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Guide for participants

This guide for participants is based on the Proftest SYKE’s instructions PT2 Guide for
laboratories version 1.3 (07.01.2019). This guide has been updated based on the current
operation procedures, also technical issues are updated and clarified, e.g. Proftest SYKE's
responsibility for the correctness of the information provided by participants, the
description of the standard deviation for proficiency assessment, the fees for reporting
multiple data and for the delayed cancellation of the registration, the description for
handling of personal data, and participant registration via ProftestWEB. Further, the
formulas for D% and En scores calculation are added.
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Content
1  INTRODUCTION  3 
2  PROFICIENCY TESTS AS PART OF THE LABORATORY MANAGEMENT SYSTEM  3 
3  SYKE AS A PROFICIENCY TEST PROVIDER  3 
3.1  The SYKE Laboratory centre  3 
3.2  Advisory group  3 
3.3  Proficiency tests organized by Proftest SYKE  4 
3.4  Confidentiality and handling of personal information  4 
3.5  Participant feedback  4 
3.6  Subcontracting and cooperation  5 
4  ORGANISING OF PROFICIENCY TESTS AT PROFTEST SYKE  5 
4.1  Planning and marketing  5 
4.2  Preparing and testing the samples  6 
4.3  Delivery of samples  6 
4.4  Processing of results  6 
4.5  Performance evaluation  6 
4.6  Reporting of results  7 
4.7  Costs and invoicing  7 
4.8  Client support and troubleshooting  8 
5  PARTICIPATION IN PROFTEST SYKE TESTS  9 
5.1  Contact person  9 
5.2  Registration  9 
5.3  Cancellation of registration  9 
5.4  Receipt of samples  10 
5.5  Storing of samples  10 
5.6  Analysis  10 
5.7  Reporting results to Proftest SYKE  11 
5.8  Preliminary results from Proftest SYKE  11 
5.9  Final report  12 
6  OTHER BACKGROUND DETAILS FOR PARTICIPANTS  12 
7  REVISIONS AND DISTRIBUTION OF THE GUIDE  12 
8  REFERENCES  13 
Appendix 1. Concepts and definitions  14 
Appendix 2. Statistical procedure for testing samples and processing results  16 
Appendix 3. Reporting results of individual participant  23 
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1 INTRODUCTION
The proficiency tests (PT) and other interlaboratory comparisons (ILC) organized by
the Finnish Environment Institute (SYKE) are provided under the name of Proftest
SYKE. Most commonly organized interlaboratory comparisons by Proftest SYKE are
the proficiency tests. This guide is mainly for proficiency test participants participating
in tests for chemical analysis, but, when applicable, may also be adapted for other
interlaboratory comparisons arranged by the Proftest SYKE. ProftestWEB
(https://wwwp5.ymparisto.fi/Labtest/en) is the electronic client interface of Proftest
SYKE.
The guide aims to provide an overview of organizing the Proftest SYKE proficiency
tests, to assist the understanding of the guides issued for each separate proficiency
test.

2 PROFICIENCY TESTS AS PART OF THE LABORATORY MANAGEMENT

SYSTEM
Most of the laboratories in Finland have a management system based on the SFS-
EN ISO/IEC 17025 standard [1], which requires effective quality control procedures
for monitoring the validity of analytical results. One widely used and accepted way to
monitor the validity is to participate in proficiency testing schemes or interlaboratory
comparisons. The primary aim of proficiency testing is to help individual participants
to monitor the reliability of their test results and to take corrective actions where
necessary to improve the quality of results. The participation in proficiency testing
schemes also increases the trust of the participant’s clients by increasing the
awareness of the quality of the results and their comparability. The important
concepts and definitions for organizing the proficiency tests are shown in Appendix 1.
Eurachem has compiled a guide to selecting, using and interpreting proficiency
testing schemes for laboratories [2], and the Finnish Accreditation Service (FINAS)
has published its own policy on proficiency testing [3].

3 SYKE AS A PROFICIENCY TEST PROVIDER

3.1 The SYKE Laboratory centre

SYKE is a national environmental reference laboratory established under the
Environmental Protection Act (2000). The duties of the reference laboratory include
providing proficiency tests and other interlaboratory comparisons for analytical
laboratories and other producers of environmental information. SYKE Laboratory
centre is responsible of the reference laboratory activities within SYKE. SYKE is
accredited by the Finnish Accreditation Service (www.finas.fi/sites/en) as a testing
laboratory (T003) and a calibration laboratory (K054, SFS-EN ISO/IEC 17025) as
well as a proficiency testing provider (Proftest SYKE, PT01, SFS-EN ISO/IEC
17043). The Proftest SYKE interlaboratory comparisons are widely utilized for
environmental measurements, environmental sampling as well as other relevant
sectors.

3.2 Advisory group

The proficiency testing services in SYKE are guided by an advisory group comprised
of representatives from different relevant sectors. The advisory group provides expert
support, proposes improvements and represents client perspective. It also facilitates
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information flow between the participants and the provider of proficiency testing. The
members of the group are informed on the Proftest SYKE website
(www.syke.fi/proftest/en).

3.3 Proficiency tests organized by Proftest SYKE

Proftest SYKE provides the proficiency tests and interlaboratory comparisons both
nationally and internationally. The yearly number of proficiency tests and other
interlaboratory comparisons varies depending on the needs of the participants as
well as on the availability of the resources at Proftest SYKE. Yearly the proficiency
tests and interlaboratory comparison have altogether over 300 participants. Number
of participants of an individual proficiency test varies from 5 to 65. More information
of the proficiency tests provided by the Proftest SYKE is given on the website
(www.syke.fi/proftest/en).

