MS 1850 14 2009 Full

MS 1850-14:2009
MALAYSIAN
STANDARD
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WATER QUALITY - SAMPLING - PART 14:

GUIDANCE ON QUALITY ASSURANCE OF
ENVIRONMENTAL WATER SAMPLING AND
HANDLING
(ISO 5667-14:1998, IDT)
ICS: 13.060.45
Descriptors: water, quality, water pollution, sampling, handling, quality assurance, rules (instructions)
© Copyright 2009
DEPARTMENT OF STANDARDS MALAYSIA
DEVELOPMENT OF MALAYSIAN STANDARDS
The Department of Standards Malaysia (STANDARDS MALAYSIA) is the national

standardisation and accreditation body.
The main function of the Department is to foster and promote standards,

standardisation and accreditation as a means of advancing the national economy,
promoting industrial efficiency and development, benefiting the health and safety of
the public, protecting the consumers, facilitating domestic and international trade and
furthering international cooperation in relation to standards and standardisation.
Malaysian Standards are developed through consensus by committees which

comprise of balanced representation of producers, users, consumers and others with
relevant interests, as may be appropriate to the subject in hand. To the greatest
extent possible, Malaysian Standards are aligned to or are adoption of international
standards. Approval of a standard as a Malaysian Standard is governed by the
Standards of Malaysia Act 1996 (Act 549). Malaysian Standards are reviewed
periodically. The use of Malaysian Standards is voluntary except in so far as they are
made mandatory by regulatory authorities by means of regulations, local by-laws or
any other similar ways.
The Department of Standards appoints SIRIM Berhad as the agent to develop

Malaysian Standards. The Department also appoints SIRIM Berhad as the agent for
distribution and sale of Malaysian Standards.
For further information on Malaysian Standards, please contact:
Department of Standards Malaysia OR SIRIM Berhad

Century Square, Level 1 & 2 (Company No. 367474 - V)
Blok 2300, Jalan Usahawan 1, Persiaran Dato’ Menteri
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http://www.standardsmalaysia.gov.my http://www.sirim.my
E-mail: [email protected]
© STANDARDS MALAYSIA 2009 – All rights reserved

MS 1850-14:2009
CONTENTS
Page
Committee representation...........................................................................................................ii
National foreword ....................................................................................................................... iii
1 Scope ............................................................................................................................ 1
2 Normative references.................................................................................................... 1
3 Definitions ..................................................................................................................... 1
4 Sources of sampling error............................................................................................. 4
5 Sampling quality control techniques ............................................................................. 5
6 Transport, stabilization and storage of samples ......................................................... 12
7 Analysis and interpretation of quality control data ...................................................... 13
8 Sample identification and records............................................................................... 13
Annex A Control charts .......................................................................................................... 14
Annex B Bibliography............................................................................................................. 18
© STANDARDS MALAYSIA 2009 - All rights reserved i

MS 1850-14:2009
Committee representation
The Industry Standards Committee on Chemical and Materials (ISC B) under whose authority this Malaysian
Standard was adopted, comprises representatives from the following organisations:
Department of Standards Malaysia

Malaysian Association of Standards Users
Malaysian Ceramic Industry Group
Malaysian Institute of Chemistry
Malaysian Paint Manufacturers Association
Malaysian Pulp and Paper Manufacturers Association
Minerals and Geoscience Department Malaysia

Ministry of Agricultural and Agro-based Industry (Department of Agriculture Malaysia)
Ministry of Defence (Science and Technology Research Institute for Defence)
Ministry of International Trade and Industry
Ministry of Science, Technology and Innovation (Department of Chemistry, Malaysia)
Universiti Malaya
Universiti Sains Malaysia
The Technical Committee on Water Quality which supervised the adoption of the ISO Standard consists of
representatives from the following organisations:
Alam Sekitar Malaysia Sdn Bhd

Atomic Energy Licensing Board
Department of Chemistry, Malaysia
Department of Environment, Malaysia
Department of Irrigation and Drainage
Lembaga Urus Air Selangor
Malaysian Nuclear Agency
Malaysian Water Association
Ministry of Energy, Water and Communication
Ministry of Health Malaysia
National Water Services Commission
SIRIM Berhad (Environmental and Bioprocess Technology Centre)
SIRIM Berhad (Secretariat)
SIRIM QAS International Sdn Bhd (Chemical Testing Section)
Syarikat Bekalan Air Selangor Sdn Bhd
Universiti Putra Malaysia
The Working Group on Sampling (Water Quality) which recommended the adoption of the ISO Standard consists of
representatives from the following organisations:
Alam Sekitar Malaysia Sdn Bhd

ALS Technichem (Malaysia) Sdn Bhd
Department of Chemistry, Malaysia
Department of Environment, Malaysia
Department of Irrigation and Drainage
Department of Occupational Safety and Health Malaysia
Fisheries Research Institute
Indah Water Konsortium Sdn Bhd
Jabatan Kerja Raya Malaysia
Malaysia Marine Department
Malaysian Nuclear Agency
Malaysian Water Association
Ministry of Health Malaysia (Engineering Services Division)
Ministry of Health Malaysia (Food Safety and Quality Division)
Ministry of Housing and Local Government
SIRIM Berhad (Environmental and Bioprocess Technology Centre)
SIRIM Berhad (Secretariat)
Syarikat Bekalan Air Selangor Sdn Bhd
ii © STANDARDS MALAYSIA 2009 – All rights reserved

