--supporting the quality system of the supporting the quality … · Oct. 26, Oct. 26, 2011. 2011....

16th WMO/IAEA Meeting on Carbon Dioxide, Other Greenhouse Gases, and Related Measurement Techniques (GGMT16th WMO/IAEA Meeting on Carbon Dioxide, Other Greenhouse Gases, and Related Measurement Techniques (GGMT16th WMO/IAEA Meeting on Carbon Dioxide, Other Greenhouse Gases, and Related Measurement Techniques (GGMT16th WMO/IAEA Meeting on Carbon Dioxide, Other Greenhouse Gases, and Related Measurement Techniques (GGMT----2011)2011)2011)2011)

WCC for SFWCC for SFWCC for SFWCC for SF6666

----supporting the quality system of the supporting the quality system of the supporting the quality system of the supporting the quality system of the global atmosphere observation global atmosphere observation global atmosphere observation global atmosphere observation

Jeongsoon Lee([email protected])

Korea Research Institute of Standards and Science (KRISS)Korea Research Institute of Standards and Science (KRISS)Korea Research Institute of Standards and Science (KRISS)Korea Research Institute of Standards and Science (KRISS)

Korea Meteorological Administration (KMA)Korea Meteorological Administration (KMA)Korea Meteorological Administration (KMA)Korea Meteorological Administration (KMA)

Oct. 26, Oct. 26, Oct. 26, Oct. 26, 2011.2011.2011.2011.


ContentsContentsContentsContents

Background

WCC scope under GAW program

Summary

former GAW activity


Operation plan

Current status

Technical evidence


CurrentCurrentCurrentCurrent status and steps towards WCCstatus and steps towards WCCstatus and steps towards WCCstatus and steps towards WCC----SFSFSFSF6666

• Feb. 2011: Submission of WCC- SF6 proposal to WMO

• ~Aug. 2011: Proposal reviewed by SAG GG

• Oct. 2011:presentation at the 16th expert meeting

• Nov. 2011~: secure funding for WCC-SF6 by KMA after decision

• 2012 ~: operation of WCC-SF6



Background

• KMA has observed several greenhouse speciessince 1998 and contributes to the GAW program asa regional GAW station.• To build up their technical ability for observation,KMA has cooperated with KRISS since 2002. KMAwould like to contribute more to WMO-GAW activity.• CCL for SF6 was established in 2010 and it is timeto designate WCC for SF6. KMA now want to offerthe service to GAW stations by systematicallysupporting their traceability and quality systemthrough WCC activities.


GAW QA system

5

• Detect small trends (through DQO)

• Detect small spatial gradients

• Ensure long-term stability of observations

• Data comparability (on the same scale)

• According to the WMO Global Atmosphere Watch (GAW) Strategic Plan: 2008 -2015 (GAW report 172) WMO-GAW have paid attention to systematically improve quality of data observed at the global or regional monitoring site. • To produce good measurement data, it is essential to ensure traceability over the world as well as to establish a controlled quality system.

-For the implementation of Quality system recommended by GAW program


Framework of a global atmospheric observations system

WCC


WCC scope

- ToR in GAW report #172

− Development of quality control procedures (in co-operation with the respective QA/SAC and SAG)

− Maintaining laboratory and transfer standards that are traceable to the WMO GAW scale

− Conducting performance and system audits for stations

− Conducting round-robin experiments (coordination of intercomparisons) and participation in international intercomparisons

− Providing training and long-term technical assistance for station scientists and technicians

− To assist members operating GAW stations to link their observations to the WMO GAW scale


Recommended compatibility Recommended compatibility Recommended compatibility Recommended compatibility

of of of of GHG measurements in GHG measurements in GHG measurements in GHG measurements in the the the the GAW programme (DQOs)GAW programme (DQOs)GAW programme (DQOs)GAW programme (DQOs)

Component Compatibility goal rangein the unpolluted troposphere

CO2 ± 0.1 ppm± 0.05 ppm: s. hemisphere

360 … 420 ppm

δ13C-CO2 ± 0.01 ‰ -7.5 … -9 ‰ vs. VPDB

δ18O-CO2 ± 0.05 ‰ -2 … +2‰ vs. VPDB

Δ14C-CO2 ± 1 ‰ 0 … 70‰

O2/N2 ± 2 per meg -250 … -550 per meg

CH4 ± 2 ppb 1700 … 2000 ppb

CO ± 2 ppb 30 … 300 ppb

N2O ± 0.1 ppb 320 … 335 ppb

H2 ± 2 ppb 450 … 600 ppb

SF6 ± 0.02 ppt 5 … 9 ppt


Central Calibration Laboratory (CCL)-WMO GAW SF6 mole fraction

WCC-SF6

GAW Stations

Other Stations or Lab.