3.4 Confidentiality and handling of personal information

The provider handles the participant results confidentially. A permanent laboratory
code is assigned for each participant when participating first time in Proftest SYKE
proficiency testing. The permanent laboratory code is shown on the ‘Customer
information’ page on ProftestWEB.
To assure the confidentiality, Proftest SYKE does not use this permanent laboratory
code on printouts or reports of any PT or ILC. For each PT and ILC the participants
get a randomly and separately chosen participant codes (Participant id). The
participant code for each test is available via the customer profile on ProftestWEB.
When especially needed, the permission to inform the participant code of a particular
PT or ILC is requested from the participant, if the participant is producing results for
the Finnish environmental authorities. If the participant codes are provided, the
environmental authorities are reminded of the confidentiality. Generally, if needed,
the participant informs their participant code directly to the environmental authorities.

When registering for a PT or ILC general participant information is collected from a

participant: the name of the contact person and participant (ie. e.g. the name of the
laboratory), address and billing information. The participants can review and update
their information via ProftestWEB. If the contact person wants to remove his/her
information from Proftest SYKE databse, this could be done by sending the request
via email: [email protected]. The personal information related to the PTs and
ILCs is handled by the personnel of Proftest SYKE and the designated persons of the
technical administration (system maintenance and user permissions).

3.5 Participant feedback

Participant feedback plays an important role in improving the proficiency testing
services at SYKE. The feedback and questions are invited to be delivered at any time
via email: [email protected]. Feedback could be given also via ProftestWEB.
Further, feedback could be delivered also via the members of the advisory board.
Proftest SYKE also arranges a feedback questionnaire for participants every few
years. Besides questions on customer satisfaction, the service provider seeks
opinions also on proficiency test timetables, sample concentration ranges, sample
types and the content of reports.
All feedback will be replied in shortest possible time.
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All feedback related to the proficiency testing services is documented and exploited
when arranging future proficiency tests and improving the activities.
For each PT (and ILC), the related feedback and comments are included in the final
report of the PT (or ILC).
General feedback related to the Proftest SYKE services could be sent directly to
Director of Laboratory ([email protected]). Where necessary, disagreements
arising between the organizer and the participants are aimed to be settled through
negotiation and conciliation.

3.6 Subcontracting and cooperation

Commonly the PTs and ILCs are organized by Proftest SYKE together with the
SYKE’s testing and calibration laboratory. Subcontracting is used when needed
analyses are not available at SYKE or needed resources are not available at the time
in question. Subcontracting could concern for example sample collection, preparation
of samples and sample testing as well as analytical expertize. Neither the permanent
laboratory codes nor the participant codes are ever disclosed to subcontractors, nor
do they ever evaluate participant performance.
The same competence requirements are applied for subcontracted functions than
those of the organizer. All details of subcontracting and competence requirements
are documented.
In the proficiency testing domestic co-operation partners are the operators whose
activities include on the basis of the laws or regulations the reference laboratory
activities or other equivalent obligations. For example, in the proficiency test of radon
in groundwater the cooperation partner is Radiation and Nuclear Safety Authority
(STUK). Coopertaion partner can also be a subcontractor, when subcontracting
includes a large entity (for example, a wide analytical expertise). Cooperation
partners' competence requirements are the same as those of proficiency test
provider.

4 ORGANISING OF PROFICIENCY TESTS AT PROFTEST SYKE

4.1 Planning and marketing

The annual program of Proftest SYKE proficiency tests is published in October–
November of the previous year on the Proftest SYKE website
(www.syke.fi/proftest/en). The participants of Proftest SYKE proficiency tests are
informed of the publication of annual program by email.
For proficiency tests organized infrequently or seldom, pre-registration or other
information might be requested.
The registration for the PT opens about two months before the planned realization of
the PT (or ILC). The registration opens on ProftestWEB and Proftest SYKE sends an
information letter by email to receivers (mainly participants of former tests) who are
potentially interested to participate in the PT. The information letter is also available
on the Proftest SYKE website (www.syke.fi/proftest/en). More information could be
asked from Proftest SYKE customer service [email protected].
Proftest SYKE reserves the right to cancel the proficiency test if the number of
participants is significantly lower than anticipated. Participants will be informed of
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cancellation latest two weeks before the planned time of realization of the proficiency
test.
Proftest SYKE promotes the upcoming PTs and ILCs also via LinkedIn
(www.linkedin.com/in/proftestsyke/) and Eptis database (www.eptis.bam.de).

4.2 Preparing and testing the samples

Homogenized sample is divided into subsamples. While most samples are delivered
ready for analysis, in certain cases participants are requested to complete the
sample preparation, e.g. by adding the solution containing the measurand(s)
provided with the sample. This procedure is applied when the sample contains
unstable measurands (e.g. BOD7).
Sample homogeneity is tested using at least one of its measurands (see Appendix 2,
part 3 Homogeneity test). E.g. the sample containers for nitrogen compounds are
tested by determining total nitrogen, as it resembles best the possible inhomogeneity
caused by particles. Stability of the measurand is tested if it is not known to be stable
based on the literature or experience (see Appendix 2, part 9 Stability test).