MS 1850-14:2009
NATIONAL FOREWORD
The adoption of the ISO Standard as a Malaysian Standard was recommended by the
Working Group on Sampling (Water Quality) under the authority of the Industry Standards
Committee on Chemical and Materials.
This Malaysian Standard is identical with ISO 5667-14:1998, Water quality - Sampling - Part
14: Guidance on quality assurance of environmental water sampling and handling, published
by the International Organization for Standardization (ISO). However, for the purposes of this
Malaysian Standard, the following apply:
a) in the source text, "this International Standard" should read "this Malaysian Standard";
b) the comma which is used as a decimal sign (if any), to read as a point; and
c) reference to International Standards should be replaced by equivalent Malaysian

Standards as follows:
Referenced International Standards Corresponding Malaysian Standards
ISO 5667-1:1980, Water quality - MS 1850-1, Water quality - Sampling - Part 1:

Sampling - Part 1: Guidance on the design Guidance on the design of sampling
of sampling programmes programmes
ISO 5667-3:1985, Water quality - MS 1850-3, Water quality - Sampling - Part 3:

Sampling - Part 3: Guidance on the Guidance on the preservation and handling of
preservation and handling of samples samples
Compliance with a Malaysian Standard does not of itself confer immunity from legal
obligations.
NOTE. IDT on the front cover indicates an identical standard i.e. a standard where the technical content, structure,
and wording (or is and identical translation) of a Malaysian Standard is exactly the same as in an International
Standard or is identical in technical content and structure although it may contain the minimal editorial changes
specified in clause 4.2 of ISO/IEC Guide 21-1.
© STANDARDS MALAYSIA 2009 - All rights reserved iii

MS 1850-14:2009
© ISO ISO 5667-14:1998(E)
Foreword
ISO (the International Organization for Standardization) is a world-wide federation of national standards bodies (ISO
member bodies). The work of preparing International Standards is normally carried out through ISO technical
committees. Each member body interested in a subject for which a technical committee has been established has
the right to be represented on that committee. International organizations, governmental and non-governmental, in
liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical
Commission (IEC) on all matters of electrotechnical standardization.
Draft International Standards adopted by the technical committees are circulated to the member bodies for voting.
Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote.
International Standard ISO 5667-14 was prepared by Technical Committee ISO/TC 147, Water quality,
Subcommittee SC 6, Sampling (general methods).
ISO 5667 consists of the following parts, under the general title Water quality — Sampling :
 Part 1: Guidance on the design of sampling programmes
 Part 2: Guidance on sampling techniques
 Part 3: Guidance on the preservation and handling of samples
 Part 4: Guidance on sampling from lakes
 Part 5: Guidance on sampling of drinking water
 Part 6: Guidance on sampling of rivers and streams
 Part 7: Guidance on sampling of water and steam in boiler plants
 Part 8: Guidance on sampling of wet deposition
 Part 9: Guidance on sampling from marine waters
 Part 10: Guidance on sampling of waste waters
 Part 11: Guidance on sampling of groundwaters
 Part 12: Guidance on sampling of bottom sediments
 Part 13: Guidance on sampling of water, wastewater and related sludges
 Part 14: Guidance on quality assurance of environmental water sampling and handling
Annexes A and B of this part of ISO 5667 are for information only.
iv © STANDARDS MALAYSIA 2009 - All rights reservediii

ISO 5667-14:1998(E) MS 1850-14:2009
1850-14: 2009
© ISO
Introduction
Quality control procedures are required for the collection of environmental water samples for the following reasons:
a) to monitor the effectiveness of sampling methodology;
b) to demonstrate that the various stages of the sample collection process are adequately controlled and suited to
the intended purpose, including adequate control over sources of error such as sample contamination, loss of
determinand and sample instability. To achieve this quality control procedures should provide a means of
detecting sampling error and hence a means of rejecting invalid or misleading data resulting from the sampling
process ;
c) to quantify and control the sources of error which arise in sampling. Quantification gives a guide to the
significance that sampling plays in the overall accuracy of data;
d) to provide information on suitably abbreviated quality assurance procedures that may be used for rapid
sampling operations such as pollution incidents or groundwater investigations.
This part of ISO 5667 is one of a group of International Standards dealing with the sampling of waters. It should be
read in conjunction with the other parts of ISO 5667 and in particular with Parts 1, 2 and 3.
The general terminology is in accordance with that published in ISO/TC 147, Water quality, and more particularly
with the terminology on sampling given in ISO 6107-2.
iv© STANDARDS MALAYSIA 2009 - All rights reserved v

