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50<br />

Direct vs. SRP 2<br />

SRP 0 as Transfer<br />

SRP Number<br />

Average Slope: 0.99850<br />

<strong>Standard</strong> Deviation: 0.00084<br />

Delta (Max - Min): 0.33%<br />

Original Comparisons<br />

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<strong>NIST</strong> Analytical Chemistry Division


Most Recent Comparison vs. SRP 2<br />

(Intercepts)<br />

Intercept (nmol/mol)<br />

1.0<br />

0.8<br />

0.6<br />

0.4<br />

0.2<br />

0.0<br />

-0.2<br />

-0.4<br />

-0.6<br />

-0.8<br />

Original Comparisons<br />

-1.0<br />

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48<br />

Direct vs. SRP 2<br />

SRP 0 as Transfer<br />

SRP Number<br />

Average Intercept: - 0.006<br />

<strong>Standard</strong> Deviation: 0.057<br />

Delta (Max - Min): 0.282 nmol/mol<br />

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<strong>NIST</strong> Analytical Chemistry Division


CCQM – P28 - Ozone Ambient Level Pilot Study<br />

(slopes)<br />

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<strong>NIST</strong> Analytical Chemistry Division


CCQM – P28 - Ozone Ambient Level Pilot Study<br />

(intercepts)<br />

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<strong>NIST</strong> Analytical Chemistry Division


BIPM.QM-K1, ozone at ambient level results<br />

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<strong>NIST</strong> Analytical Chemistry Division Division


BIPM.QM-K1, ozone at ambient level results<br />

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<strong>NIST</strong> Analytical Chemistry Division Division


Regional Metrology Organizations<br />

Planned GULFMET and AFRIMETS sub-region NEWMET<br />

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<strong>NIST</strong> Analytical Chemistry Division Division


NORAMET<br />

• Canada<br />

• Mexico<br />

• United States of America<br />

CAMET<br />

• Belize<br />

• Costa Rica<br />

• El Salvador<br />

• Guatemala<br />

• Honduras<br />

• Nicaragua<br />

• Panama<br />

SISTEMA INTERAMERICANO DE METROLOGÍA (SIM)<br />

(INTERAMERICAN METROLOGY SYSTEM)<br />

ANDIMET<br />

• Bolivia<br />

• Colombia<br />

• Ecuador<br />

• Peru<br />

• Venezuela<br />

CARIMET<br />

• Antigua & Barbuda<br />

• Bahamas<br />

• Barbados<br />

• Dominica<br />

• Dominican Republic<br />

• Grenada<br />

• Guyana<br />

• Haiti<br />

• Jamaica<br />

• Saint Kitts and Nevis<br />

• Saint Lucia<br />

• St. Vincent and the<br />

Grenadines<br />

• Suriname<br />

• Trinidad and Tobago<br />

SURAMET<br />

• Argentina<br />

• Brazil<br />

• Chile<br />

• Paraguay<br />

• Uruguay<br />

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<strong>NIST</strong> Analytical Chemistry Division Division


Ozone Instrument Comparisons<br />

• <strong>NIST</strong> Calibrations<br />

• NASA<br />

• NOAA<br />

• Universities<br />

• Commercial Organizations<br />

• World Meteorological Organization (WMO)<br />

• Global Atmospheric Watch (GAW)<br />

• Euromet Programs<br />

• Intercomparison of National Ozone Primary <strong>Standard</strong>s,<br />

project 414<br />

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<strong>NIST</strong> Analytical Chemistry Division


WMO-Global Atmospheric Watch (GAW)<br />

<strong>NIST</strong> is WMO-GAW Central Calibration Laboratory (CCL)<br />

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<strong>NIST</strong> Analytical Chemistry Division


Acknowledgements<br />

<strong>NIST</strong> - Franklin Guenther<br />

Willie May<br />

Dana Strawbridge<br />

Jeff Anderson<br />

Jack Fuller<br />

Bob Zarr<br />

BIPM - Robert Wielgosz<br />

Joele Viallon<br />

Phillipe Moussay<br />

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<strong>NIST</strong> Analytical Chemistry Division


Summary<br />

• <strong>NIST</strong> <strong>Standard</strong> <strong>Reference</strong> <strong>Photometer</strong><br />

– Stable, Accurate Ozone <strong>Reference</strong> <strong>Standard</strong> for 27 Years.<br />

– Network agreement maintained within 1%.<br />

– Maintained in 22 Countries, designated National <strong>Standard</strong> in 13 Countries.<br />

– Total of 48 instruments Worldwide (currently).<br />

• SRP Bias Upgrade:<br />

– Significantly reduced measurement biases<br />

– Improved overall SRP measurement agreement.<br />

– Manuscript in review process.<br />

• BIPM – <strong>NIST</strong> Collaboration<br />

– Well Established.<br />

– Developed International Traceability through CCQM.<br />

– Research with GPT, UV Laser, Improved Optical Systems.<br />

• CCQM Ozone Key Comparisons<br />

– P28 Pilot Study Completed – Results Published.<br />

– BIPM.QM-K1 Official Key Comparison (ongoing).<br />

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<strong>NIST</strong> Analytical Chemistry Division Division

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