Introduction to Quality Management for EDXRF practice - Pursuing ISO/IEC 17025:2005 accreditation.

Section 3: Recommendations for the implementation of the QMS

3 SECTION 3: RECOMMENDATIONS FOR THE IMPLEMENTATION

OF THE QMS
This section will provide you recommendations for the implementation of the Quality
Management System in your XRF laboratory. Further, Section 4 will supply the
templates of QM documentation that you can adapt to your specifics.

Considering the activities typically performed in XRF Analytical Laboratories, we propose

you a QMS structure following a combination of the recommendations from ISO/IEC
17025:2005 and ISO 9001:2000 guides.

3.1 MAIN ACTIONS FOR QMS IMPLEMENTATION

According to the ISO 9001:2000 recommendations, for the implementation of the

QMS, your organization shall:

• Identify the scope of its QMS, as well as the normative references it complies with.
• Identify the processes needed for its quality management system and their
application.
• Determine the sequence and interaction of such processes.
• Establish criteria and methods needed to ensure that the operation and the control of
such processes are effective.
• Ensure the availability of resources and information necessary to support the
operation and monitoring of these processes.
• Monitor, measure and analyze the results of these processes.
• Implement actions aimed to achieve the planned results and to seek continual
improvement of the system.

3.2 DEFINING THE SCOPE OF THE QMS

The scope of the Quality Management System is the provision of some of the
following services:

o the repair and maintenance of electronic equipment,

o the electrical calibration of testing equipment and nuclear instruments,
o the design and development of interfaces/adaptors for scientific equipment
and instruments not available commercially

IT IS ADVISABLE THAT YOU DECLARE IN YOUR QUALITY MANUAL EXPLICITLY THAT THE
IMPLEMENTATION OF YOUR SYSTEM HAS BEEN PERFORMED T HROUGH A DOPTING
GENERAL PROCEDURES TO ENSURE CONSISTENCY IN OVERALL SYSTEM OPERATION.

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Section 3: Recommendations for the implementation of the QMS

3.3 DEFINING THE ORGANIZATIONAL STRUCTURE

A relation of the authorities and subordination chain from the highest levels of the
parent organization (if any) must be described and stated. A typical structure
diagram for a public organization could be:

3.3.1 DEFINING THE ORGANIZATIONAL RESPONSIBILITIES

The responsibilities and authorities of the members of the organization in relation to

the Quality Management System shall be defined. A typical structure could be:

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Section 3: Recommendations for the implementation of the QMS

3.4 DEFINING THE MISSION STATEMENT

The organization mission shall be clearly declared. If the organization is subordinated to
a parent organization, the mission shall be declared as to comprise from general (parent
organization) to the particular (organization) mission statement.

As an example, the mission of the Nuclear Spectroscopy and Application Laboratory

(NSAL) of the IAEA Laboratories is provided:

“The I AEA is s eeking to a ccelerate a nd e nlarge th e c ontribution o f atomic e nergy to

peace, he alth a nd p rosperity t hroughout t he wo rld. T he A gency s hall e ncourage a nd
assist research and make provisions for materials, services, equipment and facilities to
meet the needs of its Member States. The Agency shall establish, apply and administer
international safeguards designed to ensure, within its abilities, that special fissionable
and o ther materials, s ervices, fa cilities, e quipment an d i nformation are on ly used f or
peaceful p urposes. W ithin t his context, t he Mission o f the A gency's La boratories a t
Seibersdorf and Vienna is:

In t he f ield of i nternational s afeguards: t o provide an alytical d ata an d s ervices, i n

support of Agency inspections, which ensure the credibility of the operation of
international s afeguards an d the monitoring in c ompliance w ith the s ignatories of t he
Safeguards Agreements to the commitments made to the Agency and the International
Community;

In the field of nuclear science, technologies and their applications: through technology
transfer, services a nd research, t o c ontribute t o t he implementation o f the Agency's
programmes o n s ustainable d evelopment b y t he e ffective us e o f nuc lear s ciences i n
monitoring of the environment, food and agriculture, human health, industry, physical
and chemical sciences, and the management of water resources.