4.3 Delivery of samples

The transport date and estimated arrival date of samples is advised to the
participants in the information letter. Samples are generally delivered within 24 hours
and special arrangements may be made to govern timely deliveries to participants
abroad. The consignment number (or reference number) is informed to the
participants abroad, thereby enabling shipments to be tracked via internet. The
provider follows the stability of samples during the shipment when the measurands
have poor stability (e.g. temperature control or weighing prior and after delivery)

4.4 Processing of results

The results of participants are processed in accordance with the ISO 13528 standard
[5]. Normality of data is studied first (see Appendix 2, part 7 Normality) and outliers
are removed based on the outlier tests performed (Appendix 2, part 2 Outlier tests).
The assigned value for the measurand is usually either the calculated value
(synthetic samples) or the robust mean, the mean or the median of results reported
by the participants. The certified value of certified reference material (CRM) or a
value determined using CRM may also serve as the assigned value. In special cases
the assigned value may be calculated using the consensus value from expert
laboratories selected in advance or by using metrologically traceable result. The
expanded uncertainty is estimated for the assigned value (see Appendix 2, part 10
Uncertainty and reliability of assigned value). If the number of participant results is
low (fewer than 6) or the results are widely scattered, either the assigned value and
method for performance evaluation are estimated separately or assigned value is not
set.

4.5 Performance evaluation

The performance evaluation is usually based on the z-scores (see Appendix 2, part
11 z score), where the provider sets the target value for the standard deviation for
proficiency assessment. The standard deviation for proficiency assessment is
estimated based on the concentration of the measurand, the type and complexity of
analytical method employed (different e.g. when determining the pH or mineral oil
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content of water), the results of homogeneity and stability tests, the uncertainty of the
assigned value, the standard deviation of results, and the long-term variation in the
former proficiency tests. The standard deviation for proficiency assessment can also
be based on the legislative requirements. Preliminary values for standard deviation
for proficiency assessment are provided in the sample letter and the values are
reviewed and finalized when processing of results.
If the standard deviation for proficiency assessment set by the provider is not
appropriate for the participant’s purpose, the participant may recalculate the z score
using the formula shown in Appendix 3.
The reliability of the assigned value is tested by comparing its uncertainty to standard
deviation for proficiency assessment (Appendix 2, part 10). The reliability of the
standard deviation for proficiency assessment is tested by comparing it to the
standard deviation of the test results (Appendix 2, part 11).
When the participant has reported their results together with the uncertainty
information, the zeta scores and their comparison to the z scores are given to the
participants as part of the preliminary results (Appendix 2, part 12).
When there are only few reported results for a measurand (n < 6), the performance
could be evaluated by the means of D% (Difference) or En (Error, normalized) scores.
D% and En scores describe the difference between the participant results and
assigned value. En score includes the expanded uncertainties of the participant result
and the assigned value.

4.6 Reporting of results

The processing, evaluation and reporting of the results is based on the information
reported by the participants. Proftest SYKE is not responsible for the correctness of
the information reported by the participants (e.g. the accreditation status of the
results). The correctness of the reported results of participants could affect to the
correctness of the final report.
Proftest SYKE publishes the preliminary results of the proficiency tests in
ProftestWEB, on the page of the test mostly within a week after receiving the results.
For the tests with wide variety of samples and measurands, the preliminary results
are published within 2 weeks. The participant code for each test is available via the
customer profile on ProftestWEB, on the page of the test and the code is official
when the preliminary results are published. The preliminary results could also be
delivered to the participant contact person via email.
The final report of the proficiency test will be released within 2–5 months of receiving
the results. The final report is published in English, when more than 10% of the
participants are from abroad, or when English report is otherwise more applicable. In
other cases the report is published in Finnish. The report includes a summary of
sample preparation and more detailed information of sample homogeneity and
stability tests are available from the provider if needed.

4.7 Costs and invoicing

Providing proficiency tests is a commercial service of SYKE governed by the Act on
Criteria for Charges Payable to the State (1992) and its subordinate statutes. All
prices are subject to valid VAT (value added tax) unless the payer is classified as a
government department.
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Costs are calculated on the basis of e.g. equipment, labour, delivery, printing and
similar expenses. Usually the price is divided into basic fee (same for all participants)
and separate fees for the samples. Basic fee for participation includes the sample
delivery costs within Europe. Participants from outside Europe are kindly instructed to
contact the provider to get more information of the delivery costs.
A cost estimate is prepared for each proficiency test at the time of the preparing the
annual program and reviewed when dispatching the information letter. The estimated
costs may change, for example, if the test program is modified by the request of
participants, or due to a substantial increase in costs.
The invoices are dispatched after publishing the preliminary results. The provider
defrays the delivery costs of the damaged or missing samples while the costs of
providing and delivering additional samples must be borne by the participants. The
participant may provide several results for measurands for each proficiency
test. The participant receives separate evaluation for each additional result set
and the provider will charge an additional fee of 40 % of the basic fee for each
additional data set.
The participation fee must be paid in full when the participant has registered and
received the samples but does not deliver the test results to the organizer. Each
participant must defray its own analysis costs and the possible customs fees and
similar.
The samples are pre-tested. However, in case of sample preparation failure
observed after sample delivery, there is no charge for the participants. If possible, a
new sample will be delivered to the participant at the standard charge.

