French Inter-laboratories campaigns Context and finality

© Ce document est la propriété de l ’INERIS formation. Il ne peut pas être reproduit ou exploité sans son accord - 2006

French Inter-laboratories campaigns

Context and finality

© Ce document est la propriété de l ’INERIS formation. Il ne peut pas être reproduit ou exploité sans son accord - 2006 2/20

Context

Arrêté du 04 septembre 2000 (agrément des organismes de contrôle)

“agréments” are issued to laboratories performing sampling that

• have been accredited (programme n°97 COFRAC or equivt)

• agree to participate to interlaboratory campaigns of 3 days organized at INERIS at least once every 3 years on the bench and every year for the analytical comparisons.


Finality of the tests on the bench• To follow and improve the quality of implementation of SRM

through the evolution of Confidence intervals of reproducibility, compared to those required by EN standards,

information and training for new EN standards (comparisons of measuring devices, of results).

• Judgment of the capacity of the laboratories conformity of measuring devices and of the implementation through audits, test of knowledge of standards,

comparison of results / Caverage...

==> - the results of these tests are evaluated by the commission in charge of delivering “agréments” to the laboratories. - the synthesis report which enlightens slips of each laboratory in implementation of the SRM may be audited by the accreditation body.


The bench


Specificity of the tests on the bench

The totality of the method is involved (sampling + analysis)

Generation of real flue gases in order to be under real conditions of operation (matrix, temperature, moisture).

Means: generation of combustion gases, doped by additions of pollutants ignorance of the generated exact concentration

Advantages: • Possibility to simulate different types of gases (LCP, WI) • provide real data and uncertainties at different level of

concentrations Drawbacks:

• true value unknown _ comparisons of the results with the average value given by the participants

• limited number of participants ==> use of statistics limited


Capacity criteria

• Respect of QA/QC procedures and associated criteria field blank Leak test absorption efficiency

• Respect of standardised procedures list of key points check of provisions (written procedures, forms) check of application


Inter-laboratories tests

Approach in the field leads to determination of the fidelity of the method characterised by a standard deviation or a repeatability or reproducibility confidence interval ==> see ISO 5725-2

Sampledgases

Sampledgases

lab A

lab A

lab A

lab A

lab B

lab C

Type uncertainty

sr

"repeatability"

Type uncertainty

sR

"reproducibility"



Flue gaseslab B - 1

lab B - 2

lab D - 1

lab D - 2la

b C

- 1

lab

C -

2

lab

A -

1

lab

A -

2



Results of the 26 first campaigns obtained with accredited laboratoriesThey relates to :

automatic analysis of O2 (5-13%), CO2, CO (10 à 500 mg/m3), NOx (75 à

1000 mg/m3), SO2 (40 à 1000 mg/m3) et COVT (0 à 50 mgC/m3)

and from the 7th campaign on manual methods for HCl, HF, Hg and at last on H2O.

From the 9th campaign participants are accredited and consequently EN standards should be applied.



Maximum value of confidence interval

fixed by directives

Target value for thereproducibility confidence

interval : t.s R

O2 - ±6 %

CO ±10 % ±5 %

SO2 ±20 % ±10 % *

NOx ±20 % ±10 %

COVT ±30 % ±15 %

HF and HCl ±40 % ±20 %

Hg - 25%

dust ±30 % ±15 %

* impossible to reach due to the manual method


Analytical inter-laboratories tests

compound concentration sr average % sR % ICR %

HF 2,1 mg/m3n 2,7 26,5 53,0

4,7 mg/m3n 2,9 18,1 36,2

HCl 20,6 mg/m3n 1,1 6,5 13,0

102,3 mg/m3n 0,9 4,3 8,6

SO2 75,7 mg/m3n 1,1 14,1 28,2

214,7 mg/m3n 1,0 3,5 7,0

Hg 43,3 µg/m3

4,8 13,8 27,6130,0 µg/m

32,5 12,7 25,4

sr: repeatability standard deviation

sR: reproducibility standard deviation

ICR : : reproducibility confidence interval


Analytical inter-laboratories tests

Compound Average

X

(µg/g)

RS absolute val

(µg/g)

RS relative val

%

CRI

relative val

%

Arsenic 2346 788 33,6 67,2

Cadmium 421 47 11,2 22,4

Cobalt 4065 264 6,5 13

Chromium 410 531 120 240

Copper 5573 416 7,5 15

Manganese 4425 356 8,0 16

Nickel 4688 411 8,8 17,6

Lead 8543 878 8,2 16,4

Antimony 8102 604 7,5 15

Tin 103 66 63,9 127,8

Thallium 451 190 42,2 84,4

Vanadium 3623 280 7,7 15,4

Tableau 2 : statistics values– heavy metals in dust


Analytical inter-laboratories testsCompound Average

X

(µg/l)

RS absolute val

(µg/l)

RS * relative val

%

CRI

relative val

%

As 101 21 20,6 41,2

Cd 19 2 8,3 16,6

Co 176 10 5,8 11,6

Cr 158 11 6,7 13,4

Cu 186 10 5,5 11

Mn 168 7 3,7 7,4

Ni 192 13 6,8 13,6

Pb 388 26 6,6 13,2

Sb 374 40 10,6 21,2

Sn 355 71 20,0 40

Tl 17 4 20,6 41,2

V 153 10 6,5 13

Tableau 3 : statistics values - low concentrations solutions


Analytical inter-laboratories testsCompounds Target value

µg/gAverage

X(µg/g)