The Nuclear Spectroscopy and Application Laboratory (NSAL) in Seibersdorf, Austria, is

part of the Physics Section, which belongs to the IAEA Division of Physical and Chemical
Sciences ( NAPC) o f t he De partment o f Nuclear Appl ications (NA) . T he main t asks
carried ou t b y t he N SAL are f ocused on p rovision of t raining i n X RF an alysis, d irect
technical s upport t o t he l aboratories i n Member S tates, c ooperation t hrough b ilateral
agreements w ith o ther X RF gr oups, e xtension o f t he a pplicability r ange a nd
improvements in accuracy, and precision of the XRF techniques. The NSAL provides also
routine a nalytical s ervices to o ther U nits o f th e IAEA L aboratories, s upports
development of c ompact / p ortable XR F s pectrometers an d d ata an alysis s oftware /
hardware f or XR F s ystems. T he Laboratory directly c ooperates w ith ot her re search /
developer g roups a nd u sers of X-ray s pectrometric methods i n t he Agency M ember
States.”

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3.5 DEFINING THE QUALITY POLICY

A typical declaration of the Quality Policy might be:

“It is t he p olicy o f t he O RGANIZATION th at i ts s ervice s upport a chieves a le vel o f

quality in execution and delivery of results that is commensurate with the
requirements of its quality system. The ORGANIZATION will endeavour to carry out
test and/or calibrations and provide results that are at a quality level consistent with
the international requirements.

To a chieve th is, th e O RGANIZATION w ill e stablish a Q uality S ystem in c ompliance

with the ISO/IEC 17025:2005 and the ISO 9001 international standards. The
Organization Leader will ensure that all the members of the staff will be acquainted
with t he Q uality S ystem a nd t he i mplemented p rocedures. T he members o f t he
ORGANIZATION w ill p erform t heir w ork a s to fu lfil the r equirements o f th e Q uality
Policy a nd will r emain f ree o f a ny k ind o f c ommitments o r m otivations o ther t han
those explicitly declared by the (PARENT, if any) ORGANIZATION.”

3.6 QUALITY OBJECTIVES AND QUALITY COMMITMENT

Typical Quality objectives might be:

A. To ensure that the management of the ORGANIZATION and the service support
provided to its customers are maintained and performed in accordance with the
principles of a QMS established in compliance with ISO/IEC 17025:2005.

B. To ensure that the tests and/or calibration are made following validated procedures
and that the provided calibration results are traceable to SI units and comply to
ISO/IEC 17025:2005;

C. To ensure that all staff members involved in activities within the scope of the
quality management system are aware of the quality policy, its documentation and
implementation, and continuously evaluate opportunities for improving the group’s
performance;

D. To provide the ORGANIZATION personnel with a stimulating and rewarding

environment; and

E. To achieve these objectives in a safe, efficient and effective manner.

NOTICE THAT OBJECTIVES A) AND B) CAN BE DEFINED DEPENDING ON THE SPECIFICS

OF Y OUR W ORK. ON T HE CONTRARY O BJECTIVES C) TO E) AR E OF OBL IGATORY
INCLUSION!

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3.6.1 DECLARING THE QUALITY COMMITMENT

The declaration can be enunciated as:

The ORGANIZATION is committed to achieve the above enunciated objectives

through the im plementation o f a Q MS s tructured to a ddress, as a pplicable, th e
criteria g iven i n i nternational standards o f t he I SO/IEC 1 7025:2005, t he I SO 9 001
and ot her re levant i nternational standards and g uides. T he Q MS s hall b e f urther
developed to meet international best practice in activities carried out.

The OR GANIZATION ma nagement a t a ll hierarchical levels, h ereby r epresented b y

the O rganization Leader, is fu lly c ommitted to endorsing the quality p olicy, t o
achieving the quality objectives and to implementing the QMS. Overall responsibility
for the implementation of the QMS resides with the Organization Leader supported
by a proper quality organizational structure.

3.7 STRUCTURE OF THE QMS

The Quality Management System shall include the following key elements:

• A Quality Manual.
• A system for keeping documented and validated calibration instructions, well
documented operational procedures and corresponding records.
• Instrumentation that is periodically calibrated and checked to ensure traceability of
the calibration results and the quality of the maintenance/repair services.
• A clear and comprehensive statement of uncertainty in the measured quantities and
in the reported values resulting from the electrical calibrations.

3.8 STRUCTURE OF THE QMS DOCUMENTATION

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NOTICE THAT DOCUMENTATION MUST BE UNAMBIGUOUSLY AND CLEARLY CODED FOR

PROPER IDENTIFICATION.