4.8 Client support and troubleshooting

The proficiency test provider and analytical experts assist the participants in solving
problems related to unforeseen performance. The analytical experts are defined for
each proficiency test. They may be contacted after the preliminary results have been
delivered, especially if the proficiency test results indicate a need for corrective
actions in the participating laboratory. If a participant has discovered a problem within
their analysis, they may use the possible spare batch of sample material for re-
analysis.
Participant may request parallel analysis together with the testing laboratory of SYKE
laboratory centre or some other laboratory. These analysis requests will be charged
separately.
If the sample measurands are stable, the proficiency test samples will be stored for a
longer period. Participants may order samples also later to resolve problems or to
test methods. Proftest SYKE stores the samples until the publication of the final
report, and samples of stable measurands are stored for two years. Samples are
subject to a delivery charge as well as the sample fee defined for the proficiency test.
On request Proftest SYKE could provide individual participants a summary of specific
determinations (in the form of z-scores) spanning a period of several years. The
charged fee for the summary of participant’s performance over the longer period will
be the cost of data retrieval.
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5 PARTICIPATION IN PROFTEST SYKE TESTS

5.1 Contact person

Proftest SYKE maintains a register of the participants of the proficiency tests.
Participants in proficiency testing must appoint a contact person and preferably a
deputy for the communication with the proficiency test provider. The contact person
should preferably be appointed on a sustained basis, and not only for individual tests.
The provider must be notified when a new contact person is appointed. The contact
person will serve as the addressee for samples and proficiency test results, and will
be advised of other substantial information related to the proficiency tests. The given
contact information is used for sample delivery as well as for invoicing the
participation. The contact person can view and update their information via the
customer profile in ProftestWEB. If the contact person wants to remove his/her
information from the register, a request could be delivered via email:
[email protected].

5.2 Registration
Participants register (Create order) to an open PTs/ILCs via the electronic client
interface, ProftestWEB (https://wwwp5.ymparisto.fi/labtest/en) according to the given
timetable. The interface could be found also via Proftest SYKE website
(www.syke.fi/proftest/en  Current proficiency tests).
When the participant has already used ProftestWEB, username and password is
used to log in. Then the contact information is filled in automatically to the New order
form. Via the Orders page on ProftestWEB, it is also possible to register to an open
PT/ILC without login. In such case, after the order is sent, the provider gives the
participant access to the interface.
When registering, the participant orders the needed samples by selecting them on
the order form. The participant may order several samples if needed. The cost for
samples is indicated on the order form. The participant could also deliver additional
set(s) of results. The participant is advised to contact the provider in such case, the
provider then creates multiple result forms for the participant. A supplementary
charge is added for this (see Chapter 4.7).
At the time of registration, participant should deliver the invoicing information
including the VAT number of foreign participant's institute, their own order number (if
needed), client code, or invoicing address, when it is not the address of the sample
delivery address.
The registration is accepted by Proftest SYKE and the acceptance is shown as a
date stamp on the information of the current test (Tests  Orders).

5.3 Cancellation of registration

The registration is binding. However, in exceptional cases the participant may cancel
their registration no later than two weeks before the sample delivery date.
Subsequent cancellations are subject to a cancellation fee of 70 per cent of the
participation fee.
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5.4 Receipt of samples

The contact person must ensure that the staff is notified of the incoming samples to
prevent them from being incorrectly stored for too long at the participating laboratory.
The proficiency test provider must be notified immediately if the samples have not
arrived within the specified period.
The sample letter, delivered together with the samples, should be read carefully
before analysing any samples. The letter is available also on the page of current
page in ProftestWEB.
The recipient should check the contents of the sample package when the samples
arrive. The proficiency test provider should be notified immediately of any broken
sample containers or missing samples to ensure that new samples are sent promptly.
Electronic “Sample arrival” form is to be downloaded on ProftestWEB, on the page of
current test. The form should be filled and delivered to the provider within the
requested time. The time of receiving the samples is filled into the form for the
unstable analytes as well as other information requested. The form is designed to
help the provider to monitor the delivery process and any problems that may arise,
such as bottle breakages or leaking, missing materials, or delays in delivery.
The participant should label the sample bottles according to their own standard
procedures. Participants should note that labels glued to sample bottles will not
withstand e.g. thermal treatment in water (pH determination) or autoclaving (Ntot).

5.5 Storing of samples

The sample letter includes storage instructions. Samples should generally be stored
in refrigerator (4 °C) until the time of analysis. Instructions are given separately in
special cases (e.g. dried solid samples: storage at 20 °C).

5.6 Analysis
The sample letter generally includes details of the concentration range of the
measurands. Samples are analysed using the standard procedures of the participant.
When necessary, the proficiency test provider may issue special instructions for
sample pretreatment and measurements.
If the participant deviates from the instructions and recommendations issued with the
sample, then this deviation and the reason for it should be informed when reporting
the results. It is particularly important to inform the provider about the deviations from
the recommended time of analysis, as these deviations could affect the evaluation of
laboratory performance. If the participant has difficulties with the measurement
deadlines, they have to contact the provider to rearrange the timetable.
The provider requests participants to report either one test result or multiple results of
parallel analysis. Parallel testing is a repeat of the whole analysis from beginning to
end, including the sample preparation stages. When parallel results are not
requested by the provider, the participant will perform the analysis with as many
parallel tests as are normally conducted for the measurement.
The test analysis is also subject to normal quality assurance procedures.
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5.7 Reporting results to Proftest SYKE

