Claudio Carbonec.carbone@consorzioproambiente.it

InterCinD annual meeting

Area della Ricerca CNR Bologna, 24 Maggio 2019

InterCinD 7:

Un Proficiency Test accreditato ISO

17043

Vecchi, nuovi e potenziali futuri inquinanti: quali sono

oggi le azioni e i controlli mirati alla salvaguardia

dell’ambiente e della salute?

History: since 2000 …

1° Cind

2001 20192013

1° Intercind

2015

+ +

2008

InterCinD77° Cind 3° InterCinD

Accreditated PT

PTP0007

ISO/IEC 17043

Accreditated

for POPs

PTP0007

ISO/IEC 17043

Accreditated

for Pesticides

2016

PTP0007

ISO/IEC 17043

New Team, New RMs

History: since 2000 …

1° Cind

2001 20192013

1° Intercind

2015

+ +

2008

InterCinD77° Cind 3° InterCinD

Accreditated PT

PTP0007

ISO/IEC 17043

Accreditated

for POPs

PTP0007

ISO/IEC 17043

Accreditated

for Pesticides

2016

PTP0007

ISO/IEC 17043

New Team, New RMs

New Schemes

IT; 15

EU; 28EXEU;

43

2018IT; 10

EU; 21EXEU; 35

2017

IT; 14

EU; 32

EXEU; 38

2016

History: since 2000 …

1° Cind

2001 20192013

1° Intercind

20152008

InterCinD77° Cind

PCDD/F

PCDD/F

PCBs dioxin-like

PCBs ICES-6

PAHs

PBDE

Heavy metals

PCDD/F

PCBs dioxin-like

PAHs

PCDD/F

PCBs dioxin-like

PCBs ICES-6

PAHs

PBDE

Sediment Sediment

Fly Ashes

Food/feed

Sediment

Fly Ashes

History: since 2000 …

1° Cind

2001 20192013

1° Intercind

20152008

InterCinD77° Cind

PCDD/F

PCDD/F

PCBs dioxin-like

PCBs ICES-6

PAHs

PBDE

Heavy metals

PCDD/F

PCBs dioxin-like

PAHs

PCDD/F

PCBs dioxin-like

PCBs ICES-6

PAHs

PBDE

Sediment Sediment

Fly Ashes

Food/feed

Sediment

Fly Ashes

new PT schemes are coming …

PTP 0007 ACCREDIA

Statistical data treatment in InterCinD is INSPIRED by ISO 13528/2015 and IUPAC Guidelines

The interlaboratory circuit is organized in agreement with international guidelines relative to the organization and management of interlaboratory circuits UNI CEI EN ISO/IEC 17043: 2010

PTP 0007 ACCREDIA

Statistical data treatment in InterCinD is INSPIRED by ISO 13528/2015 and IUPAC Guidelines

Peculiarities of INTERCIND1) Natural matrixes (unknown concentration)

The interlaboratory circuit is organized in agreement with international guidelines relative to the organization and management of interlaboratory circuits UNI CEI EN ISO/IEC 17043: 2010

3 different samples of “natural” matrixes:

1) Environmental: Natural Sediment (SEDIMENT)

2) Industrial: ash (ASH)

3) Food/feed

PTP 0007 ACCREDIA

Statistical data treatment in InterCinD is INSPIRED by ISO 13528/2015 and IUPAC Guidelines

Peculiarities of INTERCIND1) Natural matrixes (unknown concentration)

The interlaboratory circuit is organized in agreement with international guidelines relative to the organization and management of interlaboratory circuits UNI CEI EN ISO/IEC 17043: 2010

Every sample was send in 3 different jars 3 different analysis (replicates)

were requested to check laboratory reproducibility. Analysis of:

- dioxins and furans (PCDD/F) [17] - PCBs dioxin-like [12]

- PCBs ICES-6 [6] - PAHs [7]

- PBDE [28] - Heavy metals [14]

CONGENERS = 84!

PTP 0007 ACCREDIA

Statistical data treatment in InterCinD is INSPIRED by ISO 13528/2015 and IUPAC Guidelines

Peculiarities of INTERCIND1) Natural matrixes (unknown concentration)

2) Replicates (accuracy&precision)

3) Statistical treatment (Determination of extremes and outliers with non-parametric method)

The interlaboratory circuit is organized in agreement with international guidelines relative to the organization and management of interlaboratory circuits UNI CEI EN ISO/IEC 17043: 2010

Water Monitoring - Main issuesInterCinD procedure

Data from

Labs

Form not

filled in

properly?no

yes

InterCinD input

form

Firs check

InterCinD statistical approach

Water Monitoring - Main issuesInterCinD procedure

Data from

Labs

Form not

filled in

properly?no

yes

Valid

data

Data

removed

no

yes

InterCinD input

form

If yes, use

mean

no

no

yes

no no

Assigned

value and its

uncertainty

Data outlier

or extreme?

Simmetry

of data?

Kernel

assessmen

t

If yes, use

median

Nlab>12 RSD%<55

%

outliers +

extremes

<20%u<0.3σp

yes

Firs check

yes

TEST2 TEST1 TEST1b TEST1b TEST3

Statistical

analysis of the

treated dataset

InterCinD statistical approach

MEAN or

MEDIAN

No

assigned

value

no

No

assigned

value

n

SMx

j

jj −

Statistical analysis is performed on

the dataset reporting the averaged

value of the three replicates for every

chemical species/index and lab

Water Monitoring - Main issuesInterCinD procedure

Data from

Labs

Form not

filled in

properly?no

yes

Valid

data

Data

removed

no

yes

InterCinD input

form

If yes, use

mean

no

no

yes

no no

Assigned

value and its

uncertainty

Data outlier

or extreme?

