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NABL
NATIONAL ACCREDITATION
BOARD FOR TESTING AND
CALIBRATION LABORATORIES
SPECIFIC GUIDELINES
for CHEMICAL TESTING
LABORATORIES
ISSUE NO : 03 AMENDMENT NO : 00
ISSUE DATE: 25.03.2008 AMENDMENT DATE: --
AMENDMENT SHEET
10
AS : American Standard
BS : British Standard
QC : Quality Control
Sl Title Page
Amendment Sheet i
Abbreviations ii
Contents iii
1. Introduction 1
2. References 2
4. Scope 7
5. Technical Requirements 9
Annexure – A 37
Annexure – B 40
Annexure – C 78
1.1 The requirements for accreditation are laid down in the International Standard ISO/IEC
17025: 2005 (General requirements for the competence of calibration and testing
laboratories). These requirements apply to all types of objective testing but in certain
instances additional guidance is necessary to take account of the type of testing and the
technologies involved.
1.2 This document has been produced by a TECHNICAL COMMITTEE constituted by NABL
for the purpose. It supplements ISO/ IEC 17025: 2005 standard and provides specific
guidance on the accreditation of chemical laboratories for both assessors and
laboratories preparing for accreditation. It gives detailed guidance for those undertaking
quantitative and qualitative examination of the composition, nature and properties of
materials, products and substances.
1.3 Laboratories conducting tests on food should also consult NABL specific criteria on
biology (NABL – 102) and the NABL guidance document on Food (NABL – 114).
ISO/ IEC 17025: 2005 General Requirements for the Competence of Testing and
Calibration Laboratories
ISO Guide 30 Terms and Definitions used in connection with reference materials.
3.1 Selectivity
Selectivity of a method refers to the extent to which it can determine particular analyte(s)
in a complex mixture without interference from the other components in the mixture. A
method which is perfectly selective for an analyte or group of analytes is said to be
specific. The applicability of the method should be studied using various samples,
ranging from pure standards to mixtures with complex matrices. In each case the
recovery of the analyte(s) of interest should be determined and the influences of
suspected interferences duly stated. Any restrictions in the applicability of the technique
should be documented in the method.
3.2 Range
For quantitative analysis the working range for a method is determined by examining
samples with different analyte concentrations and determining the concentration range
for which acceptable accuracy and precision can be achieved. The working range is
generally more extensive than the linear range, which is determined by the analysis of a
number of samples of varying analyte concentrations and calculating the regression from
the results, usually using the method of least squares. The relationship of analyte
response to concentration does not have to be perfectly linear for a method to be
effective. For methods showing good linearity 5 different standards (plus a blank) are
usually sufficient for producing calibration curves. More standards will be required where
linearity is poor. In qualitative analysis, it is commonplace to examine replicate samples
and standards over a range of concentrations to establish at what concentration a
reliable cut-off point can be drawn between detection and non-detection.
3.3 Linearity
Linearity is determined by the analysis of samples with analyte concentrations spanning
the claimed range of the method. The results are used to calculate a regression line
against analyte calculation using the least squares method. It is convenient if a method
is linear over a particular range but it is not an absolute requirement. Where linearity is
unattainable for a particular procedure, a suitable algorithm for calculations should be
determined
3.7 Ruggedness
Sometimes also called robustness. Where different laboratories use the same method
they inevitably introduce small variations in the procedure, which may or may not have a
significant influence on the performance of the method. The ruggedness of a method is
tested by deliberately introducing small changes to the method and examining the
consequences. A large number of factors may need to be considered, but because most
of these will have a negligible effect, it will normally be possible to vary several at once.
The technique is covered in detail by the AOAC (8). Ruggedness is normally evaluated
by the originating laboratory, before other laboratories collaborate
3.9 Precision
Precision of a method is a statement of the closeness of agreement between mutually
independent test results and is usually stated in terms of standard deviation. It is
generally dependent on analyte concentration, and this dependence should be
determined and documented. It may be stated in different ways depending on the
conditions in which it is calculated. Repeatability is a type of precision relating to
measurements made under repeatable conditions, i.e. same method; same material;
same operator; same laboratory; narrow time period. Reproducibility is a concept of
precision relating to measurements made under reproducibility conditions, i.e. same
method; different operator, different laboratories; different equipment; long time period.
3.12 Sample
A portion of material selected to represent a larger body of material.
3.14 Sub-sample
This refers to a portion of the sample obtained by selection or division; an individual unit
of the lot taken as part of the sample or; the final unit of multistage sampling
4.1 The Scope of accreditation of a laboratory is the formal statement of the range of
activities for which the laboratory has been accredited; the scope is recorded in detail on
a laboratory’s accreditation certificate. A laboratory’s scope should be defined as
precisely as possible so that all parties concerned know accurately and unambiguously
the range of tests and/or analyses covered by that particular laboratory’s accreditation.
The schedule format should typically define the laboratory’s accreditation in terms of:
4.2 Where non-routine testing is carried out, it is recognised that a more flexible approach to
scope may be necessary, but the scope must be as specific as is feasible and the quality
assurance system maintained by the laboratory must ensure that the quality of the
results is under control. Frequently, a single measurement technique may be used for
different analytes in a wide variety of samples. This measurement stage may be covered
by a single method. However, the methods used to prepare the samples for subsequent
analysis may vary considerably according to the nature of the analyte and sample
matrix. Thus several methods may be required to cover each different analyte matrix
combination. This is illustrated by gas chromatography, a technique applicable to a wide
variety of analytes. Depending on the matrix, a diverse range of methods may be used
to prepare analytes for gas chromatographic analysis; however, the procedures involved
in the final analytical stage vary little.
4.3 Where a laboratory uses analytical tools such as mass spectrometry, NMR or FTIR, it
may be appropriate to use the terms qualitative and/or quantitative chemical analysis
under the type of test heading. However, the onus will be on the laboratory to
demonstrate to the assessors that in using these techniques, it is meeting all of the
criteria for accreditation. In particular, the experience, expertise and training of the staff
carrying out the tests and those interpreting the data involved will be a major factor in
determining whether or not such analyses can be accredited.
4.4 The approach to extending or amending the scope of accreditation should be as flexible
as possible. Normally the laboratory will give written notice to NABL of the tests, which it
wishes to add to its scope, quoting Standard method references (where applicable) and
providing copies of documented validated in-house methods before surveillance and re-
assessment.
5.2 Personnel
5.2.1 The chemical testing laboratory shall be headed by a person preferably having a post
graduate degree in chemistry or equivalent or Bachelor degree in chemical engineering /
technology or equivalent with adequate experience in the relevant area especially in the
analysis of testing of relevant products.
The minimum qualification for the technical staff in a chemical testing laboratory shall be
Graduate in Science with chemistry as one of the subjects or Diploma in chemical
engineering / technology or equivalent or specialization in relevant fields like Textile,
Polymer etc. The staff shall have sufficient training and exposure in analytical chemistry
and in analysis and testing of appropriate products.
5.2.2 The minimum requirement for an Authorized Signatory shall be a Graduate in Science
with chemistry as one of the subjects / Diploma in Chemical engineering / technology or
equivalent from a recognized university with at least 5 years experience in relevant field,
or Post-graduate in chemistry / specialization in relevant subject / Degree in Chemical
engineering / technology or equivalent from a recognized university with at least 2 years
experience in relevant field.
