qualimetry in spectrochemical...

QUALIMETRY IN

SPECTROCHEMICAL

ANALYSIS

Quality control on analytical laboratory

V. KmetovUniversity of Plovdiv, BULGARIA

EuRopean Community Action Scheme for the Mobility of University Students)

Academic exchange

University of Alicante,

March 2015

V. Kmetov, Alicante 2015

LONG AND FRUITFUL PARTNERSHIP

TEMPUS S_JEP12451-97



ERASMUS MOBILITY

Plovdiv –> Alicante - 24 Students

Alicante -> Plovdiv – 2 Student

Alicante –> Plovdiv - 7 professors + 2 admin.

Plovdiv –> Alicante - 7 professors + 1 Rector


GGGreen

AAAnalytical

MMMethods

AAAcademic Centre

http://gama.argon.uni-plovdiv.bg/

National Science Found of Bulgaria

INTIGRATED RESEARCH CENTRES AT THE

UNIVERSITIES

UNIVERSITY CENTRE FOR DEVELOPMENT OF

GREEN CHEMISTRY METHODS FOR TRACE

ANALYSIS OF ENVIRONMENTAL OBJECTS



Prof. Dr. Antonio Canals – DOCTOR HONORIS CAUSA

OF THE UNIVESRITY OF PLOVDIV “Paisii Hilendarski”


QUALIMETRY IN

SPECTROCHEMICAL

ANALYSIS

Quality control on analytical laboratory

V. KmetovUniversity of Plovdiv, BULGARIA

EuRopean Community Action Scheme for the Mobility of University Students)

Academic exchange

University of Alicante,

March 2015


1.The new trends in the global economy and

the needs of measurements with demonstrated quality

- Basic motivations of this course

- Qualimetry - as a tool for estimation of the results reliability

2. Validation of the measurement procedure

- method performance characteristics

- verification of fit-for-porpoise relevance

- EXCEL models for computing the quantities

of the characteristics

3. Uncertainty budget calculation in spectrochemical measurements

Kragten approach- constructing by EXCEL

4. Practical examples – training in EXCEL

HEADLINES three lectures + one practice


All here starts with the question:

What is a QUALITY ?

QUALITY –

the characteristics of a product or

service that bear on its ability to

satisfy stated or implied needs

ISO8402 1994 Quality Measurement and Quality

Assurance - Vocabilary

The ability of the qualitative (analyte identification)

and quantitative (accuracy, precision) data to satisfy

the requirements of their purpose


QUALIMETRY – what is it ?

- a part of the metrology science dealing with

quality estimation of the measurements and tests, including the

QUALITY OF THE INFORMATION provided from chemical analysis.

Systems for quality assurance and management

of the chemical analysis

Statistical tools for performance evaluations

andcomputing of the

estimators

This lecture will show how to create and apply algorithms supporting the process of

quality assessment.


“The analytical chemistry is a metrologicaldiscipline, which develops, optimizes and

applies processes of measurement, aiming to

receive reliable (bio-)chemical informationfrom global and certain kind from natural and

artificial objects or systems, for solving

analytical problems that arrived from the

informational needs”

Analytical Chemistry

II edition (2004 г.)

DEFINITION

Can we measure correctly ?

Is this the true result ?


Does the TRUE value

EXIST ?!Let each of you show how many

YELOW coins has got just now ?

The winner who has the maximum

score will receive

Bulgarian rose oil premium!

What is the number ?

Particularity?

CONVENTION!

Metrology - science of measurement and its

application

NOTE Metrology includes all theoretical and practical aspects of measurement,

whatever the measurement uncertainty and field of application

VIM (2012) (2.2)

Metrological aspects are part of any measurement even the simplest one

Metrology in chemistry (MiC)is metrology applied to chemical analysis

The main goal of metrology is to prevent the problems between

people in the process of quantity characterization !!