3.9 THE QUALITY MANUAL

The Quality Manual shall relate:
• the scope of the Quality Management System.
• the statements of quality commitment, quality policy and quality objectives.
• a list of responsibilities and authorities in regard to QMS.
• the different procedures established for quality management, or a reference to them.
The latter allows to prepare a less voluminous QM.
• the interaction between the processes of the QMS.

3.9.1 THE QUALITY MANUAL STRUCTURE

It is advisable to arrange the contents of the Quality Manual following the contents
outline of the chosen ISO Standard to comply with (ISO 9001:2000 or ISO/IEC
17025:2005).

The ISO/IEC 17025:2005 outline provides a thorough and easy readable drawing-up.
The addition of some sections to this outline is a practical choice to ensure compliance
to both standards in an easy way.

There are two approaches in outlining the Quality Manual structure:

1) an extensive Manual, containing detailed description of most of the processes

and;

2) a more succinct Manual, providing references to operational procedures

describing in turn the processes.

A template of QM is provided in Section 4 for your consideration.

3.10 A MASTER LIST OF GENERAL OPERATIONAL PROCEDURES

The following table comprises a list of procedures that are needed to ensure the
harmonic functioning of the quality management system and to establish the inter-
relation between some of its components:

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3.10.1 FORMAT FOR PROCEDURES, INSTRUCTIONS AND FORMS

The reasons for establishing a standard format are:

• It is beneficial to the user who learns to look for information in set places.
• It acts as a check list for the person who prepares the procedure or instruction.
• It makes the use of different forms related to the Quality Management System more
transparent and allows the use of cross references.
• To maintain the standard format and to minimize the hazard for requirements to be
overlooked.
• To make clear the status of a current document (approval date and current version).

3.10.2 APPROVAL, REVISION, CONTROL AND DISTRIBUTION OF QUALITY

DOCUMENTATION
This procedure establishes the authorities for the approval, dissemination, revision
and changes in the quality documentation. In principle, the documentation must be
prepared by the technical staff responsible for the process to which the given
procedure or document is related with. Major revision shall be performed by the
Technical Manager or the Quality Manager, as appropriate.

For example: Procedures and records related to workflow control and IQC
must be reviewed by the QM, whereas technical procedures must be reviewed
by the Technical Manager.

All the documentation must be approved by the top manager of the organization.

ORIGINALS OF T HE QUALITY D OCUMENTATION M UST B E KE PT IN A S AFE P LACE.

AUTHORISED COPIES OF PROCEDURES SHALL BE AVAILABLE IN THE WORKPLACES FOR
THE USE OF THE STAFF INVOLVED IN EACH PARTICULAR PROCEDURE.

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3.10.3 INTERNAL AUDITS

This procedure shall describe the basic internal audit practices, and provide guidelines
for establishing, planning, carrying out and documenting internal audits.
Responsibilities, time frame, and operations to be taken as part of the audit shall be
defined, as well as the outputs of the audits and their interrelation with management
actions.

The Quality Manager shall control the accomplishment of the plan of audits and to
participate in all of the activities related with the audits. The Technical Manager and the
top management shall design the remediation plans and to make them effective in
realization.

3.10.4 NONCONFORMITIES
The laboratory shall have a policy and procedures that shall be implemented when any
aspect of its management system and testing and/or calibration work, or the results of
this work, do not conform to its own procedures or the agreed requirements of the
customer.

The purpose of this procedure is to allow a proper response to the customer's

complains, to provide the evidence on corrective and preventive actions undertaken and
to allow management review and related process and quality system improvements.

Top management is responsible for ensuring that the causes of the complaints are
thoroughly investigated, proper actions planned and realized in due time.

ANY POTENTIAL NONCONFORMITY REVEALED BY ANY MEMBER OF THE STAFF SHALL BE

TREATED AS A COMPLAINT.

3.10.5 OUTSOURCING
When an XRF laboratory subcontracts work, this work shall be placed with a competent
subcontractor (the subcontractor must complies with ISO/IEC 17025:2005 for the work
in question).

The laboratory shall advise the customer of the arrangement in writing and, when
appropriate, gain the approval of the customer, preferably in writing.

The laboratory is responsible to the customer for the subcontractor’s work, except in the
case where the customer or a regulatory authority specifies which subcontractor is to be
used.