Note: The Assessment team may however recommend Authorized Signatory who does
not meet the above specified minimum experience requirement with specific
recommendations to NABL, after adjudging the competence of the Authorized Signatory
during on-site assessment.
5.2.3 Chemical testing laboratory involved in testing variety of products shall have a group in-
charge for each area. The group in-charge shall have adequate relevant experience in
addition to the minimum qualification as specified in 5.2.1.
5.2.5 For meeting the requirement of internal audit, there should be at least one technical
personnel apart from the head with suitable qualification and experience, irrespective of
the size of the laboratory, who has received a formal training on internal audit.
The laboratory shall normally use personnel who are permanently employed by the
laboratory or appointed on long-term contract basis, provided laboratory ensures
availability of technical personnel with adequate experience. A laboratory is not expected
to be operated by trainees. Where additional personnel are required, the laboratory shall
ensure that such personnel are supervised and that their work does not put at risk of the
laboratory’s compliance.
5.2.6 Any testing conducted away from the base laboratory (such as in field laboratories, in a
mobile testing laboratory or in the field) must also be under adequate technical control.
This would normally require either the location of Authorized Signatory at each facility or
having an Authorized Signatory visit each facility at appropriate intervals commensurate
with the volume, complexity and range of such tests and the maintenance of a diary
recording the dates and relevant activities of each visit. An authorized signatory must be
involved in the setting up of field or site laboratory.
5.3.1 Samples, reagents and standards should be stored so as to ensure their integrity. The
laboratory should guard against deterioration, contamination and loss of identity.
5.3.2 The Laboratory shall meet the safety requirements applicable to the test procedure
wherever the published standard specifications mention the requirements.
5.3.3 It may be necessary to restrict access to particular areas of laboratory because of the
nature of the work carried out there. Restrictions might be made because of security,
safety, or sensitivity to contamination. Typical examples might be work involving
explosives, radioactive materials, carcinogens, toxic materials and trace analysis. Where
such restrictions are in force, staff should be aware of:
i. the intended use of a particular area;
ii. the restrictions imposed on working within such areas;
iii. the reasons for imposing such restrictions
5.3.4 Frequently, it will be necessary to segregate certain types of work which are prone to
interferences from other work, or which present particular problems or hazards.
Examples are trace analysis (where physical separation from high-level is necessary)
and carcinogen analysis. When selecting designated areas for special work, account
must be taken of the previous use of the area. Before use, checks should be made to
ensure that the area is free of contamination. Once in use, access to such areas should
be restricted, and the type of work undertaken there carefully controlled.
5.3.5 The laboratory shall provide appropriate environmental conditions and controls
necessary for particular tests, including temperature, humidity, freedom from vibration,
freedom from airborne and dustborne microbiological contamination, special lighting,
radiation screening. Critical environmental conditions should be monitored.
5.3.6 One key responsibility of the laboratory management is to provide an adequate and safe
working environment. Laboratory facilities should reflect due consideration of space,
design, security, health and safety. It is recognised that laboratories will be required to
comply with Government building and safety legislation. The provisions of such
legislation shall be considered as additional essential requirements.
Accessories should be preferably stored near each instrument to facilitate its use and
operation. (Labs in which usable space falls below adequate levels may experience
health and safety problems, compromised efficiency, adversely affected morale and
productivity and an increased risk of mishandling and contaminating the evidence. In
designing and planning for additional space or a new facility, future space requirements
should also be projected.
5.3.8 Design
The relative locations of functional areas should facilitate the use of equipment and
instruments. Adequate and proper lighting of minimum 100 lumen must be available for
personnel to carry out assigned tasks. Adequate and proper plumbing and wiring must
be available and accessible. The laboratory must have proper ventilation, adequate
heating, cooling and humidity control as per the requirements. Bench and floor surfaces
must be appropriate for the work being performed. The design should maximise
laboratory functions and activities, safeguard the physical evidence, protect the
confidential nature of the laboratory operations and provide a safe and healthy
environment. (Lack of fiscal resources are not acceptable reasons for unacceptable
laboratory practices).
Where a laboratory exists within a host agency facility, documented procedures may be
required to permit entry during off hours for emergencies.
The laboratory should have a fire detection system wherever applicable. In keeping with
any relevant statutory requirements appropriate fire extinguishing devices must be
available and policies and procedures of laboratory security must be clearly
documented. Laboratory personnel should be trained in fire fighting.
National Accreditation Board for Testing and Calibration Laboratories
Doc. No: NABL 103 Specific Guidelines for Chemical Testing Laboratories
Issue No: 03 Issue Date: 25.03.2008 Last Amend No: 00 Amend Date: -- Page No: 12/ 88
5.3.9 Health and Safety
Health and safety aspects are to be taken seriously. Details about the same are given in
Annexure A.
5.4 Validation
5.4.1 Laboratory, whenever using non-standard methods or a standard method beyond the
stated limits of operation is required to validate such test methods. The guidance
document on Validation of Test Methods, NABL 212 may be referred. Validation of a
method establishes, by systematic laboratory studies, that the performance
characteristics of the method meet the specifications related to the intended use of the
analytical results. The performance characteristics determined include:
- Selectivity & specificity
- Range
- Linearity
- Sensitivity
- Limit of Detection
- Limit of Quantitation
- Ruggedness
- Accuracy
- Precision
These parameters should be clearly stated in the documented method so that the user
can assess the suitability of the method for their particular needs.
In theory the development should include consideration of all of the necessary aspects
of validation. However, the responsibility remains firmly with the user to ensure that the
validation documented in the method is sufficiently complete to fully meet his or her
needs. Even if the validation is complete, the user will still need to verify that the
documented performance can be met
5.4.2.1 A laboratory seeking accreditation for a more open set of terms of accreditation (where
groups of analytes, for example, “organochlorine pesticides” are specified rather than
individual analytes) must have fully documented procedures covering such elements as:
method selection, method development, method validation or verification, acquisition of
appropriate reference standards or reference materials and staff training. Records of the
application of these procedures will be reviewed as part of each assessment.
5.4.2.2 When standard methods are used, laboratories should verify their own satisfactory
performance against the documented performance characteristics of the method, before
any samples are analysed. Records of the verification must be retained. For published
test methods that do not include precision data, the laboratory must determine its own
precision data based on test data. All methods should include criteria for rejecting
suspect results.
Where a test can be performed by more than one method there must be documented
criteria for method selection. Where relevant the degree of correlation between the
methods should be established and documented.
5.4.2.3 Methods developed in-house must be validated and authorized before use. Where they
are available, certified reference materials should be used to determine any systematic
bias, or where this is not possible results compared with other technique(s), preferably
based on different principles of analysis.
5.4.2.4 All methods shall be fully documented including procedures for quality control, and the
use of reference materials. It is preferable that a common format be adopted for writing
up methods and suitable guidance is given in ISO 78-2:1982, Layout for Standards –
part 2: Standards for chemical Analysis.
Where a change in method involves only minor adjustments, such as sample size,
different reagents, the amended method should be validated and the changes brought to
the attention of NABL at their next visit. Where the proposed change in method involves
a change of scope, such as a significant change in technology or methodology, the
laboratory. Shall inform NABL for appropriate action.
