inter laboratory comparisons for sulphur dioxide in …...performanceenvironment(regulatory) the...

Inter laboratory comparisons for

sulphur dioxide in nitrogen for

ambient air and stack gas emission

© NMISA 2011

sulphur dioxide in nitrogen for

ambient air and stack gas emission

monitoring.

James Tshilongo

20 September 2011, T & M Workshop

Overview

� Gas Metrology.� Regulatory.� Gas Metrology of South Africa.� Preparation strategy.� International measurement equivalence.� Why Regional Comparison is important

© NMISA 2011

� Why Regional Comparison is important� Comparison with local industry (Gas Suppliers)� Background of SO2 Comparison� Proposed Schedule for Two Comparison.� Price for participation� Coordinating Laboratory

Gas Metrology

Partially stable

StableCO, CO2, O2, propane

Natural gas (CH4)

© NMISA 2011

Partially stableSO2, NO, NO2, H2S, VOCs

and H2O

UnstableHCl, NH3, Ozone,

Formaldehyde

Gases

Partially stable

StableCO, CO2, O2, propane

Natural gas (CH4)

Stable in Cylinders

© NMISA 2011

Partially stableSO2, NO, NO2, H2S,

VOCs and H2O

UnstableHCl, NH3, Ozone,

Formaldehyde

Stable in Cylinders at High Concentrations

Dynamic Methods

Industry sector

© NMISA 2011

Green House Gases (GHG’s) Air pollution

Performance environment (Regulatory)

� The Kyoto Protocol for reducing greenhouse gas (GHG) emissions; South Africa acceded to the Kyoto protocol in mid 2002

� The National Air Quality Act No. 39 of 2004

� The Stockholm convention (a global treaty to protect human health and the environment); SA signed this treaty

© NMISA 2011

human health and the environment); SA signed this treaty in 2001

� Countries and trade regions impose regulations and directives to trade goods, protect the health of their people and the environment;

� Stricter legislation and the initiation of environmental programs are being applied globally

Gas Metrology Laboratory of the NMISA

� The NMISA is mandated to provide measurementtraceability for air pollution monitoring in SouthAfrica.

� NMISA has been identified by the Department of

© NMISA 2011

� NMISA has been identified by the Department ofEnvironmental Affairs to host the NationalReference Laboratory (NRL) for Air QualityManagement.

Gas Metrology Laboratory

Preparation and certification of Primary Reference Gas Mixtures (stack gas emissions, automotive exhaust emissions, ambient air monitoring)

Preparation and certification of Primary Reference Gas Mixtures (stack gas emissions, automotive exhaust emissions, ambient air monitoring)

© NMISA 2011

ambient air monitoring)ambient air monitoring)

Calibration of breathalysers, & air pollution analysers

Calibration of breathalysers, & air pollution analysers

Purity AnalysisPurity Analysis

Multi-component & Condensable gas mixtures

Multi-component & Condensable gas mixtures

PREPARATION STRATEGY OF GAS

STANDARDS

Gravimetric Preparation (ISO 6142:2001)

Verification of Primary Standard Gas Materials (PSMs) vs Other NMIs Mixtures (ISO 6143)

Pure Gases/Liquids (Purity Analysis)

© NMISA 2011

(PSMs) vs Other NMIs Mixtures (ISO 6143)

NMISA Certificates (PRGMs)

Verification of Primary References Gas Materials (PRGMs) vs PSMs

Gas Metrology Laboratory of the NMISA

� The NMISA is mandated to provide measurementtraceability for air pollution monitoring in South Africa.

� NMISA has been identified by the Department ofEnvironmental Affairs in South Africa to host the National

© NMISA 2011

Environmental Affairs in South Africa to host the NationalReference Laboratory (NRL) for Air Quality Management.

� NMISA (Gas metrology Lab) has participated in variousInternational Key Comparisons.

WHAT IS THE NEXT STEP!!!!!

Key Comparison with Other Key Comparison with Other NMI’s around the WORLDNMI’s around the WORLD

© NMISA 2011

Establishing international measurement

equivalence for gas metrology in SA

� In the beginning…�CCQM-K3.