The laboratory shall maintain a register of all subcontractors that it uses for tests and/or
calibrations.

3.11 SPECIFIC OPERATIONAL PROCEDURES FOR EDXRF PRACTICE

The following pad illustrates some of the procedures related to the specific case of
EDXRF practice:

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3.11.1 DEFINITION OF WORKING ASSIGNMENTS AND MONITORING THE SERVICE

FLOW

Due to the wide range of applications for XRF techniques, changes in any a-priori
defined requirement for analytical services should occur in order to solve
challenges. Keeping a constant communication with the customer is the only way to
pursue agreement in regard to any modifications or changes arising from
unexpected findings. Be always sure that:

• the laboratory has the capability to perform the modified task.

• an agreement is reached with the customer before to proceed.

ON A L ONG T ERM, I T I S A LWAYS PR EFERABLE TO R EFUSE A S ERVICE REQUEST,

RATHER THAN TO FAIL TO CUSTOMER EXPECTATIONS.

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3.11.2 A GENERAL WORKFLOW CHART

3.11.3 EDXRF ANALYTICAL INSTRUCTIONS

Your QMS will incorporate as many analytical instructions as new procedures will be
implemented and validated. Due to the great versatility of the XRF technique, it is
expected that with time the field of applications will be wider. Some examples of
analytical instructions might be:

• Mineral resources: Determination of ore grade in copper minerals by XRF analysis.

Fundamental Parameters Method
• Steel alloys: Classification of stainless steels by XRF analysis. Normalized
Fundamental Parameters Method.
• Food products: Determination of essential elements in cereals by XRF analysis.
Emission-Transmission method.
• Water quality: Heavy metal determination in drinking water by TXRF.
• Archaeometry: Identification of pigments in paintings by micro-XRF.

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3.11.4 INTERNAL QUALITY CONTROL PRACTICE

The laboratory shall have quality control procedures for monitoring the validity of tests
undertaken. The resulting data shall be recorded in such a way that trends are
detectable and, where practicable, statistical techniques shall be applied to the
reviewing of the results.

Quality control data shall be analysed and, where they are found to be outside pre-
defined criteria, planned action shall be taken to correct the problem and to prevent
incorrect results from being reported.

The control encompasses the analytical process starting with the sample entering the
laboratory and ending with the analytical report. The most important tools in XRF quality
control are the analysis of duplicate samples and the use of control charts. Blind
duplicates are included in the analysis to monitor the precision, whereas reference
materials are analyzed as control samples to monitor in control charts the long term
stability in method performance. The results of each run (group of samples analyzed
within a request for service) are then accepted or rejected if both IQC requirements are
met.

When a quality control program is established, it is essential to have in mind the

requirement on the analytical results and for what purposes the analytical results are
produced (the concept of fit for purpose).

From the requirement on the analytical results the analyst sets up the control program:

• type of quality control sample,

• type of quality control chart,
• control limits (simple, warning and action limits),
• control frequency,
• amount of duplicates and control samples for each run.

3.11.4.1 C ONTROL SAMPLES

Control samples are reference materials with a matrix composition close to that of the
analyzed samples, and which elemental mass fractions are close to the expected ones in
the unknown samples. They should also be stable over time, and be available in
sufficient amount as to be used for years. The control samples should go through the
whole measurement procedure.

Samples fulfilling all these requirements are not always available. Therefore there are
several choices of control samples:

• Certified Reference Material which elemental mass fractions are known with
inaccuracies less than those resulting from the intended analytical method are the
ideal choice
• Test routine sample characterized by alternate analytical methods (in-house material)
• Reference material, standard solution or in-house material
• Reference materials, standard solutions or spiked materials

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Blank samples shall be analyzed for assessment of instrumental blanks or

contaminations. Blank samples must be selected or prepared with a matrix similar to
that of the unknowns, but with mass fraction of the elements of interest below the
detection limits.

3.11.4.2 P RINCIPLES OF Q UALITY C ONTROL C HARTING

Control charting is a powerful and a simple tool for the daily quality control of routine
analytical work. Statistical control pursues to verify the stability of operation. For such
verification the laboratory analyzes control samples together with the routine samples in
every analytical run. The results of the analyses of control samples can be interpreted
following different ways, including the use of control charts.

Though there are several types of control charts, these two are the most important used
for the internal quality control in XRF laboratories:

• X-charts
• Range-charts

3.11.4.3 X-C HARTS

An X-chart has a central line, upper and lower warning limits and upper and lower action
limits.