5.4.2.6 Laboratories are required to estimate uncertainty of measurement for the tests being
carried out. This should be on the basis of EURACHEM and GUM where standard
methods include uncertainty factors, laboratories may use them for the estimates.
5.4.3.1 In chemical testing laboratories, computers have a wide variety of uses including:
• control of critical environmental conditions;
• monitoring and control of inventories;
• calibration and maintenance schedules;
• stock control of reagents and standard materials;
• design and performance of statistical experiments;
• scheduling of samples and monitoring of work throughput;
• control chart generation;
• monitoring of test procedures;
• control of automated instrumentation;
• capture, storage, retrieval, processing of data, manually or automatically;
• matching of sample and library data;
• generation of test reports;
• word processing;
• communication
If a testing instrument cannot be isolated from the data processing system, the system
as a whole must be calibrated either statically or dynamically. Each such system will
have to be examined individually.
If the testing instrument can be isolated from the data processing system, the
opportunity is available to calibrate each component of the system separately. The
testing instrument can be calibrated (again, statically or dynamically) in the conventional
manner and a separate verification of the data processing system can be undertaken
incorporating the A/D converters and interfacing systems
Electronic transfer of data should be checked to ensure that no corruption has occurred
during transmission. This can be achieved on the computer by the use of `verification
files’ but wherever practical the transmission should be backed up by a hard copy of the
data.
5.5 Equipment
5.5.1 As part of its quality system, a laboratory is required to operate a programme for the
maintenance and calibration of equipment used in the laboratory. Equipment normally
found in the chemical laboratory can be categorised as:
i) general service equipment not used for making measurements or with minimal
influence on measurements (eg hotplates, stirrers, non-volumetric glassware and
glassware used for rough volume measurements such as measuring cylinders)
and laboratory heating or ventilation systems;
5.5.3.1 The correct use of volumetric equipment is critical to analytical measurements and it
shall be suitably maintained and calibrated. The correct functioning of some specialist
volumetric (and related) glassware is dependent on particular factors, eg the
performance of pyknometers and U-tube viscometers is dependent on ‘wetting’ and
surface tension characteristics, which may be affected by cleaning methods etc. Such
apparatus may therefore require more regular calibration, depending on use. For the
highest accuracy, measurements can often be made by mass depending on properly
calibrated weighing mechanism with traceability to accredited calibration laboratories in
INDIA or abroad APLAC/EA Member Countries rather than by volume.
5.5.3.2 Attention should be paid to the possibility of contamination arising from the equipment or
cross-contamination from previous use. The type used (glass, PTFE, etc), cleaning,
storage, and segregation of volumetric equipment is critical, particularly for trace
analyses when leaching and adsorption can be significant.
5.5.4.1 Correct use combined with periodic servicing, cleaning and calibration will not
necessarily ensure an instrument is performing adequately. Where appropriate, periodic
performance checks should be carried out (eg to check the response, stability and
linearity of sources, sensors and detectors, the separating efficiency of chromatographic
systems, the resolution, alignment and wavelength accuracy of spectrometers etc). See
guidelines published by NATA relating to calibration of equipments / instruments
provided at Annexure B as guidance to the laboratories.
5.5.4.2 The frequency of such performance checks will be determined by experience and based
on need, type and previous performance of the equipment. Intervals between checks
should be shorter than the time the equipment has been found to take to drift outside
acceptable limits.
5.5.4.3 It is often possible to build performance checks – system suitability checks – into test
methods (eg based on the levels of expected detector or sensor response to calibrants,
the resolution of calibrants in separating systems, the spectral characteristics of
calibrants etc). These checks should be satisfactorily completed before the equipment is
used.
5.5.5.1 Wherever physical parameters are critical to the correct performance of a particular test,
the laboratory shall have or have access to the relevant reference standard, as a means
of calibration.
5.5.5.2 Reference standards and accompanying certificates should be stored and used in a
manner consistent with preserving the calibration status. Particular consideration should
be given to any storage advice given in the documentation supplied with the standard.
5.6.1 The overall programme for the calibration of measuring equipment in the chemical
laboratory shall be designed to ensure that, where the concept is applicable, all
measurements are traceable through certificates held by the laboratory, either to a
national or international standard or to a certified reference material. Where no such
reference standard or certified reference material is available, a material with suitable
properties and stability should be selected or prepared by the laboratory and used as a
laboratory reference. The required properties of this material should be characterised by
repeat testing, preferably by more than one laboratory and using a variety of methods,
see ISO Guide 35, Certification of reference materials – General and statistical
principles.
5.6.2 Analytical tests may be sub-divided into three general classes depending on the type of
calibration required:
- See Annexure ‘C’ for calibration of the parameters associated with chemical
analysis. This is taken from ILAC proceedings 1993.
Reference materials and certified reference materials are defined in terms and
definitions.
5.6.4.1 Reference materials provide essential traceability in chemical measurements and are
used to demonstrate the accuracy of results, calibrate equipment and methods, monitor
laboratory performance and validate methods, and enable comparison of methods by
use as transfer standards. Their use is encouraged wherever possible.
5.6.4.2 Where matrix interferences exist, ideally a method should be validated using a matched
matrix reference material certified in a reliable manner. If such a material is not available
it may be acceptable to use a sample spiked with a chemical standard.
5.6.4.4 For many types of analysis, calibration may be carried out using standards prepared
within the laboratory from chemicals of known purity and composition. Some chemicals
may be purchased with manufacturers certificates stating purity. Whatever the source, it
is the users’ responsibility to verify that quality of such standards is satisfactory.
Normally a new batch of a standard should be checked against the old. All chemical
standards should be subjected to inter/intra laboratory comparisons (amongst referred
laboratories).
Standards for compounds (for example: organic compounds) which are not available
with international traceability, should be procured from reputed manufacturers with
assured quality supported by certificate of analysis from the manufacturer
5.6.4.5 The purity requirements of chemical standards may be considered in relation to the
permitted tolerance of the method. For example, a tolerance of <0.1% of the target value
will require a chemical standard to have a certainty of concentration significantly better
than 99.9%.
5.6.4.6 Reference materials and chemical standards should be clearly labeled so that they are
unambiguously identified and referenced against accompanying certificates or other
documentation. Information should be available indicating shelf-life, storage conditions,
applicability, restrictions of use, etc.
5.6.4.7 Reference materials and standards should be handled in order to safeguard against
contamination or loss of determinant. Training procedures should reflect these
requirements.
5.7.1 Selection of an appropriate sample or samples from a larger amount of material is a very
important stage in chemical analysis. It is rarely straight forward. Ideally, if the final
results produced are to be of any practical value, the sampling stages should be carried
out by, or under the direction of an experienced person, with an understanding of the
overall context of the analysis. Sampling is the operation of selecting part of the
elements of a set, so that it precisely represents the distribution of the properties that we
wish to measure in the total set.
5.7.2 The various terms used in sampling are dealt with in detail in recommendations
published by IUPAC. For the purposes of this guidance the definitions of sample, sample
handling, sub-sample, sample preparation and test portion are given in terms and
definitions.