Simmetry

of data?

Kernel

assessmen

t

If yes, use

median

Nlab>12 RSD%<55

%

outliers +

extremes

<20%u<0.3σp

yes

Firs check

yes

TEST2 TEST1 TEST1b TEST1b TEST3

Statistical

analysis of the

treated dataset

InterCinD statistical approach

MEAN or

MEDIAN

No

assigned

value

no

No

assigned

value

n

SMx

j

jj −

Statistical analysis is performed on

the dataset reporting the averaged

value of the three replicates for every

chemical species/index and lab

Water Monitoring - Main issuesInterCinD procedure

Data from

Labs

Form not

filled in

properly?no

yes

Valid

data

Data

removed

no

yes

InterCinD input

form

If yes, use

mean

no

no

yes

no no

Assigned

value and its

uncertainty

Use σp

22' psp s +=

yes

no

The final step is the

EVALUATION OF

PERFORMANCE

on the entire

dataset including

replicates

Precision (r-range)

Accuracy (z-score)

Data outlier

or extreme?

Simmetry

of data?

Kernel

assessmen

t

If yes, use

median

Nlab>12 RSD%<55

%

outliers +

extremes

<20%u<0.3σp

yes

Firs check Ss<= 0.3

σp

Homogeneity (and

stability) assessment

yes

TEST2 TEST1 TEST1b TEST1b TEST3

Statistical

analysis of the

treated dataset

InterCinD statistical approach

MEAN or

MEDIAN

No

assigned

value

no

No

assigned

value

n

SMx

j

jj −

Statistical analysis is performed on

the dataset reporting the averaged

value of the three replicates for every

chemical species/index and lab

Water Monitoring - Main issuesDetermination assigned value

from: Piotr Robouch (JRC) - 9th International Workshop on Proficiency Testing (9-12 October 2017,

Portoroz, Slovenia)

SEDIMENT

PCDD/F PCB-DL PCB-ICES PAH PBDE HM

SEDIMENT

PCDD/F PCB-DL PCB-ICES PAH PBDE HM

SEDIMENT

PCDD/F PCB-DL PCB-ICES PAH PBDE HM

SEDIMENT

PCDD/F PCB-DL PCB-ICES PAH PBDE HM

SEDIMENT

PCDD/F PCB-DL PCB-ICES PAH PBDE HM

SEDIMENT

PCDD/F PCB-DL PCB-ICES PAH PBDE HM

2,3,4,7,8-PeCDF

1,2,3,7,8,9-HxCDF

SEDIMENT

2,3,4,7,8-PeCDF

1,2,3,7,8,9-HxCDF

44

42

SEDIMENT

2,3,4,7,8-PeCDF

1,2,3,7,8,9-HxCDF

44

42

OK!

KO!

Sediment: z-scores (accuracy)

Sediment: r-range (precision)

FLY ASHES

Lab num. Simmetry test kernel outliers < 20% & RSD<55% u<0.3S

Test1 Test2 Test2b Test 1b Test3 Final

2,3,7,8-TeCDD Y N median Y Y Y

1,2,3,7,8-PeCDD Y Y median N Y Y

1,2,3,4,7,8-HxCDD Y N median N Y Y

1,2,3,6,7,8-HxCDD Y N median N Y Y

1,2,3,7,8,9-HxCDD Y Y median N Y Y

1,2,3,4,6,7,8-HpCDD Y N median N Y Y

OCDD Y N median Y Y Y

2,3,7,8-TeCDF Y N median Y Y Y

1,2,3,7,8-PeCDF Y N median Y Y Y

2,3,4,7,8-PeCDF Y N median Y Y Y

1,2,3,4,7,8-HxCDF Y N median Y Y Y

1,2,3,6,7,8-HxCDF Y N median Y Y Y

1,2,3,7,8,9-HxCDF Y N median N Y Y

2,3,4,6,7,8-HxCDF Y Y median N Y Y

1,2,3,4,6,7,8-HpCDF Y N median Y Y Y

1,2,3,4,7,8,9-HpCDF Y N median Y Y Y

OCDF Y Y Y Y Y

TEQ (PCDD/F) Y N median Y Y Y

TEQ (PCDD/F) Upperbound (UpB) Y N median Y Y Y

Weight Analysed (g):

PCB #77 Y Y median N N N

PCB #81 N Y N N N

PCB #105 Y N median N N N

PCB #114 N N N N N

PCB #118 Y Y median Y Y Y

PCB #123 N N N N N

PCB #126 Y Y Y Y Y

PCB #156 Y Y median Y N N

PCB #157 Y N median Y N N

PCB #167 N Y N N N

PCB #169 Y N median Y N N

PCB #189 Y N median N N N

TEQ (PCB) Y Y median N Y Y

TEQ (PCB) Upperbound Y Y median N Y Y

TEQ Total (PCDD/F+PCB) Y N median N N N

TEQ Total (PCDD/F+PCB) UpB Y N median Y N N

Test 1) Minimum number of

valid data 12 (from min 12

different labs)

Fly ashes: z-scores (accuracy)

Fly ashes: r-range (precision)

Water Monitoring - Main issuesComparing methods

Data synthetically generated: n=150; µ = 1; σ = 0.2

Water Monitoring - Main issuesComparing methods

SEDIMENT: 123789HxCDF

Grazie e buon appetito!

Claudio Carbone

c.carbone@consorzioproambiente.it

www.consorzioprombiente.it