INTERNATIONAL STANDARD © ISO MS5667-14:1998(E)
ISO 1850-14:2009
1850-14: 2009
Water quality — Sampling —
Part 14:
Guidance on quality assurance of environmental water sampling and
handling
WARNING: Consider and minimize any risks and obey safety rules. See ISO 5667-1 for certain safety
precautions, including sampling from boats and from ice-covered waters.
1 Scope
This part of ISO 5667 provides guidance on the selection and use of various quality assurance techniques relating
to the manual sampling of surface, potable, waste, marine and ground waters;
NOTE The general principles outlined in this part of ISO 5667 in some circumstances may be applicable to sludge and
sediment sampling.
2 Normative references
The following standards contain provisions which, through reference in this text, constitute provisions of this part of
ISO 5667. At the time of publication, the editions indicated were valid. All standards are subject to revision, and
parties to agreements based on this part of ISO 5667 are encouraged to investigate the possibility of applying the
most recent editions of the standards indicated below. Members of ISO and IEC maintain registers of currently valid
International Standards.
ISO 5667-1:1980, Water quality — Sampling — Part 1: Guidance on the design of sampling programmes.
ISO 5667-3:1985, Water quality — Sampling — Part 3: Guidance on the preservation and handling of samples.
3 Definitions
For the purposes of this part of ISO 5667, the following definitions apply.
3.1
accuracy
closeness of agreement between a test result and the accepted reference value
[ISO 3534-1]
NOTE The term accuracy, when applied to a set of test results, involves a combination of random and systematic error or bias
components.
3.2
bias
difference between the expectation of the test results and an accepted reference value
[ISO 3534-1]
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NOTE Bias is the total systematic error as contrasted to random error. There may be one or more systematic error
components contributing to the bias. A larger systematic difference from the accepted reference value is reflected by a larger
bias value.
3.3
precision
closeness of agreement between independent results obtained under stipulated conditions
[ISO 3534-1]
NOTE 1 The variation associated with test results from repeated sampling operations will be subject to variation from
analytical sources as well as from sources connected with the sampling process. A comparison of random error from repeated
sampling operations with that from repeated analysis of the same sample can be used to deduce the contribution of sampling
to overall random error.
NOTE 2 Precision depends only on the distribution of random errors and does not relate to the true value or the specified
value, (ISO 3534-1). The measure of precision is expressed in terms of a standard deviation value. Improved precision is
reflected in a smaller standard deviation value.
NOTE 3 The ‘independence’ of test results reflects the extent to which results are obtained in a manner not influenced by
any previous result on the same test object (ISO 3534-1). Quantitative measures of precision depend critically on stipulated
conditions. The well-known terms ‘repeatability’ and ‘reproducibility’ relate to specific types of stipulated conditions. The former
term corresponds to measurements made under the same controlled (same method, strictly adhered to in the same laboratory)
conditions; the latter term refers to the same method used in different laboratories.
3.4
representativeness
extent to which the condition of all the samples taken from the body of water reflects conditions in water of interest
3.5
comparability
degree of agreement with respect to control over random and systematic errors
3.6
Certified Reference Material
CRM
stable, homogeneous material, with a composition closely matching that of the sample to be analysed, for which the
concentrations of the determinands of interest in that material are known with a known degree of uncertainty
NOTE In most chemical analyses the traceability of measurement can be obtained by a series of calibrations that
demonstrates that no loss of determinand or contamination occurs during the sample treatment. This traceability can be based
on the analysis of a CRM.
3.7
blank
observed value obtained when measurement is made on a sample identical to the sample of interest, but in the
absence of the determinand.
NOTE Field blank samples are laboratory blank samples which are taken into the field, treated as samples and analysed as a
check on sampling procedures.
[ISO/TR 13530]
3.8
spike
known quantity of determinand which is added to a sample, usually for the purpose of estimating the systematic
error of an analytical system by means of a recovery exercise
[ISO/TR 13530]
2 © STANDARDS MALAYSIA 2009 - All rights reserved

© ISO MS5667-14:1998(E)
ISO 1850-14:2009
3.9
recovery
extent to which a known, added quantity of determinand in a sample can be measured by an analytical system.
NOTE Recovery is calculated from the difference between results obtained from a spiked and an unspiked aliquot of sample
and is usually expressed as a percentage.
[ISO/TR 13530]
3.10
control chart
chart, with upper and lower control limits, on which values of some statistical measure for a series of samples,
spiked samples and blanks, are plotted, usually in date or sample number order
NOTE 1 The chart frequently shows a central line to assist detection of a trend of plotted values toward either control limit.
[ISO 3534-2]
NOTE 2 In some control charts, the control limits are based on the within-batch data plotted on the chart; in others, the
control limits are based on adopted standard or specified values applicable to the statistical measures used.
NOTE 3 The cumulative sum (cusum) chart is a type of control chart. Cusum charts are used for detecting small permanent
shifts in trends that may remain undetected when using the Shewhart control chart. The basic principle of the most common
type of cusum chart is based on the plotted value, which is the cumulative sum of deviations of successive sample statistics
from a target value. When a process change is made, the sum is returned to zero. The ordinate of each plotted point
represents the algebraic sum of the previous ordinate and the most recent deviation from the target.
Cusum charts are generally interpreted by masks superimposed on the chart, a signal occurring if the path of the cusum inter-
sects or touches the boundary of the mask (ISO 3534-2).
3.11
Shewhart control chart
control chart to show if a process is in statistical control
[ISO 3534-2 and ISO 8258]
NOTE It may be a chart using attributes (for example, proportion nonconforming) for evaluating a process, or it may be a
chart using variables (for example, average and range) for evaluating a process. Examples are:
 X-bar chart - the sample means are plotted in order to control the mean value of a variable.;
 R chart - the sample ranges are plotted in order to control the variability of a variable;
 s chart - the sample standard deviations are plotted in order to control the variability of a variable;
 s2 chart - the sample variances are plotted in order to control the variability of a variable;
 C chart - the number of defectives (per batch, per day, per machine, etc.) is plotted.
3.12
action control upper [lower] limit
limit above [below] which, or the limits outside which, the statistic under consideration lies when action should be
taken
[ISO 3534-2]
NOTE These limits are based on the assumption that only 0,3 % of normally distributed results will fall outside these limits.
Such an occurrence would strongly indicate that additional, assignable causes of variation may be present and that action may
be required to identify and reduce them.
© STANDARDS MALAYSIA 2009 - All rights reserved