5.7.3 If the test portion is not representative of the original material, it will not be possible to
relate the analytical result measured to that in the original material, no matter how good
the analytical method is nor how carefully the analysis is performed. The final result may
be dependent on the analytical method, it will always be dependent on the sampling
process.
5.7.4 As analytical methodology improves and methods allow or require the use of smaller test
portions the errors associated with sampling become increasingly important. Sampling
errors cannot be controlled by the use of standards or reference materials. Sampling is
always an error generating process and hence demands utmost care.
5.7.6 The extent to which laboratories become involved in sampling varies. Some laboratories
have no responsibility for sampling, others have partial involvement, while many have
total responsibility for both sampling and testing. It is essential that the laboratory have
available fully documented procedures for sampling. These may take the form of existing
National or International Standards. For in-house procedures, these will be assessed on
the basis of the suitability of the documented procedures for their intended purposes. All
sampling equipments and devices specified in a procedure will need to be available, be
well maintained and fully comply with dimensional and other tolerances specified in the
relevant standard.
Supervisory staff, responsible for the design and documentation of sampling procedures,
must be able to demonstrate the validity of the design of these procedures. The training
and supervision of samplers must be shown to be satisfactory. Sampling procedures will
usually be witnessed as part of on-site assessments of laboratories seeking such
registration.
5.7.7.1 All samples must be uniquely and clearly identified. Identification labels must be secure
and legible. Labelling on caps or lids is considered poor practice as it can lead to
possible mixing of sample identities during testing of like batches.
5.7.8.1 On receipt, a sample must be registered into the laboratory records. The form of
registration may vary. In most laboratories, a sample register will be used, but in some
cases, the sample details may be written directly on worksheets or into workbooks.
Some sample information is essential and such criteria are covered in the subsequent
section “Records System”.
5.7.9.1 Sample retention criteria cannot be standardised due to the varying stability and storage
considerations which apply for different materials. Each laboratory’s sample retention
and storage practices are, therefore, examined individually in the light of the types of
materials tested, the use-life of the products or materials which the samples represent
and the likely periods within which a recipient of the test results may request a retest.
5.7.9.2 Samples should be stored so that there is no hazard to laboratory staff and the integrity
of the samples is preserved. Storage areas should be kept clean and organised so that
there is no risk of contamination or cross-contamination, nor of packaging and any
related seals being damaged. Extremes of environmental conditions should be avoided,
which might change the composition of the sample, for example, causing loss of analyte
through degradation or adsorption. If necessary environmental monitoring should be
used. An appropriate level of security should be exercised to restrict unauthorised
access to the samples.
5.7.9.3 All staff concerned with administration of the sample handling system should be properly
trained. The laboratory should have a documented policy for the retention and disposal
of samples. The disposal procedure should take into account the guidelines set out
above
The laboratory should purchase reagents only from reliable and reputed manufacturers.
The laboratory should also ensure that the quality of the reagents used is appropriate for
the tests concerned. The grade of reagent used (including water) should be as stated in
the method together with guidance on any specific precautions which should be
observed in its preparation or use. These precautions include toxicity; flammability;
stability to heat, air and light; reactivity to other chemicals; reactivity to particular
containers; and other hazards.
Labelling of reagents should identify substance, strength, solvent (where not water), any
special precautions or hazards, restrictions of use, and date of preparation and/or expiry.
The person responsible for the preparation of the reagent shall be identifiable either from
the label or from records.
Reagents used as primary standards for volumetric and gravimetric methods should
have a traceability to National and International standards. In cases where primary
standards are not available the reagents should be analytical grade (e.g. AR or GR) and
it should have certificate of analysis from the manufacturer along with it.
Acids and alkalies prepared for volumetric analysis should be periodically checked for
their strength and documented properly.
reference collections
statistical tables
control charts
replicate testing
alternative methods
The level adopted should be demonstrably sufficient to ensure the validity of the results.
As a guide, for routine analysis the level of internal QC typically should be not less than
5% of the sample throughout, i.e. 1 in every 20 samples analysed should be a QC
sample. For more complex procedures, 20% is not unusual and on occasions even 50%
may be required. For analyses performed infrequently, a full system validation should be
performed on each occasion. This may typically involve the use of a reference material
containing a certified or known concentration of analyte, followed by replicate analyses
of the sample and spiked sample (a sample to which a known amount of the analyte has
been deliberately added). Those analyses undertaken more frequently should be subject
to systematic QC procedures incorporating the use of control charts and check samples.
This is a guideline for the applicant laboratories to describe the scope of testing w.r.t.
accreditation
• Industrial alcohols
6.3. Adhesives
• Starch based adhesives
• Natural gums
• Glues
• Polymer based adhesives (Synthetic)
• Coal/coke
• Coal carbonization products
• Coaltar/bitumen
• Charcoal
• Briquetted solid fuels
• Perfumes
• Essential oils
• Cosmetics and toiletries
• Intermediates and miscellaneous chemicals for cosmetics
• Herbal-based cosmetics
• Synthetic dyes
• Dye intermediates
• Natural dyes & colouring materials
6.8. Disinfectants
• Synthetic drugs
• Natural drugs (medicinal plant preparations)
• Pharmaceutical formulation
• Drug intermediates and raw materials
• Veterinary preparations (herbal & synthetic)
• Vitamins
• Vaccines & sera
• Antibiotics
• Enzymes
• Hormones
• Chemicals used in compounding pharmaceuticals
• Ammunitions
• Industrial explosives & associated material
• Pyrotechnics
• Explosives chemicals and allied materials
6.11. Fertilizers
• Nitrogeneous fertilizers
• Phosphatic fertilizers
• Fertilizer mixtures
• Potash fertilizers
• Micronutrients
• Bio-fertilizers
6.13. Inks
• Printing inks
• Writing inks
• Duplicating inks
• Inorganic chemicals
• Organic chemicals
• Electroplating chemicals
• Solvents
• Laboratory chemicals
• Analytical reagents
• Speciality chemicals for:
_ Leather industry
_ Rubber industry
_ Textiles industry
_ Electronics industry
_ Photographic industry
• Agricultural chemicals
• Firefighting chemicals
• Trace elements analysis
• Carbon black
• Wood and timber treatment chemicals
• Lac
• Lac products
6.16. Leather
• Leather
• Synthetic leather
6.17. Lubricants
• Trace elements
• Oils & greases
• Solid lubricants
• Aviation lubricants
• Lubricant additives
• Microcrystalline wax
• Iron ores
• Copper ores
• Zinc ores
• Nickel ores
• Manganese ores
• Tin ores
• Lead ores
• Titanium ores
• Molybdenum and tungsten ores
• Chromium ores
• Precious metals ores
• Rare metals ores
• Radio active metals ores
• Bauxite
• Limestone & dolomite
• Rock phosphate
• Gypsum
• Silica sands
• Mineral sands
• Mineral for refractories
• Mineral for insulation materials
• Other minerals
• Minor elements
• Gem & semi-precious stones
• Geochemical samples for trace elements
• Pulp
• Paper, paper board and speciality papers
• Newsprint and board packing materials
• Composite packing materials
6.22. Petroleum
• Crude petroleum
• Fuels-gaseous, liquid & solid
• Aviation fuels
• Waxes and jellies
• Miscellaneous products, white oil, anti-freeze, solvents insulation oils, feed-stock
• Bituminous asphalt, tars and allied products
• Pour point depressants (flow improvers)
• Resin
• Plastics & polymers
• Raw materials
• Plastic films
6.24. Pesticides
• Liquid effluents
• Solid wastes
• Hazardous solid wastes
• Toxic waste
• Tests related to work place environment & hazards
• Natural rubber
• Synthetic rubber
• Soaps
• Synthetic detergents
• Wetting and emulsifying agents
6.29. Water
• Metallic coatings
• Conversion coatings
• Plating solutions
• Anodizing solutions
• Metal finishing materials
Health and safety are everyone’s responsibility and require the commitment of each employee
to be effective. Management’s commitment is essential for long term success of a health and
safety programme. Such a cooperative relationship will safeguard the employees of the
Laboratory as well as address management’s responsibility and liability.