One of the oldest and simplest types of control chart is the X-chart, which is based on
the distribution of the control values around a true or expected value. It can be used to
monitor the combination of systematic and random effects for control values, based on
single results or on a mean of multiple analyses. Using a reference material as control
sample, the bias may be monitored by comparing the mean control value over time with
the reference value.

X-charts are used to monitor if a bias arise in the results of analysis of a control
materials, thus serving to prove whether the method performance remains under stable
operation. It is worth to notice that the latter is valid for any sample matrix and
elemental concentration order similar to those of the control sample. If a run comprises
different types of matrices or different concentration ranges, it is advisable to include
more than a control sample on each run.

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3.11.4.3.1 S ETTING THE CONTROL LIMITS AND THE CENTRAL LINE IN X- CHART
The control limits can be set based on method performance – statistical control limits
or according to the requirement on within-laboratory re producibility – target control
limits.

Statistical control limits Target control limits

The control limits are calculated from the The control limits are set based on
historical results obtained during the the requirement on the analytical
analysis of the control sample. For at least quality. The standard deviation for
12 analysis carried out during a certain time the control chart, s, is estimated
period, e.g. a month, the standard deviation from the requirement on
(s) of the results is calculated. This reproducibility.
population of results must be free of out-of-
control results.

Warning limits shall be set at +2s and – 2s. Warning limits shall be set at +2s
and – 2s.
Action limits shall be set at +3s and – 3s.
Action limits shall be set at +3s
Note: The statistical control limits are and – 3s.
constantly updated with the more recent
results under statistical control.

The central line in the control chart can be the calculated mean value of the control
values or a reference value for the control sample. In most cases a mean central line is
used.

Mean central line Reference central line

The mean value is estimated from control The control sample is a reference
values obtained during a longer time. material or a well-characterised
material.
The central line is set to this mean value.
The central line is set to the
assigned (reference or certified)
value.

3.11.4.4 R ANGE C HARTS

Control Chart of the Range of Duplicates are used to control if the precision of the
method remains within the boundaries evaluated during the method validation. The
difference between duplicate results is compared to the target uncertainty of the results.

The uncertainty of the range (absolute difference) of replicate values R = |x1 - x2|can
be assessed as

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If the values of the replicate results can be considered as part of a Gaussian probability
distribution, then in only 5 % of the cases the differences will exceed

and in only 0.3 % of the cases will exceed

As in XRF the precision of the results is mainly conditioned by the counting statistics,
the precision of the results improves with the increase in the concentration of the
element. There are two possible scenarios for a run of analysis: the concentration of the
element is similar in all the samples, or the concentration spans within a broad range.

Case 1: The results of duplicate analysis of a control material having the concentration
of the element similar to those expected in the unknown samples can serve to assess if
the precision correspond to the expected value.

Case 2: Samples contain the element in a broad range of concentration, and therefore
the precision of the results changes in a relatively broad range. The quality control
manager must request a second run of analysis, this time including duplicates of some
of the analyzed samples, as to cover the range of concentrations found during the initial
analysis.

Examples of these two charts are provided next.

3.11.4.4.1 R ANGE CHART FOR A NARROW CONCENTRATION RANGE IN THE SAMPLES

It is possible to control the precision of the results by performing duplicate analysis of
the selected control sample. A range quality control chart (R mean ) can be used to
monitor the results of the analysis. The R mean -chart is set up by analyzing a series of 15
to 20 duplicates and calculating the range (absolute value of the difference). The mean
range can then be calculated and plotted on the R mean -chart as shown in the Figure 1.
The method proposed by Youden and Steiner [Statistical Manual of the Association of
the Official analytical Chemists, Washington DC, 1975] is based in the assumption that
50 % of the ranges should greater than a value corresponding to 0.845 R mean , only 5 %
greater than 2.456 R mean (95 % limit) and only 1 % greater than 3.27 R mean (99 %
limit).

Figure 1: Typical R mean -quality control chart

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If 5 or more consecutive points are above the 50 % limit then the analysis is moving out
of control and corrective action is needed. Occasionally points will lie above the 95 %
limit (about 1 in every 20 points) but points falling above the 99 % limit indicate the
need for corrective action. If too many zero values occur it is likely that the results have
been rounded to a digit not representing the meaningful precision.