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3.13
warning control upper [lower] limit
limit below [above] which (upper [lower] limit), or the limits between which, the statistic under consideration lies with
a high probability when the process is under control
[ISO 3534-2]
NOTE 1 When the value of the statistic computed from a sample is outside the warning limits but inside the action limits,
increased supervision of the process is generally necessary and rules may be applied for action in particular processes.
NOTE 2 At the warning limits, attention is called to the possibility of out-of-control conditions, but further action is not
necessarily required.
NOTE 3 The warning limits will always be within the action limits.
NOTE 4 Warning limits are usually set so that only 5 % of results should normally fall outside them. Under certain
circumstances, successive results outside warning limits indicate that assignable causes of variation are present and that
actions are required to identify and reduce errors.
NOTE 5 The limits are calculated from the standard deviation of the statistic under consideration of at least 20 samples.
Warning and action control limits are applied to individual sampling results.
3.14
central line
line on a control chart representing the long-term average or a prespecified value of the statistical measure being
plotted
[ISO 3534-2]
4 Sources of sampling error
Sources of error include the following:
a) Contamination
Contamination can be caused by sampling equipment materials (sampling containers and sample containers)
by cross contamination between samples and by sample preservation and inappropriate storage and transport
arrangements.
b) Sample instability
The type of sampling vessels and containers used can affect the stability of the determinand between sampling
and analysis due to the inherent instability of the sample itself and the conditions in which samples are stored
and transported.
c) Incorrect preservation
The choice of sampling vessels and containers affect the integrity of the determinand and the options for
preservation which may be available, as detailed in ISO 5667-3.
d) Incorrect sampling
Deviation from the sampling procedure, or the procedure itself, may be a source of error.
e) Sampling from nonhomogenized water bodies
f) Sample transportation (see clause 6).

© ISO MS5667-14:1998(E)
ISO 1850-14:2009
5 Sampling quality control techniques
5.1 General
Sampling is defined in ISO 5667-2 as the process of removing a portion, intended to be representative, of a body of
water (or sludge or sediment) for the purpose of examination for various defined characteristics.
Guidance is given below with respect to quality control procedures which can be used to identify and quantify errors
associated with sampling.
A complete overview of quality assurance applied to sampling is outside the scope of this document. However, it is
important to emphasize that the quality control measures discussed below should ideally be applied in the context of
a well organized approach to quality control. This would include a review of the whole approach to sampling with
respect to its fitness for the intended purpose. Within this, the choice of sampling techniques, sampling locations,
numbers and types of sample taken, training of sampling staff, sample transport, preservation and storage should
be considered. The chosen approach should be adequately documented and a system of record-keeping
established. A suitable quality control programme could contain any or all of the techniques listed below. The effort
expended on sampling quality control is dependent on the objectives of the programme, but it is recommended that
at least 2 % of analytical efforts should be devoted to quality control for sampling.
As noted earlier, quality control measures in sampling have three main objectives:
a) to provide a way of monitoring and detecting sampling errors and hence a means of rejecting invalid or
misleading data;
b) to act as a demonstration that sampling errors have been controlled adequately; and
c) to indicate the variability of sampling and thereby to give a guide to this important aspect of error.
The following quality control techniques are described below.
 the collection of replicate samples as a check on the precision of sampling;
 the use of field blank samples to monitor sources of sample contamination;
 the use of spiked samples as quality controls to assess sample stability during transport and storage.
5.2 Replicate quality control samples
This term can be used to cover a range of approaches to quality control which aim to assess the random error
associated with different levels of the sampling process:
a) analytical variance: replicate analyses of the same sample prepared in the laboratory can be used to estimate
short-term analytical error;
b) analytical + subsampling/transport variance: analyses of replicate samples taken in the field (B 1 and B2) from
the bulk sample (B) (the sample obtained by a single application of the sampling procedure). The difference
between such data gives an estimate of analytical plus sampling variance (includes storage but excludes the
effect from sampling containers).
c) analytical + total sampling variance: analysis of bulk samples obtained by separate application of the sampling
procedure. This provides an indication of the variance of the whole process of sampling and analysis (A 1
and A2).
The relationship between the different sampling variances in examples b) and c) is illustrated schematically in
figure 1.

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Figure 1 — Relationship between different sampling variances
The difference between A1 and A2 gives an estimate of total sampling variance (sampling, containers, storage and
analysis).
The difference between B1 and B2 (expressed as the mean of b11 & b12 and b21 & b22) gives an estimate of
analytical plus sampling variance (including storage, excluding sampling container).
The difference between replicate analyses b11 & b12 and b21 & b22 gives an estimate of analytical precision.
The analysis of replicate samples provides an estimate of the contribution of analytical error for all of the examples
in figures 2 to 7.
Comparison between the different estimates of variance described above can be used to identify the most important
sources of measurement uncertainty. This is illustrated in tables 1 and 2 below.
Table 1 — Analytical variance
Sample No. 1 2 3 4 5 6 7
Duplicate results -1 1,61 1,72 2,21 1,38 2,25 2,8 1,74
-2 1,55 1,98 1,99 1,55 2,44 2,55 1,55
Estimate of variance 0,001 8 0,033 8 0,024 2 0,014 45 0,018 05 0,031 25 0,018 05

(1 degree of freedom)
NOTE Pooled estimate of variance (the average of the above estimates) with 7 degrees of freedom = 0,020 23.
The following duplicate results were obtained for a series of wastewater samples, each of which was divided into
two analytical portions. These were analysed to give the results shown below.