All elements of the laboratory’s health and safety programme must be clearly documented in a
manual which is readily available to all staff.
evaluation procedures including a plan of the facility showing the location of safety
equipments and fire extinguishers,
policy on the use of protective clothing eg. gowns, coats, gloves, goggles etc.
routine cleaning and disinfection procedures for work benches, floors, centrifuges,
refrigerators, etc,
Material safety data sheets must be available in conjunction with the safety manual. Work
related ‘Accident Insurance’ coverage for all employees shall be provided by the Management.
In large laboratories an officer may be designated as the Health and Safety Manager. Ideally,
the Health and Safety Manager should have received training in occupational health and safety
concepts and in the relevant legislative requirements. The health and safety programme must
be monitored regularly and audited at least annually to ensure that its requirements are being
met.
Sufficient exhaust hoods must be available to maintain a safe work environment. Fume cabinets
must comply with relevant National/International Standards.
Sufficient first aid kits must be available and strategically located. An adequate number of
personnel must be trained in first aid procedures. Appropriate storage must be provided for
volatile, flammable, explosive and other hazardous materials. A flammable liquids storage
cabinet is required for all but small volumes. Acids and solvents should not be stored together. It
may be necessary to store some material in locked cabinets/cupboards and magazines.
Storage on high shelves is discouraged. Suitable carriers must be available to carry large
bottles. The emergency exits from the laboratory must provide safe passage in an emergency.
Evacuation routes must always be kept clear. General cleanliness and good house keeping
must be apparent. Food stuffs must not be kept in laboratory refrigerators/freezers/ ovens. .
There must be a documented ‘waste management programme’ which includes procedures for
the disposal of:
chemical wastes
radioactive waste
A register must be maintained of laboratory accidents, injuries and other incidents and the
follow-up action taken. Suitable protective clothing/equipment must be available at all the times.
The nature of these items will be dependent on the work being undertaken and might include:
laboratory coats/gowns
disposable gloves
rubber gloves
face masks
plastic/rubber aprons
foot wear
When radioactive and X-ray work are performed, detectors must be used regularly to monitor
radiation levels and the wearing of film badges by staff may be necessary. Radiation badges are
to be worn by personnel working in X-ray and radiative hazardous areas. Laboratory shall
monitor control and record radiation levels as required by relevant specification methods and
procedures or where they influence the safety of personnel. Staff must be advised of
appropriate precautionary measures. It is recommended that relevant records be kept.
Appropriate hand-washing and hand-drying facilities must be available. Hand-basins should not
be fitted with domestic taps but with a suitable alternative, for example, elbow or foot-activated
devices. The use of communal towels is discouraged. Single use towels or automatic hand-
drying devices are preferred. A suitable cleaning agent must be available. Gas cylinders must
be secured. Samples/ specimens/exhibits referred to other laboratories must be transported in
accordance with the Indian Post or other relevant requirements.
c) periodic checking (interim but more extensive checking, possibly including partial
calibration);
e) complete recalibration.
Some items of equipment, such as balances, require rechecking or recalibration if they are
moved or repaired. In general, NATA will accept recalibrations by laboratory staff of items
marked * if the laboratory is suitably equipped, appropriate calibration procedures are
documented (along with the applicable measurement of uncertainty) and the staff has
demonstrated it is competent to perform such recalibrations.
Where calibrations are performed by laboratory staff, full records of these measurements must
be maintained, including details of the numerical results, date of calibration and other relevant
observations.
Note: These are not NABL requirements, but are being provided as a reference guideline
for the benefit of the laboratories and their users.
The following requirements for frequency of recalibration and checks on test equipment with
reference to specific calibration and check procedures to be followed. The time intervals
indicated are maximum intervals and are dependent on the accuracy required and the type of
use the instrument is exposed to.
In general, the calibrations are carried out by an external calibrating authority and an endorsed
test report is obtained for this work. If a laboratory wishes to carry out these calibrations in-
house they must demonstrate the capability to do so according to the criteria set out in ISO/IEC
17025: 2005 sub-clause 5.6.2.1.
Checks are normally carried out in-house by the laboratory staff. If however, the checks are
carried out by an external authority then an endorsed test report must be obtained.
12 Service
6 Repeatability check.
BAROMETERS
Fortin Initial
Aneroid 1 60 One point check with transfer instrument.
CALLIPERS (VERNIER) 2 AS 1984
DIAL GAUGES 2 AS 2103
Pressure transducers 1
Calibrators 1
Hand-held, bench type and Initial Check efficacy of automatic cold junction
temperature loggers compensation with the temperature sensor
at the ice point.
Check at ice point.
6
The following table sets out the nominal maximum periods between successive calibrations of
general equipment, not listed in the previous table, for laboratories holding accreditation in the
field of Chemical Testing. Subsequent appendices in this section list specific calibration
requirements for special purpose testing. This table also contains information that expands on
the previous table to aid the chemical laboratories.
Pitot tubes *Initial Check dimensional compliance with BS 1042 Sec 2.1
Annex A.
*On use Inspect tip for damage, blockage, etc as required by BS
1042 Sec 2.1
FURNACES (FOR USE AT *On use Monitor temperature with an appropriate sensor
SPECIFIED TEMPERATURES)
(In addition to other requirements)
GAS METERS *2 years
GAUGE BLOCKS 4years Calibration by an approved testing authority
(reference)
*2 years(working) Check against reference blocks.
† GLASSWARE
(1) Specialised calibrated *Initial AS 2162.1
glassware water traps,
sulphonation flasks,
centrifuge tubes etc
(2) Piston operated *Initial AS *Initial AS 2162.1
2162.2 volumetric apparatus
(see below)
Pipetters *Initial Check volume delivered. For adjustable devices check
volume delivered at several settings (refer to AS 2162.2).
*3 months Check volume delivered at settings in use.
Dispensers *Initial Check volume delivered. For adjustable devices check
volume delivered at several settings (refer to AS 2162.2).
*3 months Check volume delivered at settings in use.
Diluters *Initial Check sample and diluent volumes or dilution ratio and
total volume (refer to AS 2162.2).
*6 months Check sample and diluent volumes or dilution ratio and
total volume (refer to AS 2162.2).
Displacement burettes *Initial Check volume delivered at maximum and two other
settings.
*When Check volume delivered at maximum and two other
barrel/plunger is settings.
changed
HYDROMETERS
In addition to other requirements *On use Check that scale has not slipped.
