CCQM – Gas Analysis Working Group

Jin Seog Kim

KRISS

Presentation to CCQM

April 2016

CCQM

GAWG

34th Meeting (participants 47: 21 Economies+BIPM/NOAA/IAEA) – 18th-19th Apr. 2016, BIPM

• 12 comparisons in 2015-2016 – K84 (CO), K101 (oxygen/nitrogen), K90 (formaldehyde),

K111 (core KC, propane), K112 (Biogas), K113 (Noble gas),

K116 (Water vapour), K117 (ammonia), K118 (Natural gas),

K119 (LPG), K121 (terpenes), K120 (ambient CO2)

• 8 comparisons in 2017-2019 – K137 (core KC, NO), K41.2017 (H2S),

– K74.2018 (NO2), K3.2018 (automotive gases), K10.2018 (BTEX)

– K26b.2019 (SO2), K68.2019 (ambient N2O)

– Pxxx (particle number/charge concentration), Pxxx (Particle mass con.)

• 3 KC, 5 RMO KC & SC in KCDB – K94 (DMS), BIPM.QM-K1 (ISCIII, DMDM)

– APMP 2, COOMET 3 2

Summary of 2015/2016

• Draft A KC reports

• 7 planed KCs (Repeat KCs)

• Approval of strategy document of track A KC

- CMC re-review for Cycle XVIII

• Other issues

- Task group on strategy of particle/black carbon

- Task group on ozone cross section

• Next meeting

3

Today’s report

4

Core KC: CCQM-K111 Propane in Nitrogen VSL

(draft A)

APMP.QM-K111 Draft A CERI

EURAMET.QM-K111 Draft A VSL

COOMET.QM-K111 Measurement VNIIM

SIM.QM-K111 Measurement INMETRO

Page

CCQM-K111

5

CERI INMETRO KRISS NIST NMISA NPL VNIIM VSL

-15

-10

-5

0

5

10

15

diffe

renc

e (µ

mol

/mol

)

Laboratory

CCQM-K111.1 NMISA, VSL draft A

CCQM-K90 Formaldehyde 2 µmol/mol in nitrogen BIPM

(Draft A) (to support air quality regulation)

NIST could not report a value, because of instrumental problem

• Cylinder still at NIST

• Draft A report written without any measurements on cylinder attributed to

NIST Subsequent comparison (K90.1)

Set of transfer standards value assigned by BIPM

CCQM-K112 Biogas VSL

(Draft A) Component Drift - min Drift - max Homogeneity

Methane -0.12% 0.04% 0.14%

Carbon dioxide -0.09% 0.12% 0.38%

Nitrogen -0.14% 0.01% 0.52%

Hydrogen -0.24% 0.13% 0.26%

Oxygen -1.54% -1.07% 9.21%

Ethane -0.15% 0.22% 0.28%

Propane -0.66% 0.34% 0.32%

A B C D E F G H J K A

-0.05

-0.04

-0.03

-0.02

-0.01

0.00

0.01

0.02

0.03

0.04

0.05

0.06 reference value

consensus value

diffe

ren

ce

(cm

ol/m

ol)

laboratory

Degrees-of-equivalence oxygen

KCRV: Reference values

CCQM-K119 LPG

(Draft A)

CCQM-K121 Terpenes NIST

Degrees of equivalence between lab value and KCRV for each monoterpene. Error bars represent expanded

uncertainties, U Diff = sqrt(uKCRV2 + uLab

2); k = 2. Dashed lines represent uncertainties of gravimetric values, k = 2.

CCQM-K116 10 µmol/mol H2O/N2 NPL June 2015: cylinders to participants, NIM

CCQM-K117 10-30 µmol/mol NH3 in nitrogen VSL Jan. 2017: cylinders to participants

CCQM-K118 Natural gas (with H2) BAM/VSL

Jan 2017: cylinders to participants

CCQM-K120a & K120b Ambient level CO2 BIPM Nov. 2016: prepared cylinders to BIPM

On-going KCs: Measurement in 2016

CCQM-K117 Ammonia 20 µmol/mol VSL

(Protocol ready, Analytical comparison)

• 50 L aluminium cylinders with UN-stamps are available

• Gas company can be filled with an ammonia in nitrogen

mixture at 150 bar with delivery time 5 months

• But the costs associated with the cylinders are approx. € 16000

• Participant will pay € 2000 for the comparison cylinder and

after finishing of KC measurement the participants will own

the Cyl.