© ISO MS5667-14:1998(E)
ISO 1850-14:2009
Table 2 — Analytical + subsampling/transport variance
Sample No. 1 2 3 4 5 6
Duplicate results -1 2,66 1,66 2,31 1,99 1,85 1,81
-2 1,85 2,22 1,44 1,55 2,54 2,65
Estimate of variance 0,328 1 0,156 8 0,378 5 0,096 8 0,238 1 0,352 8

(1 degree of freedom)
NOTE 1 Pooled estimate of analytical + sample handling variance - with 6 degrees of freedom = 0,258.
NOTE 2 The concentrations of the sample chosen should be similar to those chosen in table 1.
These two estimates of analytical and analytical + subsampling/transport variance can be compared using an
appropriate F-test: observed F value = 12,75.
The F value from these tables (for 7 and 6 degrees of freedom and at the 95 % probability level) = 4,2.
The observed F value is larger than the table 1 and table 2 values — hence there is reason to believe that there are
important sources of variation at the sampling/handling stage. In the case of samples taken, for example, for the
determination of ammonia, it might be reasonable to investigate the possibility that sample preservation may need
attention or that concentrations have changed during the period in which the samples were taken.
5.3 Field blank samples
This technique can be used to identify any errors relating to contamination of sampling containers and the sampling
process (see figure 2).
At the laboratory, divide a sample of deionized water into two parts, Part A and Part B. Part A is retained in the
laboratory. Part B is transported into the field and subdivided into portions b1 and b2.
Portion b1 should be processed using the sampling container, as far as is practical using the same technique as real
samples.
Portion b2 should be retained and returned to the laboratory without any further processing in the field.
Portion b1 processed as a real sample, together with the unused portion b 2, should be returned to the laboratory for
analysis.
Figure 2 — Field blank samples using deionized water

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The comparison of results of Part A and the portion b1 identifies errors due to sampling, processing and
transportation.
The comparison of results of Part A and the portion b2 identifies errors due to sample transportation.
The comparison of results of portion b1 and portion b2 identifies errors due to contamination of sampling containers
or sampling processes.
5.4 Rinsing of equipment (sampling containers)
This technique can be used to identify any errors relating to contamination of sampling devices and the sampling
process caused by incomplete cleaning of the sampling vessels (see figure 3).
The procedures relating to field blanks can be used on-site immediately after the sampling episode.
Portion b1 should be processed to rinse the sampling container, as far as is practical using the same technique as
for real samples.
Portion b1 with the unused portion b2 should be returned to the laboratory for analysis.
The comparison of results of Part A and the portion b1 identifies errors due to incomplete cleaning of the sampling
vessels.
or sampling processes due to incomplete cleaning of sampling vessels.
Figure 3 — Rinsing using deionized water blank

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© ISO MS5667-14:1998(E)
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5.5 Filtration recovery
5.5.1 General
This technique can be used to identify any errors relating to contamination of sampling containers and the sampling
process associated with filtration of samples.
When there is a requirement to filter samples on site, then field blanks and/or standard quality assurance samples
should be processed using the same filtering procedures as for real samples.
5.5.2 Filtering of deionized water blank
This technique can be used to identify any errors relating to sampling containers, filtration equipment, sampling
processes and contamination of the samples (see figure 4).
Portion b1 should be processed using the sampling container and filtration equipment, as far as is practical using
the same technique as real samples.
Portion b1 processed as a real sample together with the unused portion b 2 should be returned to the laboratory for
analysis.
Figure 4 — Filtering of deionized water blank
The comparison of results of Part A and the portion b1 identifies errors due to sampling filtration, processing and
transportation.
or sampling processes during filtration.
5.5.3 Filtering of spiked quality assurance sample
This technique can be used to identify any errors relating to sampling containers, filtration equipment, sampling
processes, and instability and contamination of the samples (see figure 5).

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At the laboratory, prepare a previously analysed environmental sample by spiking the sample with the determinand
of interest. The quantity of the determinand in the spike should be chosen so that the measurements are made at
the concentration where the best precision is obtained.
Divide this sample into two parts, Part A and Part B. Part A is retained in the laboratory. Part B is transported into
the field and subdivided into portions b1 and b2.
Portion b1 should be processed using the sampling container and filtration equipment, as far as is practical using
the same technique as for real samples.
Portion b1 processed as a real sample, together with the unused portion b 2, should be returned to the laboratory for
analysis.
Figure 5 — Filtering of spiked quality assurance sample
The comparison of results of Part A and the portion b1 identifies errors due to sampling, including sampling
processes and filtration equipment, sample instability and transportation.
The comparison of results of portion b1 and portion b2 identifies errors due to contamination of sampling containers,
filtration equipment and sampling processes and errors due to instability and contamination of the sample.
5.6 Spiked samples
5.6.1 General
This technique can be used for estimating the systematic error of the sampling processes which includes identifying
errors relating to contamination of sampling containers, sampling processes. It is particularly valuable in identifying
errors due to sample instability, including loss of determinands by volatilization, adsorption and biological factors; for
example, determinands such as volatile organic compounds, trace metals (where samples are filtered) and
nutrients. There are two main techniques, spiking deionized water samples (see figure 6) and spiking environmental
samples (see figure 7).
5.6.2 Spiked deionized water samples
At the laboratory, divide a sample of spiked deionized water into two parts, Part A and Part B. Part A is retained in
the laboratory. Part B is transported into the field and subdivided into three portions b1, b2, and b3.