UNCERTAINTY - a parameter associated with the result of a measurement, that characterises

the dispersion of the values that could reasonably be attributed to the measurand

Non-negative parameter characterizing the dispersion of the quantity values being

attributed to a measurand, based on the information used

International Vocabulary of Basic and General Terms in Metrology


TrainMiCTra in in g in Me t ro log y in Ch e m is t ry

TrainMiC is organised and conducted by

JRC-IRMM as a common international

information platform to be used as a tool for

the education in metrology in chemistry.


www.bipm.org/utils/.

../jcgm/JCGM_200_2012.pdf

http://www.cem.es/sites/default/files/vim-cem-2012web.pdf


http://www.erm-

crm.org/ERM_products/application_notes/application_note_1/D

ocuments/erm_application_note_1_spanish_rev3.pdf


UNCERTAINTY

Every PROCESS predetermines a PRODUCT

Every PRODUCT possess characteristics – qualities

Every quantitatively defined characteristics can be measured

the total uncertainty:

Dispersion of the product characteristics

+

Dispersion of the measurement procedure

_____________________________________________________

= total dispersion -> UNCERTAINTY

Result = Value ± Uncertainty (units)

a parameter associated with the result of a measurement, that characterises

the dispersion of the values that could reasonably be attributed to the measurand

Non-negative parameter characterizing the dispersion of the quantity values

being attributed to a measurand, based on the information used

International Vocabulary of Basic and General Terms in Metrology

there is a change in the treatment

of measurement uncertainty from

an

Error Approach (sometimes

called Traditional Approach or True

Value Approach)

to

an Uncertainty Approach


..from an Error Approach (Traditional or True

Value Approach) to an Uncertainty Approach..

The objective of measurement in the Error Approach

is to determine an estimate of the true value that is

as close as possible to that single true value. The

deviation from the true value is composed of random

and systematic errors.

… The objective of measurement in the Uncertainty

Approach is not to determine a true value as closely

as possible. Rather, it is assumed that the information

from measurement only permits

assignment of an interval

of reasonable values to the measurand,

based on the assumption that no mistakes have been

made in performing the measurement. Joint Committee for

Guides in Metrology


Do you believe,

that one table spoon of water contains

more water molecules

than spoons of water into the ocean ?

OCEAN (volume) = 𝟏. 𝟑 𝟏𝟎𝟗 𝒌𝒎𝟑 = 𝟏. 𝟑 𝟏𝟎𝟗x 𝟔. 𝟔𝟕 𝟏𝟎 𝟏𝟑 spoons = 𝟖. 𝟔𝟕 𝟏𝟎𝟐𝟐 spoons

𝑯𝟐𝑶 𝒊𝒏𝒕𝒐 𝒕𝒉𝒆 𝑶𝑪𝑬𝑨 𝑵 = 𝟗 𝟏𝟎𝟐𝟐 spoons

𝟏𝒎𝒐𝒍 𝑯𝟐𝑶 = 𝟔. 𝟎𝟐𝟐 𝟏𝟎𝟐𝟑 H−O−H = 𝟏𝟖. 𝟎𝟏𝟓𝟑 𝒈

1 spoon = 𝟏𝟓 𝒈 =𝟏𝟓

𝟏𝟖𝒈 = 𝟎. 𝟖𝟑 mol

1 table spoon = 𝟎. 𝟖𝟑 x 𝟔. 𝟎𝟐𝟐 𝟏𝟎𝟐𝟑 H−O−H = 5 𝟏𝟎𝟐𝟑 H−O−H

1 table spoon = 50 𝟏𝟎𝟐𝟐 H−O−H / 2

x 2


How to GUARANTEE

reliability of the measurement result

Standartirized

MethodsValidated

Methods

THE TRUST

Fully documented

measurement procedure

by a transparent, clear

and standartirized

approach

Conformation trough

examination of a given item

and provision of objective

evidence that it fulfils the

requirements for a stated

intended use (VIM 2.28)