The results for the PTs and ILCs are reported mainly via ProftestWEB. In special
cases, e.g. for rarely conducted ILCs, a case-specific results sheet (Excel) or other
means of result reporting could be used. In such cases the participants are
separately instructed.
The results are to be reported according to the given timetable enabling the provider
to report the preliminary results on time. While overdue results are generally
excluded from result processing (unless otherwise agreed), participants remain liable
for the participation charge.
The results are to be reported with one more significant number than specified in the
analytical instructions. Results are reported with as many parallel results and in the
units as requested. Should the participant have not followed the given instructions, in
general, their result will be excluded when defining the assigned value.
The used test methods are reported by choosing the appropriate method from the
drop-down menu on the Save results page. If no method is appropriate, then “Other
method” is selected and briefly described. Literature reference does not suffice, as
the provider will not necessarily have access to all references. Details of analytical
methods are important, as they enable the provider to compare the results of various
methods. Sample pre-treatment details are particularly crucial, for example, when
interpreting the results of organic analyses.
When reporting results, special attention should be paid to result units, to the
requested number of parallel results, to the amount of significant numbers, and
to ensuring that result is entered on the correct line. These points have proved to
be the most common sources of error when reporting results.

5.8 Preliminary results from Proftest SYKE

The preliminary results are available in ProftestWEB, on the page of the test. The
preliminary results are also sent via email to the contact person of the participant.
Participant’s participation code is available on ProftestWEB, on the page of the test.
When required, the participation code could be obtained from the provider.
The purpose of the preliminary results is to:
 Provide feedback to participants on their results and performance in the PT or
ILC at the earliest, and
 Enable the participant to verify that no errors have occurred in reporting the
result data. Therefore the preliminary results are mostly provided both in
Finnish and in English.

The following appendices are usually provided with the preliminary results:
 results reported by participant
 when results are reported as parallel results, the preliminary results have the
mean value
 result tables for individual participants (see Appendix 3 for an example)
 definitions of statistical parameters
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 summary of the PT/ILC

 summary of z scores
 zeta scores (Appendix 2, part 12)
 summary of D% and En scores, when applicable
Participants should check that their results are correct in the data treatments.
Participants may comment the preliminary results within the given commenting
period. After publication of the preliminary results, the participant results will be
corrected only in exceptional cases, but details of errors will assist the performance
evaluation. Exceptions could be the errors caused by the provider or errors in
reporting units in cases where the number of results is too low for statistical data
processing.
Participants are kindly requested to report the causes of deviant results, as these
may help other participants encountering similar deviations. Additionally, it enables
the provider to classify the causes of deviant results in the final report.

5.9 Final report

The final report for each proficiency test is published electronically in the publication
series Reports of Finnish Environment Institute and stored permanently to HELDA,
the open digital repository maintained by the University of Helsinki
(https://helda.helsinki.fi/syke). The participants are informed of the published final
report and the link is found from the test page on ProftestWEB as well as on Proftest
SYKE website (www.syke.fi/proftest/en). A printout is available on request for an
additional fee. Only the electronic publication is official and may be cited in for
example bibliographies. If any factual mistakes are observed in the published final
report, the page of corrections will be included in the report. All participants of the
proficiency test will be informed of the updated report by e-mail.

6 OTHER BACKGROUND DETAILS FOR PARTICIPANTS

Information on proficiency tests arranged by other proficiency test providers is
available from Eptis, the European information system (http://www.eptis.bam.de).
Nordtest has published two useful guides in English: A Handbook for Chemical
Analytical Laboratories [8] and a Handbook for calculation of measurement
uncertainty in environmental laboratories [9]. A measurement uncertainty software
application based on the latter handbook is developed by SYKE’s Calibration and
contract laboratory and is available on their webpage [10]. Both guides are available
in several languages.

7 REVISIONS AND DISTRIBUTION OF THE GUIDE

This guide is available on the Proftest SYKE website and will be revised as
necessary. Participants are responsible for discarding any outdated versions.
Revised version will be advertised on the Proftest SYKE website
(www.syke.fi/proftest/en).
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8 REFERENCES
1. SFS-EN ISO/IEC 17025, 2005. General requirements for the competence of testing
and calibration laboratories. Finnish Standard Association (SFS), Helsinki.
2. EURACHEM Guide, 2011. Selection, use and interpretation of proficiency testing
(PT) schemes (http://www.eurachem.org).
3. FINAS A2/2012. The principals for the assessment of the quality assurance and the
intercomparison practices in laboratories (in Finnish, http://www.finas.fi).
4. ISO/IEC 17043, 2010. Conformity assessment — General requirements for
proficiency testing. Finnish Standard Association (SFS), Helsinki.
5. ISO 13528, 2015. Statistical methods for use in proficiency testing by interlaboratory
comparisons.
6. ISO 5725-2, 1994. Accuracy (trueness and precision) of Measurement Methods and
Results - Part 2: Basic Method for the Determination of Repeatability and
Reproducibility of a Standard Measurement Method.
7. Thompson, M., Ellison, S.L. R., Wood, R., 2006. The International Harmonized
Protocol for the Proficiency Testing of Analytical Chemistry laboratories (IUPAC
Technical report). Pure Appl. Chem. 78: 145-196. www.iupac.org.
8. Nordtest Report TR 569, Edition 5.1, 2018. Internal Quality Control – Handbook for
Chemical Analytical Laboratories. (http://www.nordtest.info).
9. Nordtest Report TR 537, Edition 4, 2017. Handbook for calculation of measurement
uncertainty in environmental laboratories (http://www.nordtest.info).
10. Näykki, T., Virtanen, A. and Leito, I., 2012. Software support for the Nordtest method
of measurement uncertainty evaluation. Accred. Qual. Assur. 17: 603-612. MUkit
website: www.syke.fi/envical.
11. Lisinger, T.P.J., Kandler, W., Krska, R., Grasserbauer, M., 1998. The influence of
different evaluation techniques on the results of interlaboratory comparisons. Accred
Qual Assur 3: 322-327.
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Appendix 1. Concepts and definitions