© ISO MS5667-14:1998(E)
ISO 1850-14:2009
Portion b1 should be processed using the sampling container, as far as is practical using the same as for real
samples.
Portion b3should be spiked with a known concentration of the determinand of interest and subdivided into portions
b3(i) and b3(ii).
Subportion b3(i) should be processed using the sampling container, as far as is practical using the same technique
as real samples.
Subportion b3(ii) should be retained and returned to the laboratory without any further processing in the field.
Figure 6 — Spiked deionized water samples
Figure 7 — Spiked environmental samples
Return portions b1, b2, b3(i) and b3(ii) to the laboratory for analysis.
The comparison of results of Part A and the portion b1 identifies errors due to sampling processing and
transportation.

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The comparison of results of Part A and the spiked portion b3(ii) identifies errors due to any instability and
contamination of the sample and transportation.
The comparison of results of Part A and spiked sub portion b3(i) identifies errors due to sample processing and
transportation and any errors due to instability and contamination of the sample.
and sampling processing (eliminates transportation errors).
The comparison of results of portion b2 and sub portion b3(ii) identifies errors due instability and contamination of
the sample.
The comparison of results of portion b3(i) and portion b3(ii) identifies errors due to contamination of sampling
containers or sampling processes.
5.6.3 Spiked environmental samples
Ideally, spiking of samples should be carried out in the field at the time of the sampling. This may require specialist
expertise and may be impractical on a routine basis.
Alternatively, prepare at the laboratory a previously analysed environmental sample by spiking the sample with the
determinand of interest. The quantity of the determinand in the spike should be chosen so that the measurements
are made at the concentration where the best precision is obtained.
Divide this sample into two parts, Part A and Part B. Part A is retained in the laboratory. Part B is transported into
the field and subdivided into portions b1 and b2.
Portion b1 should be processed using the sampling container, as far as is practical using the same technique as real
samples.
Portion b1 processed as a real sample together with the unused portion b 2 sample should be returned to the
laboratory for analysis.
The comparison of results of Part A and the portion b1 identifies errors due to sampling processing and
transportation.
and sampling processes and errors due to instability and contamination of the sample.
6 Transport, stabilization and storage of samples
Reference should be made to ISO 5667-3 for guidance on sample handling and preservation. Care is essential to
ensure that any preservatives are accurately prepared and dispensed. Measure and record the temperature of the
sample on the site. Physical parameters (for example pH, dissolved gases, suspended solids) should be
determined on site or as soon as possible afterwards.
Ensure that sample containers are delivered to the laboratory as routine samples. It is recommended that sample
containers are tightly sealed and protected from the effects of light and excessive heat, because the characteristics
of the sample may rapidly deteriorate due to gas exchange, chemical reactions and the metabolism of organisms
o
which may be present. Ensure that samples which cannot be analysed quickly are stabilized. Cooling to 4 C may
be applied; for longer periods, freezing to 220 C as recommended in ISO 5667-3. In the latter case, ensure that the
o
sample is completely thawed before use, as the freezing process may have the effect of concentrating some
components in the inner part of the sample which freezes last. Samples may be preserved by the addition of

© ISO MS5667-14:1998(E)
ISO 1850-14:2009
chemicals of suitable quality. Ensure that the chosen method of preservation does not interfere with the subsequent
examination or influence the results. Record all preservation steps in the test report.
NOTE Quality assurance samples used for transportation, stabilization and storage should be treated to the same
processes as test samples.
7 Analysis and interpretation of quality control data
The aim of the quality control system is to ensure that the reliability of the sampling data is consistent with the
performance criteria required.
7.1 Shewhart control charts
The most widely used form of control chart is the Shewhart chart (see ISO 8258). This takes the form of a chart on
which the variable of interest is plotted sequentially. The measured values are compared with the control value.
Much information can be gained merely by a visual examination of the chart. (See figures A.1 and A.2.)
7.2 Construction of duplicate control charts
This takes the form of a chart on which the difference, d, between duplicate determinations is plotted.
d = R1 2 R2,
where
R1 is the result of the first sample analysed;
R2 is the result of the second sample analysed.
It is essential always to subtract the second result from the first and plot the difference with due regard to its sign.
The expected value for the chart is zero. The relevant sample standard deviation, sd, is calculated from:
(d i − D)
2
m
sd = ∑ m -1
(1)
i =1
where
D is the mean difference between duplicates over m batches of samples and
di are individual differences.
Examples of a control chart for duplicate data and recovery are given in annex A.
8 Sample identification and records
Describe each sampling point. In the case of a long-term programme, conditions which are agreed and remain
unchanged need not be restated. In this case only a statement of the in situ measurements and variables such as
weather conditions and unusual observations need be recorded.
When sampling for special reasons, detailed information should be given, including the reasons for sampling and
any preservation steps taken.

13
MS
ISO1850-14:2009
5667-14:1998(E) © ISO
Annex A
(informative)
Control charts
A.1 Example of a control chart for duplicate data (figure A.1)

Figure A.1 — Shewhart chart for duplicate control samples
Suspended solids are determined in a range of industrial effluents to monitor compliance with a discharge limit of
30 mg/l.
A series of duplicate samples, examples as shown in figure A.1, have been taken for effluent samples of suspended
solids concentrations in the range of interest 220 mg/l to 40 mg/l. It is assumed that the standard deviation of
sampling and analysis is constant across this restricted range. This will allow the precision of sampling to be
estimated and checked on a routine basis.
In each case, a single bulk sample of effluent was taken and thoroughly homogenized. The bulk sample was then
subsampled using the routine sampling procedure to produce duplicate test samples. Each of these test samples
was analysed once.
Analytical data for 20 duplicate samples are shown in table A.1.
The corresponding control chart is attached. The central value of the chart is fixed at the mean value of the
differences between duplicate data. The action and warning limits are drawn at + 3 and + 2 standard deviations,
respectively.