Recovery rate

%Arsenic 3020 2346 77,7

Cadmium 520 421 81,0

Cobalt 4480 4065 90,7

Chrome 2690 410 15,2

Copper 6310 5573 88,3

Manganese 4920 4425 89,9

Nickel 5390 4688 87,0

Lead 10150 8543 84,2

Antimony 9190 8102 88,2

Tin 7250 103 1,4

Thallium 690 451 65,4

Selenium 7009 2082 29,7

Tellurium 6205 1082 27,4

Zinc 27478 25316 92,1

Vanadium 4050 3623 89,5

Table 4 : statistics values– digestion efficiency


Inter-laboratories tests O2 and CO2

Ic reference Ic average Ic 2005 Ic avrIcref Ic2005/IcrefO2 0,9 4,2 1,7 5,0 2,0CO2 4,0 3,8

Target value for O2 and CO22 : 6%Target reached in 2005 for 4 campaigns out of 4 for O2:: 2,75 / 0,45 / 1,9 / 1.7 improvement Target reached

Target reached in 2005 for 4 campaigns out of 4 for CO22: 3,7 / 5,05 / 4,4 / 2,2 Stability Target reached

2

0123456789

101112131415

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

Number of campaigns

I

C

%

O2 4-13%

CO2 4-10%


Inter-laboratories testsNOx

Ic reference Ic average Ic 2005 Ic ave/Icref Ic 2005/Icref

NOx 80-1000mg/m3

2 11,1 11,9 5,5 6,0

Target for NOx : 10 %Target reached in 2005 2 times : 10 / 11,2 / 19,3 / 7,2 Light improvement Target reached at 50%

Improvements to be brought :respect warm up time of the analysersLeak testsContrôle of driftscontrôle of converter (efft > 95 %)Losses of NO2

05

101520253035404550

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

Number of campaigns

I

c

%

NOx 80-1000mg/m3


Inter-laboratories testsCO and TOC

Ic reference Ic average Ic 2005 Ic av/Icref Ic 2005/Icref

CO 30-500mg/m3

3,1 15,1 5,2 5,0 1,7

CO 10-30mg/m32,4 50,9 43,5 21,2 18,1

TOC 5-40mgC/m336,2 36,8

Target for CO : 5%Target reached 2 timesout of 4 in 2005 : 7,9 / 5,7 / 4,3 / 2,7 Improvement Target reached at 50%

Target for TOC : 15%Target not reached in 2005 : 20,9 / 46,4 / 42,9 / 37 Improvement Target not reached

)

020406080

100120140160180200

0 1 2 3 4 5 6 7 8 9 10111213141516171819202122232425262728

Number of campaigns

I

c

%

CO 30-500mg/m3

TOC 5-40mgC/m3

CO 10-30mg/m3


Inter-laboratories testsH2O

Ic reference Ic average Ic 2005 Ic av/Icref Ic 2005/Icref

H2O % 20 23,6 19,1 1,2 1,0

Target for H2O : 20 %Target reached in 2005 1 time out of 4 : 12 / 20,2 / 20,6 / 23,4 Improvement Targetr reached at 25%

Improvements to be brought :Leak testGlobal weighing of the whole water capture system with a balance of 0,1g precisionHeating of the sampling line

2

05

101520253035404550

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

Number of campaigns

I

c

%

H2O %


Inter-laboratories testsSO2 , HCl and HF,

Ic reference Ic average Ic2005 Ic moy/Icref Ic2005/Icref

SO2 70-300mg/m310 41,5 32,1 4,1 3,2

HF 5mg/m3

30 75,4 29,9 2,5 1,0HCl 40mg/m3

5 43,1 34,2 8,6 6,8

Target for SO 2 3 : 20 %

Target not reached in 2005 : 43,5 / 39,8 / 21,4 / 23,8 Improvement Target not reached

Ic analytique 2002 : 29,8 % at 76 mg/m3 and11 % at 212 mg/m

3

Target for HCl : 20 %Target not reached in 2005 : 25 / 40 / 50 / 30 Light improvement Target not reached

Ic analytique 2002 at 20 mg/m3 : 13 %

Target for HF pour 5 mg/m 3 : 20 %Target not reached in 2005 : 25 / nd / 52 / 29 Improvement Target not reached

4 2

0102030405060708090

100110

4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

Number of campaigns

I

c

%

HF 1-20mg/m3

HCl 40mg/m3

SO2 70-300mg/m3


Inter-laboratories testsHg

Ic reference Ic average Ic 2005 Ic ave/ Icref Ic 2005 /Icref

Hg 40-100µg/m 325 63,0 94,2 2,5 3,2

Target for Hg : 20 %Target not reached in 2005 : 90 / 52,6 / 140 / nd No improvementIc analytique 2002 : 27,6 to 29,4%

0102030405060708090

100

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28

Number of campaigns

Icin%

Hg 40-100µg/m3

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French Inter-laboratories campaigns Context and finality

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