Assigned value, reference value
Value attributed to a particular quantity and accepted, sometimes by convention, as having
an appropriate uncertainty for a given purpose.
Certified reference material, CRM
A reference material, accompanied by a certificate or other official document, one or more
of whose property values are certified by a technical procedure.
Homogeneity
All delivered samples have the same composition.
Interlaboratory comparison
Organization, performance and evaluation of measurements or tests on the same or
similar items by two or more laboratories in accordance with predetermined conditions.
Normality
The extent to which the observed distribution approximates to a normal distribution in a
test result.
Outlier
Extreme value locating far from the rest of the domain values. Outliers are determined
using the Cochran, Grubbs or Hampel statistical tests.
Precision
The closeness of results when measurements are repeated several times under stipulated
conditions. The smaller the random error distribution, the more precise the method.
Proficiency testing
Evaluation of participant performance against pre-established criteria by means of
interlaboratory comparisons.
Provider
Organization which takes responsibility for lall tasks in the development and operation of a
proficiency testing scheme.
Reference laboratory
A laboratory that issues reference values with a known uncertainty for a given material.
Reference material, RM
Material or substance of whose property values are sufficiently homogenous and well
established to be used for calibrating an apparatus, assessing a measurement method,
and assigning values to materials.
Repeatability
Identical test results from repeated tests performed within a short period by the same
operator, or by another operator using the same method, on identical test items, using the
same equipment or different equipment in the same laboratory.
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Replicate determination
Two or more parallel determinations, where the determination is repeated from beginning
to end (including the pre-process stages).
Reproducibility
Measurement conformity where test results are obtained using different methods, different
equipment, in different laboratories, by different operators and at intervals that are long in
relation to a single test. The reproducibility deviation is usually greater than the
repeatability deviation. It is generally used in proficiency testing schemes.
Stability
Samples remain unchanged (stable) until they are analysed.
Standard deviation for proficiency assessment
Measure of dispersion used in assessing proficiency, based on the available information.
Traceability
The relation of measured results through an unbroken chain of measurements to the
appropriate national or international standards.
Trueness
The closeness of agreement between the average value obtained from a large series of
test results and an accepted reference value.
Uncertainty of measurements
A parameter associated with the result of a measurement that characterizes the dispersion
of the values that could reasonably be attributed to the measurand.
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Appendix 2. Statistical procedure for testing samples and processing results

1 ANOVA test
The ANOVA test can be used when participants report several replicate results to estimate
the standard errors within and between participant results [6].
The repeatability standard error sw (within participant results) is calculated using the
participants’ replicate results and also the between participants’ results standard error sb is
calculated. Finally, the reproducibility standard error st is calculated according to the
equation:

st  sw 2  sb 2

2 Outlier tests
Outlier tests are used to identify the results that differ statistically significantly from the
other results in the data set (in practice, the values outside the 95 % confidence level).
The parallel results are tested with Cochran’s test and the deviation of the participant
result (or the mean of parallel measurements) from the data set is tested with the Grubbs
or Hampel test.

Cochran’s test
Cochran’s test is designed to assess the within-laboratory deviation, i.e. to determine
excessive discrepancies between participants [6]. Participants are numbered 1, 2, ..., p
and iterated distributions s1, s2,…, sp. The test value is:
s 2 max
C p
, where
 si2
i 1

si = the standard deviation of the replicate (parallel) results

smax = the maximum standard deviation of the replicate results
p = the number of the result series.

Cochran’s test is performed when there are parallel results from at least three participants
in the result data.
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Grubbs test
In the Grubbs test the result deviation is tested either one by one (biggest or smallest
results, Grubbs) or two by two (biggest or smallest, Grubbs2). In the test the values are
calculated for the minimum and maximum results. For the Grubbs test the test value G is
the bigger from the results of minimum value / and maximum value
/ , where is mean of reported results, is smallest result, is
maximum result and s is standard deviation of the reported results. The Grubbs2 test
compares the variance of whole data to the variance observed when two highest or lowest
results have been eliminated from data. The result is outlier if test value G is higher than
critical value in the 5 % significance level. The Grubbs test could be repeated and applied
to the data until no more outliers have been found [6]. However, after the test at least three
valid values should remain.

Hampel test
Hampel test is based on the median and the absolute value of a single value. The median
xmed (see part 6) of the results x1, x2,…, xp is calculated together with the absolute residuals
(di) of the single results from the median (di = |xmed- xi|). The median of the absolute
residuals MAD (Median Absolute Deviation) is then calculated. The result xi is an outlier if
di > 5.06 × MAD [11].
When interpreting the results of the outlier tests, the standard deviation for proficiency
assessment (spt) is taken into account. The outlier test is performed when the data
consists of at least seven results.