EUROMET.QM-K3, APMP.QM-K3

�CCQM-K4, APMP.QM-K4, EUROMET. QM-K4

© NMISA 2011

�Today…�EURO.QM-K4.1�EURO.QM-S4

� CCQM-K52� CCQM-K53� CCQM-K51

CCQM-K3: Automotive emission gases

© NMISA 2011

CCQM-K4: Ethanol in air

© NMISA 2011

EURO.QM-K4.1: 120 µmol/mol

Ethanol in air

1.00

2.00

3.00

4.00

5.00

6.00

Deg

rees

of E

quiv

alen

ce

Euramet.QM-K4.1 Ethanol in Nitrogen

© NMISA 2011

-3.00

-2.00

-1.00

0.00

1.00

CEM INMETRO NMISA NPL VNIIM VSL

Deg

rees

of E

quiv

alen

ce

Laboratory

EURO.QM-S4: Preparative study for

automotive exhaust emissions

- 0 .1

0 .0

0 .1

0 .2

0 .3

0 .4

Deg

ree

of e

quiv

alen

ce (

mm

ol m

ol-1)

© NMISA 2011

IPQ

INM

ET

RO

VS

L

NM

ISA

SM

U

- 0 .4

- 0 .3

- 0 .2

- 0 .1

Deg

ree

of e

quiv

alen

ce (

mm

ol m

ol

L a b o r a to r y

CO results – 2 % mol/mol



- 0 .5

0 .0

0 .5

1 .0

1 .5

2 .0D

egre

e of

equ

ival

ence

(m

mol

mol

-1)

© NMISA 2011

INM

ET

RO

VS

L

NM

ISA

IPQ

SM

U

- 2 .0

- 1 .5

- 1 .0

- 0 .5

Deg

ree

of e

quiv

alen

ce (

mm

ol m

ol

L a b o r a to r y

CO2 results – 12 % mol/mol



- 5

0

5

1 0

1 5D

egre

e of

equ

ival

ence

(µ

mol

mol

-1)

© NMISA 2011

IPQ

VS

L

INM

ET

RO

NM

ISA

SM

U

- 1 5

- 1 0

- 5

Deg

ree

of e

quiv

alen

ce (

µm

ol m

ol

L a b o r a to r y

Propane results – 1000 µmol/mol

CCQM-K52: 360 µmol/mol CO2 in air

© NMISA 2011

CCQM-K51: 5 µmol/mol CO in nitrogen

0

1

2

3

4

Deg

rees

of e

quiv

alen

ce (

%)

CCQM-K51 Carbon monoxide in nitrogen

© NMISA 2011

-3

-2

-1

0

NM

IJ

NM

ISA

UB

A (

D)

VN

IIM

SM

U

NP

L

CE

RI

BA

M

CE

M

CE

NA

M

GU

M

INM

ET

RO

IPQ

JRC

KR

ISS

LNE

ME

TA

S

NIM

NIM

T

NIS

T

VS

L

NP

LI

FM

I

NM

IA

Deg

rees

of e

quiv

alen

ce (

%)

Laboratory

Some challenging key comparison.

�Challenges…�CCQM-P73�CCQM-K71�CCQM-K74, CCQM-P110�CCQM-K76

© NMISA 2011

�APMP.QM-K41

�CCQM-P28, BIPM.QM-K1

CCQM-P73: 30 to 70 µmol/mol

NO in nitrogen (Gravimetry)

-2.000

-1.000

0.000

1.000

2.000

3.000

mol

/mol

© NMISA 2011

-7.000

-6.000

-5.000

-4.000

-3.000

-2.000

KR

ISS

(M

1)

KR

ISS

(M

15)

CS

IR-N

ML

(M2)

CS

IR-N

ML

(M16

)

CE

RI (

M3)

CE

RI (

M14

)

VA

LCR

M1

(M4)

VA

LCR

M2

(M11

)

VA

LCR

M3

(M17

)

LNE

(M

5)

LNE

(M

19)

SM

U (

M6)

SM

U (

M18

)

CE

NA

M (

M7)

CE

NA

M (

M20

)

VN

IIM (

M8)

VN

IIM (

M22

)

NIS

T (

M9)

NIS

T (

M24

)

NM

IA (

M10

)

NM

IA (

M23

)

IPQ

(M

12)

IPQ

(M

25)

NM

i-VS

L (M

13)

NM

i-VS

L (M

21)

NP

L

NIS

T

NM

i-VS

L

BN

M-L

NE

KR

ISS

NR

LM*

NR

CC

RM

VN

IIM

OM

H

BN

M-L

NE

NP

L

VN

IIM

NM

i-VS

L G

UM

CE

M

ME

TA

S

CH

MI

FM

I

IPQ

Laboratory (cylinder)

D/ �m

ol/m

ol

CCQM-P73 (LIMAS 11UV analysis) CCQM-K1.c EUROMET-K1.c

CCQM-K71: Stack gas mixtures

© NMISA 2011

CO results – 40 ppm


© NMISA 2011

CO2 results – 12 % mol/mol


© NMISA 2011

Propane results – 6 ppm


© NMISA 2011

NO results – 80 ppm

CCQM-K74: 10 µmol/mol NO2 in

nitrogen

0.450

0.600

0.750

0.900

1.050

1.200

1.350

1.500

1.650

© NMISA 2011

-1.500

-1.350

-1.200

-1.050

-0.900

-0.750

-0.600

-0.450

-0.300

-0.150

0.000

0.150

0.300

D(µ

mol

/mol

)

Laboratory1 2 3 4 NMISA 6 7 8 9 10 11 12 13 14 15 16 17

WHY THIS REGIONAL COMPARISON IS IMPORTANT

�NMISA – Gas metrology as part of Gas Analysis WorkingGroup (GAWG) has a mandate to provide measurementtraceability to the air pollution monitoring industry.