Terminology: analytical & preparative

Analytical comparison: Coordinator Lab prepare comparison Cyl.

Distribute Cyl. to participants

Preparative comparison: Participant prepare comparison Cyl.

Transfer Cyl to coordinator

CCQM-K137 Core KC 30-70 µmol/mol NO/N2 BIPM June 2017: prepared 2 cylinders to BIPM

CCQM-K41.2017 10 µmol/mol H2S/N2 KRISS May 2017: cylinders to participants

CCQM-K74.2017 10 µmol/mol NO2/N2 BIPM March 2018: prepared cylinders to BIPM

CCQM-K3.2018 Automobile gases VSL April 2018: cylinders to participants

CCQM-K10.2018 BTEX NIST April 2018: prepared cylinders to NIST

CCQM-K26b.2019 300 nmol/mol SO2 NIST 2019: cylinders to participants

CCQM-K68.2019 ambient N2O BIPM 2019: prepared cylinders to BIPM

Planed KCs: Measurement during 2017-2019

Outline programme

Reference No. Description Coordinating

Laboratory

Expected

Start date Status

Rational for Key

Comparison

BIPM.QM-K1 KC (Ozone at ambient level) BIPM / 20

2007 -

ongoing on-going Atmospheric and air quality

CCQM-K90 KC (Formaldehyde in air) BIPM 2015 A Atmospheric and air quality

CCQM-K111 Core KC (Propane in Nitrogen) VSL 2014 A Core mixtures

CCQM-K112 KC (Biogas) VSL 2014 A Energy gases (Renewable)

CCQM-K113 KC (Noble Gases Mixture) KRISS 2014 A New emerging requirements

CCQM-K116 KC (Water vapour 10ppm) NPL 2015 M New emerging requirements

CCQM-K117 KC (NH3) VSL&NIST 2015 P Atmospheric and air quality

CCQM-K118 KC (Natural gas) VSL & BAM 2015 P Energy gases

CCQM-K119 KC (LPG) NPL 2015 A Energy gases

CCQM-K121 KC (Monoterpenes in Nitrogen) NIST 2015 A Atmospheric and air quality

CCQM-K120a KC (Ambient CO2, 380 to 480 μmol/mol) BIPM with NIST 2016 P Atmospheric and air quality

CCQM-K120b

Core KC (Ambient CO2, 380 to 800

μmol/mol) BIPM with NIST 2016 P Atmospheric and air quality

CCQM-K137

Core KC (NO in Nitrogen, 30-70

μmol/mol) BIPM 2017

Atmospheric and air quality

(Core mixtures)

CCQM-K41.2017 KC (H2S in Nitrogen, 10 μmol/mol) KRISS 2017

Atmospheric and air quality

(Non core mixture)

CCQM-PXX

PC(Micro-scale particles, number/charge

concentration) PTB/NPL 2017 New emerging requirements

CCQM-PXX

PC(Micro-scale particles, mass

concentration) VNIIM 2017 New emerging requirements

CCQM-K74.2018 KC (NO2 in Nitrogen, 10 μmol/mol) BIPM 2018 Atmospheric and air quality

CCQM-K3.2018 KC (Automotive gases) VSL 2018 Car emission gases

CCQM-K10,2018 BTEX/VOC NIST 2018 Air Quality

CCQM-K26b.2019 KC (300 nmol/mol SO2) NPL 2019 Analytical capability

CCQM-K68.2019 KC (Ambient N2O)