Robust analysis
The use of robust statistics also allows discarding of extreme results before calculating the
final robust mean (see part 8, [5]).

3 Homogeneity test
For homogeneity testing 4–15 bottles (circa 10 % of the total amount) from the prepared
sample series are used and at least one measurand is determined.
Test results are assessed by analysing the variance between groups (ANOVA), with at
least two parallel analyses performed for each sample. Finally the F-test is used to decide
whether the discrepancies between the concentrations of measurand in different bottles
are significant [5, 7].

4 Mean
The mean value of results is calculated using the formula:

1n
x  xi , where
n i1

x = the mean value of results

xi = the single result
n = the number of results.
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5 Standard deviation
The standard deviation is the size of result distribution around the mean and is calculated
using the formula:
n

 (x i  x) 2
s i 1
n 1 , where

s = the standard deviation

xi = the single result
x = the mean value of results
n = the number of results
The standard deviation can also be expressed as a percentage (relative standard
deviation).

6 Median
The median is the middle result of a series arranged in order of ascending size (when n is
odd number) or the mean of the two middle results (when n is even).

7 Normality test
The normality of the result material is tested using the Kolmogorov-Smirnov test, where
the results x1, x2, … ,xp are combined in an empirical cumulative distribution function of the
x value. The number of results xi smaller than x is calculated and normalized by dividing by
the number of results p. The derived cumulative distribution is compared to the standard
cumulative distribution function (the maximum deviation of these is computed and
compared to the test value distribution).

8 Robust mean and robust standard deviation

The robust mean is commonly used in evaluating assigned values for proficiency tests and
is also recommended in international guides [5, 7]. The impact of deviations on the robust
mean is theoretically smaller than on the arithmetic mean.
Although highly deviant values are commonly not discarded when computing the robust
mean, their impact is reduced by down-weighting and recalculating [7]. Experience has
shown, however, that the robust mean can also be affected by some extreme values (e.g.
values differing from the data more than 5 × srob or more than 50 % from the robust mean)
[7]. In such cases these extreme values may be discarded before final calculation of the
robust mean.
The robust mean and robust standard deviation are calculated using Algorithm A, as set
out in standard ISO 13528 [5]:
The data items are sorted in increasing order: x1, x2, …, xi,…,xp.
Initial values for x* and s* are calculated as:
x* = median of xi (i = 1, 2, ...., p)
s* = 1.483 × median of ‫׀‬xi – x*‫( ׀‬i = 1, 2, ...., p)
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The mean x* and s* are updated as follows:

Calculate φ = 1.5 × s*. A new value is then calculated for each result xi (i = 1, 2, …, p):

{ x* - φ, if xi < x* - φ
xi* = { x* + φ, if xi > x* + φ
{ xi otherwise.
The new values of x* and s* are calculated from:
∗ ∗
∑ /

p
s *  1.134  ( xi *  x * ) 2 /( p  1)
i 1

To determine the final robust estimates xrob and srob the robust mean x* and the robust
standard deviation s* may be derived by an iterative calculation, i.e. by updating the values
of x* and s* several times until the process converges.

9 Stability test
The stability of samples is tested when the analysed compound has poor stability e.g.
during transport of samples (e.g. determining pH, BOD7, chlorophyll a). Stability is tested
after keeping the samples cool (4 °C) and at room temperature (20 °C) during the period of
transport. Both samples are tested and the results are processed using the difference in
results obtained by analysing samples kept at different temperatures. The difference
should be smaller than 0.3 × standard deviation [5, 7]:
D =│c20°- c4°│< 0.3 × spt, where

c20° = the concentration after storing at 20 °C

c4° = the concentration after storing at 4 °C
spt = the standard deviation for proficiency assessment.

10 Uncertainty and reliability of the assigned value

The measurement uncertainty assessment related to the characterization of the
concentrations depends on the estimation of the assigned value. When using CRM as test
sample, the uncertainty of the assigned value is taken directly from the certificate of the
reference material. The uncertainty of the theoretical concentration of the synthetic sample
is calculated by using GUM calculation where the uncertainties of the sample preparation
steps are used and combined. When using consensus value as assigned value,
measurement uncertainty for synthetic sample could be assessed using robust standard
deviation of the result data.
The uncertainty of an assigned value estimated using the participant results may be
estimated as follows:
If the assigned value is calculated as the mean value, then the expanded uncertainty (Upt)
is calculated as a mean error at the 95 % confidence level [5]:
2 ∙ /√ , where

s = the standard deviation and n = the number of the results.

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If the assigned value is calculated as the robust mean, then the uncertainty is calculated
using the robust standard deviation at the 95 % confidence level [5]:
2 ∙ 1,25 ∙ /√ , where

srob = the robust standard deviation and n = the number of the results.
The standard uncertainty of the assigned value (upt) is compared to the standard deviation
for the proficiency assessment (spt) with the following criterion [7]:
upt/spt  0.3

The assigned value is reliable when the criterion is fulfilled. If 0.3 < upt/spt  l, where 0.3 < l
< 0.7, then the assigned value has high uncertainty. If upt/spt > l, z scores will not be
reported [5, 7].

When metrologically traceable result (eg. ID-ICP-MS) is used as assigned value, the
standard uncertainty of the measurement (GUM calculated) is used as the standard
uncertainty of the assigned value.