QA/QC:Audits & Roundrobin test

Traceability of Calibrations and Audits

Round-Robin

test

Transfer standard

Working/Lab. standard

Transfer of the WMO GAW scale


10

year 2011 2012 2013 2014 2015 2016 2017

Traceability

Audit

Technical assistance

Planning WCC-SF6

- purchase of cylinders with the WMO GAW scale (every 5 year)- WS will be checked its stability every six month

- SOP preparation for instrument calibration- SOP preparation for Working standard preparation

- Audit : Procedure (2013) then audit report after finishing 1 cycle - system audit: quality system based on GAW report or some

recommendation of SAG- performance audit (RRT): SF6 measurement stations (37, WDCGG,

< 10 Lab.): every 4 year for global stations)

- WMO/IAEA expert meeting- Workshop (bi annually : SF6) including training, technical assistance- visiting GAW station

WCC activity: QA/QC


year 2011 2012 2013 2014 2015 2016 2017

Equipment

SOP Documents

Cooperationfor

operatingWCC

11

-the WMO GAW scale, analysis system (GC/ECD), Air compression device- cylinders, cylinder evacuation system

- SOP: instrument calibration, Air sampling: 2011-2012

- Audit procedure: 2012-2013

- preparation of working standard, annual report (2013 ~)

Planning WCC-SF6

- KMA Cooperates with KRISS to satisfy the QA/QC recommended by WMO/GAW, SAG-GG.

- KMA: Develop WCC program for financial supporting the operation and maintenance of WCC as well as for the cooperation with KRISS

- KRISS: technical support under long term program (RRT, development of procedure, maintenance of QC, Audit)


Global network of SF6

observationshttp://gaw.empa.ch/gawsis/default.asp

- Total # of site: 37- By regionally grouping the sites: ① EU② AM③ Asia-Oceania④ others - Regular RRT Every 4

years- About 10 Lab. Which

analyze SF6 including AGAGE net.

Management practice

Stations monitoring SF6 (total: 37)


<< GC/ECD Analytical Condition >>

* Detector : μECD (6890A, Agilent)

* Heater temp. : 375 ℃

* Oven temp. : 57 ℃, 16.5 min

25 ℃/min to 165 ℃, 7.7 min

25 ℃/min to 170 ℃, 16.5 min

* Carrier gas : P5 (CH4 5 % in Ar), 80 psi (~28 mL/min)

* Column : RESTEK Alumina F-1 12 ft*2 ea, 1/8 inch SS

* Valve box temp. : 110 ℃

* Sample loop size : 7 mL

* Sample flow : ~200 mL/min (MFC 1000)

* New regulator without gauge, outlet P. 40 psig

* Integration : slope 2, width 0.35 Reject(1,1)

but manually integrated, 7.5 min-9.5min

SF6 analytical capability

WMO scale

air


min5 10 15 20 25 30 35 40

Hz

100

150

200

250

300

350

400

450

ECD1 A, (110924\FB344403.D)

(b) Baking Column after three injections

min0 2 4 6 8 10 12 14

Hz

100

110

120

130

140

150

ECD1 A, (110924\FB344302.D)

(a) Separation: SF6 and N2O peaks

SF6 chromatogram


WMO GAW SFWMO GAW SFWMO GAW SFWMO GAW SF6666

mole fraction scalemole fraction scalemole fraction scalemole fraction scale

• Internal Consistency

min0 2 4 6 8

Hz

100

110

120

130

140

ECD1 A, (110924\FB344108.D) ECD1 A, (110924\FB344302.D) ECD1 A, (110924\FB344402.D) ECD1 A, (110924\FB344702.D) ECD1 A, (110924\BF345002.D)

CylCylCylCyl. #. #. #. #CCCCCRMCRMCRMCRM

[pmol/mol]SDSDSDSD AreaAreaAreaArea

CCCCcalcalcalcal....

[pmol/mol]Diff.Diff.Diff.Diff.[[[[pptpptpptppt]]]]

Sens.Sens.Sens.Sens.