© ISO MS
ISO 1850-14:2009
5667-14:1998(E)
Table A.1 — Suspended solids data for quality control duplicate samples
Measured values Difference
mg/l mg/l
1st 2nd
33,2 36,0 - 2,8
25,6 26,2 - 0,6
38,2 34,8 3,4
28,8 27,2 1,6
31,4 29,8 1,6
34,6 32,2 2,4
22,4 24,6 - 2,2
27,2 26,8 0,4
22,0 23,2 - 1,2
34,0 32,8 1,2

24,6 22,6 2,0
23,8 23,0 0,8
33,6 35,2 - 1,6
37,4 36,6 0,8
29,2 31,4 - 2,2
30,0 31,2 - 1,2
36,4 35,8 0,6
37,2 39,4 - 2,2
33,6 35,0 - 1,4
28,0 26,4 1,6
Mean difference 1,0
Standard deviation of differences 0,471 8
NOTE The observed standard deviation reflects analytical precision as well as
that of sampling.
A.2 Example of a control chart for recovery (figure A.2)
The data below (see table A.2) relate to the determination of trace concentrations of mercury in river waters. For
each batch of analysis a spiking recovery test was carried out by analysing a river sample before and after spiking
with 90 ng/l. The details of spiking were as follows:
C = Concentration of spiking solution = 100 µg/l
V = Volume of sample taken = 1 998,2 ml
W = Volume of spike = 1,8 ml
S = Measured concentration in the spiked sample (see below)
U = Measured concentration in the unspiked sample (see below)
Percentage recovery is calculated as:
% Recovery = 100 ◊ [S ◊ (V + W ) 2 U ◊ V ]/C ◊ W (2)

15
MS
ISO1850-14:2009
5667-14:1998(E) © ISO
Table A.2 — Data from spiking recovery test

Batch No. Unspiked Spiked Recovery
concentration, U concentration, S
ng/l ng/l %
1 14 90 84,5
2 15 100 94,5
3 25 115 100
4 8 103 105.6
5 15 104 98,9
6 3 88 94,4
7 8 95 96,7
8 25 108 92,2
9 13 92 87,8
10 19 104 94,5
11 7 94 96,7
12 28 108 88,9
13 9 98 98,9
14 8 87 87,8
15 33 120 96,7
16 2 84 91,1
17 1 84 92,2
18 8 88 88,9
19 14 89 83,3
20 34 120 95,3
21 12 91 87,8
Mean recovery (%) 93,2
Standard deviation of recovery (%) 5,55
The recovery control chart (see figure A.2) is constructed using the mean or the initial estimation of standard
deviation.
NOTE The expected recovery of 100% should not be used if the observed recovery appears to be biased. The best
approach is to base the chart on the mean recovery for the initial 20 or so estimates. Having done this, it is important to review
any changes in true recovery with respect to analytical targets and to update the chart accordingly.

© ISO MS
ISO 1850-14:2009
5667-14:1998(E)
NOTE Estimated standard deviation = 5,5 (used to construct chart);

Calculated standard deviation = 5,55 from a minimum of 20 results.
Figure A.2 — Shewhart control chart for recovery

MS
ISO 1850-14:2009
5667-14:1998(E) © ISO
Annex B
(informative)
Bibliography
[1] ISO 3534-1:1993, Statistics — Vocabulary and symbols — Part 1: Probability and general statistical terms.
[2] ISO 3534-2:1993, Statistics — Vocabulary and symbols — Part 2: Statistical quality control.
[3] ISO 5667-2:1991, Water quality — Sampling — Part 2: Guidance on sampling techniques.
[4] ISO 8258:1991, Shewhart control charts.
[5] ISO/TR 13530:1997, General guidance to analytical quality control for water analysis.
[6] Gardner, M.J., Wilson, A.L., and Cheesman, R.J. A Manual on Analytical Quality Control for the Water Industry,
NS30, (1989). WRc, Medmenham, UK.

Acknowledgements
Members of Technical Committee on Water Quality
Ms Wong Fook Lian (Chairperson) Department of Chemistry, Malaysia

Ms Masrina Mansor (Secretary) SIRIM Berhad
Mr Amirul Shazli Mohamed Alam Sekitar Malaysia Sdn Bhd
Mr Hasmadi Hassan Atomic Energy Licensing Board
Ms Rusnah Rohani Department of Chemistry, Malaysia
Mr Jamaludin Mahmud A Bakar Department of Environment, Malaysia

Ms Yuhaslin Yusof Department of Irrigation and Drainage
Ms Bidasari Bahashim Lembaga Urus Air Selangor
Mr Mohd Shahid Ayub Malaysian Nuclear Malaysia
Ir Chan Chiang Heng Malaysian Water Association
Mr Ismail C Mohamed/ Minerals and Geoscience Department
Ms Maizatul Akmar Aros Malaysia
Ms Mariah Hassan Ministry of Health Malaysia
Mr Mohd Razif Bahari Ministry of Energy, Water and
Communication
Mr Marzuki Mohamad/ National Water Services Commission
Mr Mohd Radzi Yunus
Dr Rajeswary K Ramasamy SIRIM Berhad (Environmental and
Bioprocess Technology Centre)
Ms Kuziah Ahmad SIRIM QAS International Sdn Bhd (Chemical
Testing Section)
Mr Mohd Yaman Mohd Zin Syarikat Bekalan Air Selangor Sdn Bhd
Assoc Prof Megat Johari Megat Mohd Noor/ Universiti Putra Malaysia
Mr Abdul Ghani Liew Abdullah
Members of Working Group on Sampling (Water Quality)
Datuk Ir Dr M. S. Pillay (Chairman) Ministry of Health Malaysia