OVENS
In addition to other *On use Monitor temperature throughout use, with appropriate
requirements sensor, and record temperature daily.
Ageing *Daily Monitor with appropriate sensor and record.
Drying *On use Monitor with appropriate sensor and record.
*1 month
*3 months
*1 year
NOTES
(I) The period given between successive calibrations is a maximum period. More frequent calibrations may be
required if the equipment is repaired, moved, is in constant use or a change in operating circumstances
occurs.
(II) Accredited coal laboratories must maintain adequate quality control in supervision of equipment performance
by the use of appropriate reference materials on a regular basis.
(III) Whenever possible, unless otherwise stated in the relevant standard, equipment should contain all items of
apparatus specified in the test method when being calibrated.
(IV) The calibration requirements for other general items of equipment used in coal and coke testing (eg. balances,
thermometers, thermocouples, volumetric glassware, etc) are found in this booklet in Calibration Appendices A
and B.
† Krebs-Stormer viscometer is considered acceptable as long as it gives a value within ± 15% of the expected
load for 200 rpm for a given oil and within ± 5% of the consistency in Krebs units.
+ If dimensions do not conform, the instrument must be calibrated with two standard viscosity oils to ASTM D562
++ Standard oils need only be replaced every 2 years if correctly stored (in the dark, at the room temperature, in
closed glass or tinned metal containers, free from contaminants).
Accreditation for colour and viscosity of resins using Gardner colour standards and Gardner-
Holdt viscosity standards (to Federal Test Method. Standard No 141a and ASTM Methods) is
granted on the basis that the applicant can obtain results comparable with laboratories already
accredited for these tests, as an alternative to fundamental calibration of these standards.
NATA Technical Note 1 details requirements for accreditation of quality control testing of paint.
These calibrations should be performed by approved testing authorities using gases of known
concentrations or NATA approved blending techniques appropriate to the gas being measured.
GAS DETECTION INSTRUMENTS Before use Span and zero 1 point span check made on 75%-90% of full
for use in mines, and also for check (weekly on field scale of range being used. (At approximately
industrial and commercial instruments used for 50% for combustible gas detectors with an
applications continuous monitoring) output scale of zero to 100% lower explosive
limit).
*6 months complete Six point (and zero) for NDIRS (with
recalibration recommended values of 15, 30, 45, 60, 75
and 90% full scale deflection).
(iv) The initial calibration must check interferences. The laboratory should be aware of the
contaminants which may create cross-sensitivity.
(v) Calibrations must be performed more frequently (see Note (ii)) if poisons are likely to be
present for any catalytic sensor.
(vi) Calibrations using 2 or 3 points (and zero) must adequately cover the range. One point
must be between 75% and 90% of full scale, except for fixed or stationary instruments
used in explosive atmospheres with scales 0 - 100% lower explosive limit, the highest
calibration point approximately 50% lower explosive limit.
(vii) For single point instrument alarms, a one-point calibration is performed at the level at
which the instrument alarms.
(viii) Fixed instruments with remote head should be calibrated in-situ, where possible, but if
calibrated in a laboratory suitable leads (same resistance) must be used. Also a polarity
check should be made when the instrument is reassembled.
(ix) The gas flow rates necessary for optimum response of flame ionisation detectors should
be checked regularly. Zero checks must be made with high purity gases (depending on
precision and accuracy required). Oxygen-quenching effects must be determined on
commissioning only.
(x) For low level alarms (and semiconductor type detectors) all operating parameters must
be included on the calibration certificate and the instrument must be calibrated with the
gas type which the instrument is to measure.
(xii) Wosthoff pumps and gas dividers should be checked annually by an accredited testing
authority.
Endorsed test documents must only relate to the calibration of the instrument. Any servicing,
maintenance or opinions on the performance of the instrument must appear on a separate, non-
endorsed attachment.
In addition, there must be traceability to the reference gases used for calibration or the method
of generating references (eg. Wosthoff Pump). This must be stated, either on the report or on
the relevant work sheets.
The following table lists the requirements for periodical calibration of instruments and test
equipment used for motor vehicle emission testing by testing laboratories holding accreditation
in the field of Chemical Testing:
CONSTANT VOLUME *500 hours of use after ADR 37/00 - Appendices 5 (Method), 12
stabilising period or
SAMPLER major maintenance
Positive Displacement Pump
Critical Flow Venturi *As indicated by CVS Reference Standard; Air Flow Meter (Laminar Flow
system verification Element, Subsonic Venturi or orifice plate).
Calibration traceable to NIST. Accuracy 1 % of air
flow.
System verification *1 week or after Using CP Propane (C3H8) or Carbon Monoxide or
Carbon Dioxide.
Propane maintenance or
servicing of system
Carbon Monoxide System accuracy in the order of 2% critical flow
orifice or “bomb” method
Carbon Dioxide NOTE: Precautions for use of pure carbon
monoxide
Correlation car *As required to Approved in-house laboratory methods.
supplement other
methods
FOR POSITIVE DISPLACEMENT PUMP (PDP) TYPE OR CRITICAL FLOW VENTURI (CFV)
TYPE.
PA
HSE/NPL TEST SLIDE *On use Used when setting up the microscope prior to
counting each batch of slides. Use to be recorded
WALTON –BECKETT *Measured on NOHSC Guidance Note, 1988
installation then every
GRATICULE 12 months and
whenever the
interpupiliary distance,
objective,
intermediate
magnification, or, on
some microscopes,
the eyepieces are
changed.
Note: For
microscopes
embodying a
magnification change,
the graticule must be
measured prior to
counting each batch
of slides.
PUMPS
(Where accreditation is
held/sought for volume
measurement.)
Direct automatic flow control *12 months. After 3 Constant flow compensation. Refer to calibration
consecutive tests consecutive tests (ie. Appendix J
2 years) showing
results within ±5% of
the expected result,
the interval can be
lengthened to 3 years.
Indirect automatic flow- *6 months. After 3 As above
control consecutive tests (ie.
12 months) showing
results within ±5% of
the expected result,
the interval can be
lengthened to 12
months
SERVICING OF MICROSCOPES
The following servicing must be done on microscopes annually and all defects rectified as
necessary. The service may be carried out either in-house by suitably trained laboratory staff or
externally.
- Checking all optical alignments such as oculars, objectives, binocular tube, condenser
and illumination system for surface and mount defects.
- Checking for vertical, horizontal and rotational displacement of images in binocular tube
- Checking, lubricating (as necessary) and adjusting all mechanical moving parts, such as
condenser rack, stage controls and field diaphragm.
- Checking all optical alignments such as oculars, objectives, binocular tube, condenser
and illumination system for surface and mount defects.
- Checking for vertical, horizontal and rotational displacement of images in binocular tube.
3. Stereo Microscopes
- Checking, lubricating (as necessary) and adjusting all mechanical moving parts, such as
focusing rack and zoom controls.
- Checking all optical alignments such as oculars, binocular tube, objective and
illumination system for surface and mount defects.