The range value on the R mean -chart can be used to calculate the standard deviation of
the analyses by using the equation:

where S is the standard deviation, R are the ranges and N is the number of samples run
in duplicate.

3.11.4.4.2 R ANGE CHART FOR A BROAD CONCENTRATION RANGE IN THE SAMPLES

If the results of a given run of analysis cover a wide concentration range, the quality
control manager can request a second run. In this run, duplicates of the samples
analyzed are submitted to analysis. The values of the ranges are the compared with the
expected uncertainty for each concentration of the element. It is understood that the
uncertainty has been established during method validation for different concentration
levels.

No range shall exceed the action limit calculated as

and only 5 % of the ranges can exceed the warning limit calculated as

Figure 2: Range chart for results spanning over a concentration interval.

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3.11.4.5 V ERIFICATION OF TRUENESS AND PRECISION OF THE ANALYTICAL METHOD

USING THE IAEA APPROACH
As part of the internal quality control of the analytical method, the measurement of a
Certified Reference Material (CRM) serves to investigate if the obtained measurement
result is or is not significantly biased in relation with the reported reference value. For
evaluating the bias, a validated trueness and precision test (the IAEA approach) can be
applied.

For trueness evaluation, the results are considered "Acceptable" if:

A1 ≤ A2

where:
A 1 = |V ref - V lab |

A 2 = 2.58 √(u2 ref + u2 lab)

V ref - reference value of CRM

V lab - value obtained in laboratory

u2 ref,lab - standard combined uncertainties associated to V ref and V lab

For evaluation of precision, the results are considered "Aceptable" if:

P ≤ ALP

where:

ALP: Acceptable Limit of Precision, set for each analyte as a function of its concentration
level and ease of determination.

A result must obtain an "Acceptable" score in both criteria to be assigned the final score
of "Acceptable".

3.11.5 UNCERTAINTY ESTIMATION

What is uncertainty of measurement?

• Any measurement result is characterised by imperfections.

• There will always be an uncertainty about the value of a result: Result = Value ±
Uncertainty.
• It is a quantitative indication of the quality of the result.
• It is the quantification of the doubt associated with a measurement result.
• It gives an answer to the question: How well does the result represent the value of
the quantity being measured?
• There is an uncertainty even when correction factors have been applied, because
there is an uncertainty on these factors.

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The uncertainty of measurement is due to:

• Trueness: the closeness of agreement between the average value obtained from a
large series of test results and the accepted reference value (true value).
• Precision: the closeness of agreement between independent test results obtained
under stipulated conditions.

3.11.5.1 M AIN SOURCES CONTRIBUTING TO UNCERTAINTY IN XRF ANALYSIS

The major contributions to uncertainty of the results in XRF analysis are often the
following:

• Uncertainty due to counting statistics: Owing to the statistical nature of the measured
signal, the standard deviation of the peak area N can be assumed as √N. In the case
of spectrum fitting, the uncertainty due to the quality of peak fit must be accounted
as well. This source becomes one of the largest in the case of low counting statistics.
• When using Certified Reference Materials for the calibration of the model, the
uncertainty of the calibration is affected by the uncertainty of the certified values of
the CRMs.
• Depending on the procedure followed to estimate the effective sample attenuation,
the uncertainty of the attenuation correction can be significant.
Other sources must be carefully evaluated in each analytical procedure.

3.11.5.2 GUM APPROACH FOR UNCERTAINTY CALCULATION

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3.11.5.3 T HE KRAGTEN SPREADSHEET APPROACH FOR UNCERTAINTY CALCULATION

This is a numerical method, suggested by Kragten which makes effective use of
spreadsheet software to provide a combined standard uncertainty from input standard
uncertainties and a known measurement model.

Spreadsheet software can be used to simplify the calculations of partial differentials. In

this sense, the procedure takes advantage of an approximate numerical method of
differentiation, and requires knowledge only of the calculation used to derive the final
result (including any necessary correction factors or influences) and of the numerical
values of the parameters and their uncertainties. The description here follows that of
Kragten.

In the expression for u(y(x 1 , x 2 ...x n ))

provided that either y(x 1 , x 2 ...x n ) is linear in x i or u(x i ) is small compared to x i , the
partial differentials (∂y/∂x i ) can be approximated by:

Multiplying by u(x i ) to obtain the uncertainty u(y,x i ) in y due to the uncertainty in x i

gives

Thus u(y,x i ) is just the difference between the values of y calculated for [x i +u(x i )] and
x i respectively.