Ms Zainorni Mohd Janis (Secretary) SIRIM Berhad
Dr Abdul Rani Abdullah Alam Sekitar Malaysia Sdn Bhd
Dr Chin Teen Teen ALS Technichem (Malaysia) Sdn Bhd
Ms Wan Rahimah Wan Ahmad Department of Chemistry, Malaysia
Mr Jamaludin Mahmud Abu Bakar Department of Environment, Malaysia
Ms Norazizah Abd Kadir Department of Irrigation and Drainage
Mr Abdul Aziz Yahaya Department of Occupational Safety and
Health Malaysia
Dr Shahunthala/Mr Md Akhir Arshad Fisheries Research Institute
Ms Khor Bee Chin/Ms Ruhaidah Md Hassan Indah Water Konsortium Sdn Bhd
Ir Mohd Hizan Kamaruzaman Jabatan Kerja Raya Malaysia
Mr Md. Badron Ismail/Mr Rosli Ahmad Malaysia Marine Department
Mr Md. Shahid Ayub Malaysian Nuclear Agency
Ir Chan Chiang Heng Malaysian Water Association

Acknowledgements (continued)
Mr Ismail C. Mohamad Minerals and Geoscience Department

Malaysia
Mr Izham Harith Ministry of Health Malaysia (Engineering
Services Division)
Mr Che Saipolliza Deraman/ Ministry of Health Malaysia (Food Safety and
Mr Mohammad Jefri Crossley Quality Division)
Mr Wan Sallehuddin Ministry of Housing and Local Government

Ms Norshidah Baharuddin SIRIM Berhad
Mr Ragbir Singh Harbans Syarikat Bekalan Air Selangor Sdn Bhd
To also acknowledge members of Working Group in Ministry of Health (Engineering

Services Division) as follows
Mr Mohd Zaharon Mohd Talha

Ms Keah Kwee Chu
Ms Mariah Hassan

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MS 1850-14:2009

WATER QUALITY - SAMPLING - PART 14:

The Department of Standards Malaysia (STANDARDS MALAYSIA) is the national

The main function of the Department is to foster and promote standards,

furthering international cooperation in relation to standards and standardisation.

Malaysian Standards are developed through consensus by committees which

The Department of Standards appoints SIRIM Berhad as the agent to develop

For further information on Malaysian Standards, please contact:

Department of Standards Malaysia OR SIRIM Berhad

Tel: 60 3 8318 0002 Tel: 60 3 5544 6000

© STANDARDS MALAYSIA 2009 – All rights reserved

National foreword ....................................................................................................................... iii

4 Sources of sampling error............................................................................................. 4

5 Sampling quality control techniques ............................................................................. 5

6 Transport, stabilization and storage of samples ......................................................... 12

7 Analysis and interpretation of quality control data ...................................................... 13

8 Sample identification and records............................................................................... 13

Annex A Control charts .......................................................................................................... 14

© STANDARDS MALAYSIA 2009 - All rights reserved i

Department of Standards Malaysia

Minerals and Geoscience Department Malaysia

Alam Sekitar Malaysia Sdn Bhd

Alam Sekitar Malaysia Sdn Bhd

ii © STANDARDS MALAYSIA 2009 – All rights reserved

Malaysian Standard, the following apply:

c) reference to International Standards should be replaced by equivalent Malaysian

Referenced International Standards Corresponding Malaysian Standards

ISO 5667-1:1980, Water quality - MS 1850-1, Water quality - Sampling - Part 1:

ISO 5667-3:1985, Water quality - MS 1850-3, Water quality - Sampling - Part 3:

© STANDARDS MALAYSIA 2009 - All rights reserved iii

 Part 1: Guidance on the design of sampling programmes

 Part 2: Guidance on sampling techniques

 Part 3: Guidance on the preservation and handling of samples

 Part 4: Guidance on sampling from lakes

 Part 5: Guidance on sampling of drinking water

 Part 6: Guidance on sampling of rivers and streams

 Part 7: Guidance on sampling of water and steam in boiler plants

 Part 8: Guidance on sampling of wet deposition

 Part 9: Guidance on sampling from marine waters

 Part 10: Guidance on sampling of waste waters

 Part 11: Guidance on sampling of groundwaters

 Part 12: Guidance on sampling of bottom sediments

 Part 13: Guidance on sampling of water, wastewater and related sludges

iv © STANDARDS MALAYSIA 2009 - All rights reservediii

a) to monitor the effectiveness of sampling methodology;

iv© STANDARDS MALAYSIA 2009 - All rights reserved v

Water quality — Sampling —

© STANDARDS MALAYSIA 2009 - All rights reserved 1

2 © STANDARDS MALAYSIA 2009 - All rights reserved

[ISO 3534-2 and ISO 8258]

© STANDARDS MALAYSIA 2009 - All rights reserved

4 Sources of sampling error

Sources of error include the following:

e) Sampling from nonhomogenized water bodies

f) Sample transportation (see clause 6).

4 © STANDARDS MALAYSIA 2009 - All rights reserved

5 Sampling quality control techniques

The following quality control techniques are described below.

 the collection of replicate samples as a check on the precision of sampling;