FB03441FB03441FB03441FB03441 3.946 0.015 174.12 3.937 -0.009 44.12

FB03443FB03443FB03443FB03443 5.920 0.017 260.51 5.941 +0.021 44.01

FB03444FB03444FB03444FB03444 7.972 0.023 346.38 7.964 -0.008 43.45

FB03447FB03447FB03447FB03447 9.595 0.018 414.28 9.585 -0.010 43.18

FB03450FB03450FB03450FB03450 11.887 0.020 509.43 11.893 +0.006 42.86

NOAA/ESRL sent 5 cylinders to KRISS in Sep. 2011


Cylinder Evacuation with turb-pumping by 10-6 torr

Air sampling system with oilesspump

Addition of an artificial air Or high concentration SF6 into air

sampled

Preparation of working standardPreparation of working standardPreparation of working standardPreparation of working standard---- traceable to traceable to traceable to traceable to the WMO the WMO the WMO the WMO scalescalescalescale

To assign the values by Comparison analysis with the

mixtures which are traceable to the WMO GAW scale


Oil free Air Sampling System

Filter

RIX SA-3E Pump

1500psiRelief valve

Pressure gauge

Mg(ClO4)2 moisture traps

Drain valve

Cylinder


Filling System for addition


y = -0.161174x2 + 44.698562x + 0.638831R² = 0.999981

100

200

300

400

500

600

3 5 7 9 11 13

Pea

k A

rea

SF6 Concentration (ppt)

Calibration curve

NOAA

ANM Air

KRISS prepared working cylinder (#CC315007) based on the WMO GAW SF6 scale

-By multi position calibration CANM is 7.520 ± 0.02 ppt

-By two points calibration (near bracketing) CANM is 7.524 ± 0.02 ppt

Value assignment Value assignment Value assignment Value assignment of working standardof working standardof working standardof working standard---- traceable to traceable to traceable to traceable to the WMO the WMO the WMO the WMO scalescalescalescale

min0 2 4 6 8 10 12 14

Hz

100

110

120

130

140

ECD1 A, (110924\FB344302.D) ECD1 A, (110924\31500732.D)

Red : Anmyeon-do Air (CC315007, 7.524 ppt)Blue : NOAA CRM (FB03443, 5.920 ppt)


GAW activities for monitoring GG

� 1st, 2nd and 3rd East Asia workshop annually since

2009

� Participation RRT and Performing Proficiency test

� For the purpose to test new instruments, KRISS/KMA

have been cooperating continuously: CRDS, FTIR,


Intercomparisons (KRISS as CCQM member) − 2002 CCQM-P41 Greenhouse gases (CO2 and CH4 in air)

− 2006 CCQM K52 CO2 in nitrogen, ambient level

− 2008 CCQM K68 N2O in air, ambient level ( KRISS coordinated)

− 2011 CCQM K84 CO in artificial air , ambient level (KRISScoordinated)

RRT (GAW activity)- JMA CH4 RRT: 2001, 2005, 2009

- WMO RRT : 2008 ~ (CO2, CH4, N2O, SF6, CO)

GHGs measurement capability improvement- Proficiency test CO2, N2O, CO, SF6

History of intercomparison participation

The 3rd Asian GAW Workshop on Greenhouse Gases


Results of Methane Reference Gas

intercomparisons in Japan(2008-2009)

- At that time, the KRISS Scale agree with the NOAA Scale within about 4 ppb. Japan Meteorological Agency (JMA), Chinese Academy of Meteorological Sciences (CMA)


Proficiency Test (2006-2007)- Methane in air

� Participants:

Special gas company

Environmental agency

KMA/GAW

20072006


Proficiency Test (2010)- Carbonmonoxide in air (500-1500 ppb)

� Participants: Anmyun site, Gosan site, Korea polar research institute, special gas company


Proficiency test (2011) Proficiency test (2011) Proficiency test (2011) Proficiency test (2011)

25

Lab. participated A B

assigned7.375

(0.074)7.429

(0.047)

reported 7.37(0.16)

7.43(0.32)

SD(precision) 0.04 0.03

# of measurement 8회 16회

(unit: pmol/mol)

• Target material: SF6 at ambient level (5 ~ 10 pmol/mol)

• Participants: KGAW(Anmyun), SNU(Gosan)

• Preparation : air sampled, 6.1 L aluminum cylinder

- As a result, the WMO GAW scale agrees with the AGAGE network scale for SF6.Still it was found that there is a need to study on the expression of uncertainty.


SummarySummarySummarySummary

� Submission of proposal for invitation of World Calibration

Center (WCC)

- variable : SF6

- Technically support that measurement scale should be

traceable to the WMO GAW scale and data quality should

satisfy DQO

- KMA is to have a role as a responsible organization of the

WCC - SF6

- Overview of management program WCC-SF6

� Some technical evidence which is complying with SF6 DQOs

� Former & ongoing GAW activities


Thank you for your attention.

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