Universität Stuttgart

Proficiency Testing in Analytical Chemistry

Current Practice and Future Directions
Michael Koch, Frank Baumeister, Jörg W. Metzger
Institute for Sanitary Engineering, Water Quality and Solid Waste Management, Dept. Hydrochemistry

Proficiency Testing (PT) by Statistical Evaluation and Assessment

Interlaboratory Comparison
• Samples are sent out to various laboratories for concurrent
testing
• To get an indication of the performance of the individual la-
boratories
• Help for the laboratory to improve its quality
• Can be used by customers or regulatory bodies for the se-
lection of qualified laboratories
• For laboratories accredited to ISO 17025 participation in
PT schemes is obligatory
Standards and Guidelines for PT
• ISO Guide 43 (1996): Proficiency testing by interlaboratory
comparisons (currently under revision to ISO/IEC 17043)
• IUPAC, ISO, AOAC (2006): The International Harmonized
Protocol for the Proficiency Testing of Analytical Chemistry
• Robust statistical methods are used for the estimation of
mean and standard deviation
• Consensus mean is used as assigned value
• Modified z-scores are used for the assessment
x = laboratory result
x−X
z= X = assigned value
σˆ
σˆ = standard deviation for proficienc y assessment
• Modification with factors k1 and k2, different for values be-
low and above assigned value to overcome problems with
skewed distribution for low values → zU-score
• Standard deviation for proficiency assessment is mainly ba-
sed on the calculated value from the dataset, but with limi-
tations and, if possible, smoothed with a variance function
• Values with |zU| ≤ 2 are judged as satisfactory
35

Laboratories
• ILAC (2000): G-13 Guidelines for the requirements for the 30

competence of providers of proficiency testing schemes

rel. standard deviation in %

calculated standard deviation

• ISO 13528 (2005): Statistical methods for the use in profici- 25
ency testing by interlaboratory comparisons upper limit
20

limited value variance function sˆ Ri = e Θ0 + Θ1⋅ln ci

AQS Baden-Württemberg –
15
standard deviation used for proficiency assessment

Largest Water PT Scheme in Germany 10

• started in 1987 5
lower limit
• PT for wastewater, drinking water and groundwater ana-
lyses 0
1 2 3 4 5 6 7 8
• For chemical laboratories and wastewater treatment concentration in mg/l
plant (WWTP) laboratories
Uncertainty in PT
Drinking Water PT Rounds The uncertainty is a parameter that characterises the dispersi-
1 BrO3-, F-, NO3-, NO2-, Cl-, SO42-, P, CN-, turbidity on that could reasonably be attributed to the value.
2 Cr, Cu, Pb, Cd, Ni, CrVI The value is expected to lie within this range with a certain
3 Al, Fe, Mn, Na, K, color probability
4 Conductivity, oxidisability, TOC, Se, Sb, As
5 B, Ca, Mg, Hg, NH4+, silicate, pH • The assigned value has an uncertainty
6 Triazines and phenyl urea herbicides • The participant’s result has an uncertainty
7 Volatile halogenated compounds and benzene 0,45

8 Polycyclic aromatic hydrocarbons

Kontakt: Dr.-Ing. Michael Koch, ISWA, Bandtäle 2, 70569 Stuttgart
michael.koch@iswa.uni-stuttgart.de, www.iswa.uni-stuttgart.de/ch

9 Phenoxy alkane carbonic acids 0,4

10 Special organic parameters 0,35

Wastewater and Groundwater PT 0,3

concentration in µg/l

laboratory specific
• Ions (NH4+-N, CrVI, NO3--N, NO2--N, total-P, CN-, Cl-, SO42-) 0,25
measurement uncertainty
• Elements (Al, As, Pb, B, Cd, Ca, Cr, Fe, Cu, Mg, Ni, Hg, Tl, Zn) assigned value participant's result
• Group and sum parameters 0,2

(AOX, TNb, BOD, COD, TOC, phenoles, TPH) uncertainty of the assigned value
• Gas chromatography 0,15

(benzene and derivatives, volatile halogenated compounds, pesticides) 0,1

• HPLC (pesticides, PAH)
for WWTP laboratories
0,05

• COD, NO3--N, NH4+-N, total-P, total-N, TOC 0

41

95

85

25

29

94

31

69

64

67

10

39

70

71

36

57

45

63

56

17

86

62

22

laboratory code

Future challenges
• To develop a method to ensure the traceability of the assig-
ned value (currently in progress)
• To facilitate and accelerate the data transfer from the parti-
cipants to the provider by using internet tools (just started)
• To harmonize PT schemes in different countries on a high
standard
• The uncertainty of the assigned value is important for the
estimation of the laboratory’s measurement uncertainty from
PT data
• Unfortunately only a few laboratories report uncertainties up
to now
• In general the understanding of the principles of measure-
ment uncertainties is very poor
www.iswa.uni-stuttgart.de