ISO/IEC
Before being placed into service, after three months, and then after a further three months,
the following tests must be done on every indirect automatic flow-control pump used by
the laboratory.
a) Test each pump at each flow rate that is used. For example, if the pump is used at
1.0, 2.0 and 4.0 litres/ minute, then it must be tested at 1.0, 2.0 and 4.0 litres/
minute.
b) Set the pump flow rate to the chosen flow rate using a flow meter. No other flow
resistance should be in the circuit.
e) If the flow rate changes by more than 5%, the pump’s constant flow compensation
must be reset.
f) Repeat steps a) to e) with the pump set to each relevant flow rate.
g) If the above tests produce results inside the +/-5% range for tests on three
consecutive occasions, ie. 12 months, then future tests need only be done at twelve-
monthly intervals.
h) If any internal components of the pumps have been serviced or changed, the test
must be repeated before the pump is placed back into service. Pumps that have the
circuit board flow compensation potentiometers accessible must not be used until
the access is blocked so as to prevent accidental adjustment.
b) If any internal components of the pumps have been serviced or changed, the test
must be repeated before the pump is placed back into service. Pumps that have the
circuit board flow compensation potentiometers accessible must not be used until
the access is blocked so as to prevent accidental adjustment.
c) If these tests produce results inside the +/-5% range after two consecutive tests (ie.
one year), then future tests need only be done at three yearly intervals.
Note: The tests are based on the flow rate/pressure drop characteristics of 25mm
diameter, 0.8mm pore size and mixed esters of cellulose membrane filters.
Different test conditions may be necessary if other types of filters are used.
a) reliably deliver the correct flow rate immediately after automatic switch-on
i. time in-built pump timer over a typical sampling period and record timer’s
“elapsed time”
ii. repeat step i for each sampling period likely to be used
iii. repeat steps i to ii for each pump used
iv. repeat steps i to iii on three separate occasions
v. accept a pump if pump timer elapsed time is within +/-1% of actual elapsed time
ISO/IEC 1
7025 APPLIC APPLICATION TION DOCU DOCUMENT
d) reliably switch off automatically in the event of a flow fault such that the final flow rate
is within +/-10% of the initial flow rate
Each pump must be tested and records kept of all of the aspects described above.
If the tests described under d) and e) above have not been done, any sample subject to
automatic switch-off due to a flow fault or low battery must be rejected.
A laboratory can submit to NATA for review and approval an alternative series of tests to
those described above, provided that they achieve the same aim. One alternative may be
the measurement of air volumes, actually sucked by a pump during automatic operation.
The test procedures for any alternative would need to be described in detail.
The reference and working equipment listed in previous appendices are calibrated (in most
cases) by reference to fundamental physical standards of measurement and their derivatives.
Other techniques have been included in the previous appendices to be consistent with the
grouping of equipment for specific testing procedures.
This Appendix lists major analytical instrumentation used in the laboratory, that are calibrated
primarily in-house by use of reference materials of known composition.
In the field of Chemical Testing the following general principles apply to the use of analytical
instrumentation.
a) Sufficient and appropriate reference materials must be used to calibrate instruments over
the full analytical range required to establish the measurement characteristics of the
instrument (linearity, sensitivity, etc).
Where Australian Standards have been published for particular instrumental techniques it is
expected that these will be used in the laboratory. Where this is not the case, relevant ASTM or
other verified procedures must be used. In many cases published procedures for the operation
of analytical instrumentation are unavailable or are specific to a particular application. NATA will
then require a laboratory to document its practice for use of analytical instrumentation. For
example, this may include a description of the operation of the instrument, calibration
procedures, specification of error-boundaries on the nominal values of calibration standards,
frequency of use and nature of quality control samples, the analytical precision at various
concentration levels, and maintenance procedures.
Calorimeters
Determine water equivalents using certified benzoic acid at six monthly intervals
Conductivity Meters
Conduct a one-point check on use and check the complete scale each year. Refer ASTM
D1125.
pH Meters
Check on use with at least 2 standard buffer solutions appropriate to the anticipated pH of the
sample being tested. A record of the checks must be kept. Refer to APHA 4500-H and BS 1647.
The reference electrode junction must also be checked at least weekly, or more frequently if
samples are solid or semi-solid. Refer AS 2300.1.6 and NATA Technical Note 21.
Turbidimeters
Conduct a one-point check appropriate to the anticipated turbidity of the sample being
measured, and a complete calibration each year. Refer APHA 2130B. (Reference standards
may be purchased or made up in the laboratory. Check Hach standards annually against
formazin standards.)
Autoanalysers
Appropriate reference materials must be analysed at regular intervals during each run of the
instrument and records kept of within batch and between batch uncertainties. (The scheduled
use of duplicates and recovery checks by spiking samples is also recommended.) Daily, weekly,
monthly and yearly maintenance and calibration checks must be carried out in accordance with
manufacturer’s specifications or with practical scientific alternatives derived from experience.
Maintenance and calibration procedures must be established and a log kept of maintenance
carried out and the results of calibration checks.
Spectrophotometers
A great number of the quantitative analyses performed in a chemical testing laboratory involve
some form of spectrophotometric or colorimetric measurement. It is essential that a laboratory
carry out regular, recorded calibration checks on all spectrophotometers or automated devices
employing spectrophotometers or colorimeters. A new calibration curve must be drawn at least
every month.
Such calibrations must include checks on wavelength accuracy, absorbance, linearity, straylight
and matching of cells. These calibrations must be carried out in accordance with the
manufacturer’s instructions and/or the codes of practice listed below at intervals appropriate to
the test procedures and the physical environment within which the instrumentation is used (but
at least every three months).
All instruments must be checked on use against appropriate reference materials. A blank and at
least two points on the calibration curve must also be checked. These calibrations should be
compared over time to detect any system deterioration.
a) Ultraviolet / visible:
b) Infrared:
Spectrometers
Instrument performance must be routinely monitored during use with reference materials.
Calibration graphs must be prepared using a blank and three to five solutions of standards
covering the expected concentration range of analyte in the sample. Linearity checks must be
done in the absorbance mode. Spectrometer components and supporting equipment must also
be adequately maintained and checked periodically in accordance with documented procedures
to ensure optimal instrument performance. (This may need to be done by external technicians.)
Relevant standards for the checking and use of spectrometers include:
The Association will consider submissions from any laboratory that proposes the use of a
factory calibrated atomic emission (arcspark) spectrometer. Each case will be considered
on its merits.
ASTM E386 Practice for data presentation relating to high resolution NMR
spectroscopy.
Chromatographs
(a) Gas chromatographs:
Instrument performance must be routinely monitored during use with reference materials.
System components (eg. integrators, ovens, electronic amplifiers and detectors) must also
be checked periodically, and records kept.
The total system must be monitored during use with reference standards. Loss of
efficiency may be detected by chronological comparison of reference material
measurements. System components (eg. pumping system and detectors) must be subject
to periodic checks and details must be recorded.
ASTM F660 Practice for comparing particle size in the use of alternative types of
particle counters.
ASTM F661 Practice for particle count and size distribution measurement in batch
samples for filter evaluation using an optical particle counter.
ASTM F662 Method for measurement of particle count and size distribution in batch
samples for filter evaluation using an electrical resistance particle counter.