The assumption of linearity or small values of u(x i )/x i will not be closely met in all
cases. Nonetheless, the method does provide acceptable accuracy for practical purposes
when considered against the necessary approximations made in estimating the values of
u(x i ).

A step by step sample animation is provided in the course.

3.11.6 VALIDATION
Confirmation by examination and provision of objective evidence that the particular
requirements for a specific intended use are fulfilled.

Validation may include procedures for:

• sampling
• handling
• transportation.

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Section 3: Recommendations for the implementation of the QMS

All influences of changes which are made in the validated methods should be
documented and a new validation should be carried out. Validation is always a balance
between costs, risks and technical possibilities

3.11.6.1 M ETHOD VALIDATION

Techniques for the determination of the performance of a method:

• calibration using reference standards or materials

• comparison of results achieved with other validated methods
• interlaboratory comparisons
• systematic assessment of the factors influencing the result
• assessment of the uncertainty based on scientific understanding of the theoretical
principles of the method and practical experience

The range and accuracy of the values obtainable from validated methods should include:

• uncertainty of the results

• detection limit
• selectivity of the method
• linearity
• limit of repeatability and/or reproducibility
• robustness against external influences and/or
• cross-sensivity against interference from the matrix as assessed for the intended use,
shall be relevant to the clients' needs.

There are many cases in which the range and uncertainty of the values can only be
given in a simplified way due to lack of information.

3.11.6.2 C HARACTERISTIC L IMITS . D ECISION THRESHOLD

It is a characteristic limit that helps one to decide if the element is present or not in the
analyzed sample.

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Section 3: Recommendations for the implementation of the QMS

When the measurement result is higher than the Decision Threshold, it is possible to
affirm that the element is present in the analyzed sample. There exists, however, an
established probability α (usually of 5 %) of finding background measurements above
the Decision Threshold, where background comprise blank signal, interferences and
continuum:

The Decision Threshold is generally expressed in number of counts. When converting

from number of counts to concentration of the element in the analyzed sample, the
Decision Threshold determines the "minimum concentration of that element that the
analytical technique is capable to detect".

For the calculation of the Decision Threshold, the only required data is the probability
function of background (standard uncertainty of background) obtained from the
measurement of background.

3.11.6.3 C HARACTERISTIC L IMITS . D ETECTION LIMITS

The Detection Limit allows a decision to be made as to wether the measuring method
satisfies certain requirements and is consequently suitable for the given purpose of
measurement. It must always be compared with the guideline value given by the client.

The Detection Limit is the characteristic limit that responds to the following question:
what would be the real concentration (of an element in the analyzed sample) that would
give a measurement result below the Decision Threshold with an established probability
β (usually of 5 %).

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Section 3: Recommendations for the implementation of the QMS

The calculation of the Detection Limit requires the knowledge of the probability function
of the measurement result (standard uncertainty of the measurement result). Validation
shall include:

3.11.6.4 N OISE SIGNAL IN XRF AND DETECTION LIMIT ESTIMATION

In EDXRF practice, detection limit for an element i is customarily calculated by using a
signal corresponding to 3 times the standard deviation of the noise signal and the
measuring time tmeas. Depending in the theoretical model, other parameters are used
to calculate the weight fractions or the mass per unit of area. In the case of analyzing
'thin' samples the detection limits can be calculated as:

DL[g/cm2] = 3√N /t meas S i

where S i (s-1cm2g-1) is the instrumental sensitivity for element i.

In the case of analyzing samples of intermediate or infinite thickness the detection limits
can be calculated as:

DL[w/w] = 3√N /t meas A i S i

where Ai (g cm-2) is the attenuation correction, which depends on sample effective

attenuation coefficient and on sample aerial density.

The main contributions to noise signal N in XRF spectra comes from:

• the continuum under the peak (N cont ),

• a peak observed in a measurement performed for a blank sample (with a net peak
area N blank ),
• a peak observed in the absence of sample (instrumental background, net peak area
N bkg ),
• a spectral interference (net peak area N SI ).

As the probability distribution of the results of a series of measurements for any of these
signals can be considered as close to a Poisson distribution, the value √N of must be
estimated in the more general case as:

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