BIPM with

KRISS 2019 Atmospheric and air quality

CCQM-PXX

PC (Carbon/Oxygen isotope ratios in

CO2 ) BIPM/IAEA 2019 New emerging requirements

CCQM-KXX Core KC (SO2) NIST 2020 Core mixtures

CCQM-KXX KC (New energy gas) 2020 Energy gases

CCQM-KXX KC (Nano & micro-scale particles) 2020 New emerging requirements

CCQM-KXX KC (ppb level of water vapour) 2021 New emerging requirements

CCQM-PXX PC(HCl or HF in workplace air) 2021 Atmospheric and air quality

CCQM-KXX Core KC (CO) 2022 Core mixtures

Page

Approval of GAWG strategy document on the 19th April, 2016

GAWG strategy for comparisons and CMC claims

by Paul Brewer and Adriaan van der Veen

- Strategy for selecting comparison studies for the GAWG

work programme

- Strategy for CMC claims

- Implementation of the flexible scheme to support CMCs

- Guidance for CMC claims for purity analysis

- Guidance for linking RMO comparisons to track A key

comparisons

- Annex A: Example calculations for track A (K52, K53 and

K76) and track B (K82)

Page

CMC Re-review for cycle XVIII

Re-review items: Track A (flexible scheme) components

• Evidence based on track record from previous core comparisons • Optional - can continue using existing approach

GAWG Strategy Plan (2017-2027) The task team for revision of strategic plan of GAWG

JS Kim, Robert, Paul, Adriaan, Jerry, Hanspeter

Page

Task group on Particulate Comparison

• Members:

Liu Junji (NIM), Paul Quincy (NPL), Andreas Nowak

(PTB), Hanspeter Andres (METAS), Shankar G.

Aggarwal (NPLI) and Yuri Kustikov (VNIIM)

• Strategy development:

June 2015: kick-off at ETHZ particle conference

Sep. 2015: first draft available to circulate

• Comparison protocols:

Presented at GAWG meeting (April 2016)

PS sizing: a) 2.5 / 10 mm

b) 1 – 10 nm

Draft Roadmap

2016 2018 2020 202X

size

key/parallel PS Number &

charge concentration

10 nm

500 nm

2.5 mm 10 mm

PS mass

concentration

PS number

concentration PS BC

time

*PS = pilot study

28.07.2016 METAS 20

Coordination: PTB/NPL

Host: TROPOS (WMO WCC physical aerosol measurements)

Participants: PTB, NPL, METAS, NPLI, KRISS, VINITFRI,

NMIJ(?), NIM (?), LNE (?), BAM (?), TROPOS (if WEM agrees)

Timescale: Protocol: October 2016

comparison in first quarter 2017

Draft A: October 2017

Draft B: April 2018

Comparison on number / charge concentration Repeat of EURAMET 1224 (charge conc.),1282 (number conc.)

CCQM.Pxxx Particle Comparison in 2017

1993

Room-temperature ozone cross sections at 253.65 nm

0.9 %

Task Group on Ozone Cross Section

GAWG: Joseph Hodges (NIST), Joëlle Viallon (BIPM), Robert Wielgosz (BIPM),

Sangil Lee (KRISS), Paul Brewer (NPL), Jari Walden (FMI)

Other: Christof Janssen (Paris-Jussieu) and !!!

Gas phase titration

Page

Sources of Measurement Uncertainty & Bias Relative weighting of published data will be influenced by uncertainties in: sample conditions: purity & stability (O3 molar fraction), temperature, pressure transmittance measurement pathlength type of source (Hg lamp, continuum, laser) instability in irradiance of light source

spectral contribution from other Hg lines baseline stability & stray light detector non-linearity

Will need to assess appropriate combined uncertainties of literature data

23

• Progress report Core KCs (K111 series), Protocols for New KCs • Approval of ‘Strategy Document’ for flexible CMC

application • Task team for GAWG strategy document (2017-

2027) • Next GAWG Meeting (11-14 October 2016, IPQ) 11-12 GAWG meeting 13 Workshop on Scientific results 14 Workshop on Standards and Measurements for Clean Air • 2017 Fall meeting: October 2017, VSL

Summary

24

34th GAWG Meeting, 18th-19th Apr. 2016, BIPM

Acknowledgements All member participants, Coordinators of comparisons,

and Experts who provide presentations.