http://www.eurachem.org/


ONCE MEASURED

ACCEPTED EVERYWHERE

the Mutual Recognition Arrangement


http://eur-lex.europa.eu/

V. Kmetov, Alicante 2015Regional coordiantor

42

47

52

57

62

67

72

77

82

87

92

97

102

107

112

117

122

c

nm

ol·

L-1

-50

-40

-30

-20

-10

0

10

20

30

40

50

De

via

tio

n f

rom

mid

dle

of c

ert

ifie

d r

an

ge

in

%

IMEP- 9 : Trace elements in Water

Certified range (±U =2u c): 81.0 - 85.4 nmol·L-1

Cd

Results from all laboratories.

3 'less than' values6 values below -50%

20 values above 50%

± 10%


the ANALYSIS IS COMPARISON

MEASURAND (C) Signal

uncertainty

St1Х1 St1 Y1

Sample Х Sаmple Y

St2Х2 St2 Y2

St3Х3 St3 Y3

Interference exists if:

)(XfY

mxSt ff

uncertainty


the ANALYSIS IS COMPARISON

Interference exists if:

mxSt ff


REGULATIONShttp://ec.europa.eu/food/food/rapidalert/docs/rasff_annual_report_2012_infogra

ph_en.pdf


Interlaboratory comperisons

PU and Komihris

ICP-OES

ICP-OES ICP-MS ppb In SOLUTION2.6 2.8 Cd Sunflower seed 1

0.89 1.0 Cd Sunflower seed 24.3 5 Cd Bread49 51 Cu Sunflower seeds 175 81.0 Cu Sunfower seeds 236 39.5 Cu Bread

174 164 Zn Sunflower seed 1245 243.0 Zn Sunflower seed 2110 115 Zn Bread

Y Rh IS

Sensitivity Drift

< 5 % < 5 %

ICP-MS


22

'

labPT

PTlab

SS

XXZ

PT estimation,

ІZ’І 2 excellent

2< ІZ’І 3 satisfied

ІZ’І >3 unsatisfied

ICP-MS ICP-MS

Interlaboratory comparisons

PU and Alimenti


ICP-MS

PT

PTlab

S

XXZ

Interlaboratory comparison

PU and Alimenti


The role of measurement

uncertainty in:

1. Repeatability and reproducibility limits

assessment

2. Accuracy assessment by using CRM

3. Conformity assessment

4. Maximum standard measurement

uncertainty (Uf).


rXX 21

rrrrrr SSSSSuuuU 82.2)41.1(222222 2222

2

2

1

rr uUr 2

Applying к=2 for P = 95%



uncertainty in:


assessment




uncertainty (Uf).


Accuracy estimation

CRMmm CC 22

CRMm uuu uU 2<

To evaluate the method accuracy one could compare the difference between

the Cm measured and the certified CCRM

The obtained Δm have to be compared with the UΔ:

if Δm ≤ UΔ,

there is no significant difference between the measured result and certified value


ACCURACY ASSESSMENT



uncertainty in:


assessment




uncertainty (Uf).


References

http://www.eurachem.org/index.php/pub

lications/guides/uncertcompliance

JCGM 106:2012 - Conformity

assessment is any activity undertaken

to determine, directly or indirectly,

whether

a product, process, system, person or

body meets relevant standards and

fulfills specified requirements.


Conformity assessment



uncertainty in:


assessment




uncertainty (Uf).


2

2

)1.0(2

CLOD

U f


Horwitz TRUMPET


Regulation 333

2

2

)1.0(2

CLOD

U f


Maximum standard

measurement

uncertainty (Uf).


The analyst must know:

CHEMISTRY

Normative and regulations

StatisticsMathematical

modeling

METROLOGYInstrumental

analysis


QUALIMETRY – what is it ?


http://web.ua.es/en/actualidad-universitaria/2015/marzo2015/marzo2015-9-15/la-universidad-bulgara-de-plovdiv-utilizara-el-campus-de-la-ua-como-

modelo.html


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welcome in

Bulgaria !

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