Computerised systems
INTRODUCTION
The calibration of the parameters associated with chemical analyses and material tests
deserves particular attention. Because major errors can be made by neglecting or ignoring the
basic principles of metrology which also apply to these areas. This text identifies a number of
general recommendations for those who are faced with this problem, either as laboratories or as
assessors.
Basic considerations
Any measurements, particularly any quantitative chemical analysis, must employ reference
elements to ensure demonstrated traceability to the relevant basic quantities. This is an
essential condition for the accuracy of the results.
• The intrinsic uncertainty of the reference used {set of calibration masses, titrated solutions,
gas mixtures, composition CRMs* etc. (see remarks)}
• The appropriateness (or fitness for purpose) of this reference under the practical
conditions of use, also taking account of the analytical method used and the samples
tested.
Figure 1
R1 > R2
Appropriateness
R1 Error : 1 %
R2 Appropriateness
Error : 0.5 %
The analyst should compare the uncertainty of calibration with the required total analytical
uncertainty (which should normally be agreed between the customer and the operator). This
comparison provides a useful guide for choosing between different available calibration
procedures and in the longer term, for improvements to the methods and procedures.
- Calculable method
- Relative method
- Comparative method
• a basic principle
• a number of basic pre-requisites.
When the user classifies a method, it should be done by means of a detailed and close
examination of all the parameters of the analytical procedure. He must never be satisfied
with simplifications which would only be applicable to the detection principle applied under
idealized conditions. This approach generally has the effect of under estimating the
necessary conditions for a reliable calibration and of generating systematic errors.
The above classification is merely designed to identify the relevant calibration mode (s). It
must not be used as a scale of value of the methods.
Calculable method
This is a method that produces the anticipated result by performing a calculation defined on
the basis of the laws governing the physical and chemical parameters involved, using
measurements taken during the analysis, such as:
o weight of the test sample, volume of titration reagent,
o weight of precipitate, volume of titration product generated.
Relative method
This method compares the sample to be analysed with a set of calibration samples of known
content, using a detection system for which the response (ideally linear) is recognised in the
relevant working area (without necessarily being calculable by theory). The value of the
sample is determined by interpolation of the sample signal with respect to the response
curve of the calibration samples.
This implies that any other difference of composition, form, etc. between the calibration set
and the different samples analysed will have no effect, or a negligible effect compared with
the uncertainty on the signal. For this condition to be satisfied the analytical procedure
could include:
o Means to reduce sensitivity to differences (e.g. spectral buffer, treatment of samples
before analysis)
o A procedure to give similar form to the calibration set and the samples:
- Reduce the complex sample to a simpler sample, by acid digestion, the removal of
major interferents or selective extraction of analyte.
For this type of method, the sample to be analysed is compared to a set of calibration
samples, using a detection system which has to be recognised to be sensitive not only to
the content of elements or molecules to be analysed, but also to differences of matrix (of
any type whatsoever). If this influence is ignored it will generate a systematic error (bias).
• To identify the type(s) of samples routinely analysed (type of matrix, type of structure
etc.) and to draw up procedures to identify the introduction of “abnormal” samples in
comparison with the identified types.
• To make up a set of CRMs suitable for each type of sample previously identified.
EXAMPLES *
2) Water in powders
Calculable method: Karl Fisher Titration
Assessors giving accreditation to such methods should take great care to check that the
method is undertaken in such a way that appropriate accuracy is ensured through relevant
procedures and means and preferably that they are widely recognized as state of the art
methods.
2. CALIBRATION PROCEDURES
• Calculable method
The basic procedure is to identify every quantity whose measurement is necessary to
establish the analytical result by calculation.
With this type of method, CRMs are used for verification (see ISO Guide 33). Note that
the CRM must be analysed as presumed unknown, the result obtained being compared
with the certified value. If an abnormal deviation is observed, the laboratory must
identify the cause and correct it. It is not recommended (except for very specific cases)
to deduce a correction factor for the difference between the value found and the certified
value.
• Calibration of the system for measuring the correction parameters applied to the
foregoing measurements (e.g. temperature, pressure, relative humidity). Since the
uncertainties of these quantities are generally of the second order with respect to
the total analytical uncertainty, a simplified calibration procedure is often adequate.
• Knowledge of the purity of the basic materials used, together with their
uncertainties.
For “diluents” particular attention must be paid to the residual level of impurities such as:
For practical or economic reasons, laboratories may decide to use commercial standard
solutions. If so, it is important to make sure that the uncertainty on their content is
known, as required, and that the basic rules set forth above are complied with by the
manufacturer, as attested by appropriate documentation.
For this type of method, CRMs are chiefly used as a means of verification.
• Comparative method
Since these methods are sensitive to matrix effects, the calibration procedures employed
must take account of these effects. The use of an appropriate CRM is the preferable
calibration method. The choice of the CRM to be used must therefore satisfy two types
of necessary conditions:
- That the matrix of the standard is sufficiently similar to the samples being analysed
and that the existing differences are not liable to generate a bias in the results that is
incompatible with the total uncertainty desired.
The selection of a suitable CRM should aim to achieve an optimum between these two
types of necessity.
The CRM must initially be defined in the form of a tentative specification; the points to be
considered include:
- What are the elements whose concentrations must be known with sufficient accuracy
to permit the establishment of the calibration? Over what concentration range? With
what uncertainty? For what sample size?
- What should be the type of matrix; type of material and main components (which
could have a “chemical” or “physical” influence on the response of the analyzer)?
- What other properties or characteristics of the samples and the standards should be
similar to avoid generating a bias in the responses of the analyzer? For example:
form, viscosity, particle size distribution, metallurgical structure, etc.
The first approach in this search is to compare the tentative specification of the CRM
required with the lists of CRMs available on the international market. The laboratory
should consult:
The laboratory must ensure that the CRMs that were short-listed after a first
examination:
- Are effectively certified for the element concerned, and that the value is not merely
indicative (see certificate)
As to similarity of matrix, the laboratory must weigh the fact that it is not economically
and technically possible to obtain a perfect match between CRMs and samples in all
cases. Reasonable similarity must be deemed acceptable. If not, the entire analytical
procedure has to be reconsidered.
The laboratory that decides not to use appropriate available CRMs should accordingly
justify the reasons for this decision in its procedures.
Should the market fail to offer a CRM to meet a laboratory’s identified needs, it may
attempt to develop its own internal RM. Since this usually means a lengthy and costly
operation, involving the use of special resources and experience, it would be wise to
firstly explore the following possibilities:
- Contact groups of users with the same need and try to set up a joint project, possibly
with the assistance of the national laboratory responsible for CRMs.
General Remarks
Calibration is an integral part of analysis and its cost is an integral part of the cost of analysis. It
must be planned and provided for, especially if it involves purchasing CRMs or developing
internal RMs. An under estimation of these costs does not justify an inadequate calibration
procedure.
The calibration of chemical analyses must meet a number of essential requirements, such as
those set forth in this Guide. Compliance to such requirements may involve different forms in
different fields. These general recommendations are not sufficient conditions for quality in
calibration. Every user must indicate:
At all events, he must identify and analyse his need in its different aspects and draw up and
implement a response for each.
Accurate analyses depend not only on the metrological quality of the calibration but also on
other factors including random and systematic errors which occurs during the analysis.
Note: This annexure may be treated as a guideline and not as NABL requirement.