11 z score in performance evaluation and reliability of the standard deviation for

proficiency assessment
Performance for a single result is calculated as follows [4]:

, where

xi = the single result

xpt = the assigned value
spt = the standard deviation for proficiency assessment
A result may be considered [4]:
 satisfactory if | z | ≤ 2
 questionable if 2 < | z | < 3
 unsatisfactory if | z | ≥ 3.
An example of the z scores is shown in Appendix 3.
The reliability of the standard deviation for proficiency assessment and the reliability of the
corresponding z score are estimated by comparing the standard deviation of test results s
(sx tai srob) with the standard deviation for proficiency assessment (spt). If srob < 1.2 × spt,
then the z scores may be considered reliable [7].
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12 zeta score and its interpretation

In the preliminary result report the zeta values are provided for the results, for which
measurement uncertainty is reported at the 95% confidence interval (k = 2) [4]:

zeta = / , where

xi = the single result

xpt = the assigned value
ui = the uncertainty of participant measurement
upt = the standard uncertainty of the assigned value
(u = the standard uncertainty = the uncertainty at the 95 per cent confidence level/2)

If the measurement uncertainty reported by a participant is realistic, then the z and zeta
scores will be similar. Neither is the discrepancy large if the difference xi - xpt is small, in
which case the result for participant will be near the assigned value. Participant
performance is not evaluated on the basis of the zeta score, but the participant could use it
when estimating the measurement uncertainty.

How to interpret these results?

z score zeta score Action to take

Satisfactory Satisfactory No action; the result is good!
Satisfactory Not satisfactory The claimed uncertainty is too low, but it
fills the requirement of the proficiency
test.
Not satisfactory Satisfactory The result is within your claimed
uncertainty, but not within the limits of
proficiency test. The uncertainty might
therefore be too high and should be
checked against the uncertainty
requirement of your client.
Not satisfactory Not satisfactory The result is too much biased and the
reason should be clarified.

13 D% values and En scores

When the number of reported results is low (n<6), the performance of the participant could
be estimated by means of D% values (’Difference’). D% values are calculated as the
difference between the participant’s result and the assigned value. D% value can be
interpreted as the measurement error for the results to the extent to which the assigned
value can be considered the reference quantity value.

% % , where
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xi = participant’s result, xpt = assigned value

The assessment of the D% values could be done by e.g. comparing the results with the
quality guidelines or by numeric assessment.

When the number of reported results is low (n < 6) and the uncertainty is set for the
assigned value, the performance could be estimated by means of En scores (’Error,
normalized’, Appendix 4). These are used to evaluate the difference between the assigned
value and participant’s result within their claimed expanded uncertainty. En scores are
calculated:

, where

xi = participant’s result, xpt = assigned value, Ui = the expanded uncertainty of a

participant’s result and Upt = the expanded uncertainty of the assigned value.
Scores of En -1,0 < En < 1,0 should be taken as an indicator of successful performance
when the uncertainties are valid. Whereas scores En ≥ 1,0 or En ≤ -1,0 could indicate a
need to review the uncertainty estimates, or to correct a measurement issue.
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Appendix 3. Reporting results of individual participant

The proficiency test report includes a result printout for each participant specifying the
z scores obtained together with the main statistically derived parameters as shown below.

Example of results reported separately to each participant and calculation of z-score

Participant 5
Measurand Unit Sample -3 0 3 z score Assigned value 2×spt, % Participant's result Md Mean s s% n (stat)
N-NH4 µg/l B2N 1.322 73.3 15 80.6 73.3 74.1 3.9 5.3 26
N-NO2+NO3 µg/l B2N 0.844 154 10 161 153 153 5.4 3.5 25
Ntot µg/l B2N 0.590 452 15 472 451 451 25.7 5.7 26
pH B2H -0.934 7.97 2.5 7.88 7.99 7.98 0.1 1.1 30
P-PO4 µg/l B2P -0.500 21.6 10 21.1 21.7 21.5 0.8 3.5 24
P-PO4-diss µg/l B2P 0.256 21.1 10 21.4 21.2 21.0 1.1 5.4 21
Ptot µg/l B2P -1.602 26.6 10 24.5 26.4 26.6 2.0 7.7 24
Ptot-diss µg/l B2P -2.056 25.2 10 22.6 25.0 25.2 1.9 7.6 19

where:
Measurand The tested parameter
z score Calculated z score(satisfactory result -2 ≤ z ≤ 2)
Assigned value: Assigned value
2×spt % Standard deviation for proficiency assessment (95 % confidence
level)
Participant's result: Result of an individual participant (when parallel results are reported,
the mean value of those) 1)
Md: Median value
s: Standard deviation (absolute)
s%: Standard deviation as percent
n (stat): Number of participants in statistical processing

1)
In performance evaluation, the z score is calculated from the precise result reported by the participant. In the result
sheet of the report, the Participant’s result might slightly differ from the reported value due to the number of visible
decimals or due to rounding.

z score:
In the example above, the assigned value for Ntot in sample B2N was 452 µg/l (= xpt) and
the standard deviation for proficiency assessment spt (2×spt %, at the 95 % confidence
level) was 15 %, thus spt = 7.5 % of the assigned value.
The result of the participant 5 was 472 µg/l (= xi)
z = (xi – xpt)/spt = (472-452) / (0.075 × 452) = 0.590.