�Environmental assets and natural resources that are wellprotected and continually enhanced (Monitoring Gases)

© NMISA 2011

�Designed to test the capabilities of the participants tomeasure the sulphur dioxide concentration levels at ambientand stack emission level. This will give evidence of thecalibration and measurement capability of the participantlaboratory for SO2.

�Strive to create a cleaner environment for all South Africansand contribute to a better and safer Africa and world

Background For Regional Comparison

� Sulphur dioxide (SO2) is a naturally occurring compound emitted from volcanoes andvarious industrial processes. This compound is regulated in many countries foremissions from point sources due to the link to acid rain.

� Reference gases of SO2 in air or nitrogen are used for the calibration of analysers usedto measure sulphur dioxide levels in ambient air and fixed sources (stacks) fromindustry.

� Sulphur dioxide is one of the most important substances in view of environmental andhuman health problems.

© NMISA 2011

� SO2 has been the subject of two prior CCQM key comparisons, CCQM-K1d (at 100µmol/mol and 1000 µmol/mol) completed in 1997, and CCQM-K26b (at 200 nmol/mol)completed in 2005.

� In 2009 the NMISA started to participate in international key comparisons for sulphurdioxide such as CCQM-K71 for stack gas mixtures, where sulphur dioxide was alsoincluded in the range of 20 to 200 µmol.mol-1.

� In 2010, the National Institute of Standards and Technology (NIST) in the USAcoordinated the international key comparison, CCQM-K76, for 100 µmol/mol SO2 innitrogen, where the NMISA also participated.

Proposed PT SCHEME/COMPARISON SCHEDULE FOR (50 to 70 µmol.mol -1 of SO 2 in nitrogen)

July 2011 Draft protocol to participating laboratory

August to September 2011 Registration of participant

October 2011 Preparation of gravimetric mixture + firstverification measurement (evaluation of short-term stability)

© NMISA 2011

October / November 2011 Shipment of cylinder to participating laboratory

November /December Start of comparison

20th January 2012 Report due to coordinating laboratory

20th January 2012 Cylinders due to coordinating laboratory

February 2012 Second verification measurement

March 2012 Final report

Proposed PT SCHEME/COMPARISON SCHEDULE FOR (800 to 850 µmol.mol -1 of SO 2 in nitrogen)

December 2011 Draft protocol to participating laboratory

January/February 2012 Registration of participant

March / April 2012 Preparation of gravimetric mixture + firstverification measurement (evaluation of short-term stability)

May / June 2012 Shipment of cylinder to participating laboratory

© NMISA 2011

May / June 2012 Shipment of cylinder to participating laboratory

June /July 2012 Start of comparison

End August 2012 Report due to coordinating laboratory

End August 2012 Cylinders due to coordinating laboratory

September 2012 Second verification measurement

October 2012 Final report

PRICE FOR COMPARISON

� Gas TAF delegates wanted us to prepare one sample, Cylinder move from one participant to another.

� Challenge: Contaminations.

� It was agree that the comparison must be R7500 per cylinder.

� Some company ask if its possible to get the cylinder

© NMISA 2011

� Some company ask if its possible to get the cylinder back to them as a Primary Reference Gas Mixture (Cost:R8500)

� Price include shipping to and from participants and renting for those who want cylinder back as PRGM.

� Time frame includes: (preparation + First & Second Verification / Analysis, Stability)

Coordinating Laboratory

� Coordinating Laboratory: Gas Metrology of National Metrology institute ofSouth Africa (NMISA)

� Field: Amount of Substance

� Subject : Sulphur Dioxide (SO2) in Nitrogen at 50 to 70 µmol/mol for theambient air monitoring and 800 to 850 µmol.mol-1 for stack gas emissions

© NMISA 2011

2ambient air monitoring and 800 to 850 µmol.mol-1 for stack gas emissionsmonitoring.

� Study co-ordinator : James Tshilongo (email: [email protected])

inter laboratory comparisons for sulphur dioxide in …...performanceenvironment(regulatory) the...

Documents