EN ISO 5667-3:1995

SLOVENSKI STANDARD
01-september-1996
.DNRYRVWYRGH9]RUþHQMHGHO1DYRGLOR]DKUDQMHQMHLQUDYQDQMH]Y]RUFL,62

Water quality - Sampling - Part 3: Guidance on the preservation and handling of samples
(ISO 5667-3:1994)
Wasserbeschaffenheit - Probenahme - Teil 3: Anleitung zur Konservierung und
Handhabung von Proben (ISO 5667-3:1994)
Qualité de l'eau - Echantillonnage - Partie 3: Guide général pour la conservation et la
manipulation des échantillons (ISO 5667-3:1994)
Ta slovenski standard je istoveten z: EN ISO 5667-3:1995
ICS:
13.060.45 Preiskava vode na splošno Examination of water in
general
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

INTERNATIONAL
IS0
STANDARD
5667-3
Second edition
1994-08-01
Water quality - Sampling -
Part 3:
Guidance on the preservation and handling of
samples
Qualit de I’eau - khantillonnage -
Partie 3: Guide g&&al pour la conservation et la manipulation des
khan tillons
Reference number
IS0 5667-3: 1994(E)
IS0 5667-3: 1994(E)
Foreword
IS0 (the International Organization for Standardization) is a worldwide
federation of national standards bodies (IS0 member bodies). The work
of preparing International Standards is normally carried out through IS0
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. IS0
collaborates closely with the International Electrotechnical Commission
(I EC) 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 IS0 5667-3 was prepared by Technical Committee
lSO/TC 147, Water quality, Subcommittee SC 6, Sampling (general
methods).
This second edition cancels and replaces the first edition
(IS0 5667-3:1985), of which it constitutes a technical revision.
IS0 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, natural and man-made
- Part 5: Guidance on sampling of drinking water and water used for
food and beverage processing
- 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 the sampling of wet deposition
0 IS0 1994
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced
or utilized in any form or by any means, electronic or mechanical, including photocopying and
microfilm, without permission in writing from the publisher.
International Organization for Standardization
Case Postale 56 l CH-1211 Geneve 20 l Switzerland
Printed in Switzerland
ii
Q IS0 IS0 5667-3: 1994(E)
- Part 9: Guidance on sampling from marine waters
- Part 10: Guidance on sampling of waste waters
- Part I I: Guidance on sampling of groundwaters
- Part 12: Guidance on sampling of bottom sediments
- Part 13: Guidance on sampling of sewage, waterworks and related
sludges
Annex A of this part of IS0 5667 is for information only.

0 IS0
IS0 5667-3: 1994(E)
Introduction
This part of IS0 5667 is intended to be used in conjunction with
IS0 5667-l and IS0 5667-2 which deal respectively with the design of
sampling programmes and sampling techniques.
iv
IS0 5667=3:1994(E)
INTERNATIONAL STANDARD 0 IS0
Water quality - Sampling -
Part 3:
Guidance on the preservation and handling of samples
1 Scope 3 Preservation of samples
This part of IS0 5667 gives general guidelines on the
3.1 General considerations
precautions to be taken to preserve and transport
water samples.
Waters, particularly surface waters and above all
waste waters, are susceptible to being changed to
These guidelines are particularly appropriate when a
differing extents as a result of physical, chemical or
sample (spot or composite sample) cannot be anal-
biological reactions which may take place between
ysed on site and has to be transported in order to be
the time of sampling and the analysis. The nature and
analysed in the laboratory.
rate of these reactions are often such that, if the
necessary precautions are not taken before and dur-
ing transport as well as during the time in which the
samples are preserved in the laboratory before being
analysed, the concentrations determined will be dif-
2 Normative references
ferent from those existing at the time of sampling.
The following standards contain provisions which,
It should be stressed that, particularly if there is any
through reference in this text, constitute provisions
doubt, the analyst and the scientist interpreting the
of this part of IS0 5667. At the time of publication, the
results should be consulted before deciding on the
editions indicated were valid. All standards are subject
precise method of handling and preservation.
to revision, and parties to agreements based on this
The causes of variations are numerous; some of these
part of IS0 5667 are encouraged to investigate the
are as follows:
possibility of applying the most recent editions of the
standards indicated below. Members of IEC and IS0
- Bacteria, algae and other organisms can consume
maintain registers of currently valid International
certain constituents present in the samples; they
Standards.
can also modify the nature of the constituents to
IS0 5667-l : 1980, Water quality - Sampling - produce new constituents. This biological activity
affects for example the contents of dissolved
Part 1: Guidance on the design of sampling pro-
carbon dioxide, nitrogen compounds,
grammes. oxygen,
phosphorus and sometimes silicon.
IS0 5667-2:1991 B Water quality - Sampling -
- Certain compounds can be oxidized by the dis-
Part 2: Guidance on sampling techniques.
solved oxygen contained in the samples or by at-
IS0 5667-8: 1993, Water quality - Sampling -
mospheric oxygen [for example organic
Part 8: Guidance on the sampling of wet deposition. compounds, iron(H), sulfides].

63 IS0
IS0 5667=3:1994(E)
On the other hand, surface waters and ground waters
- Certain substances can precipitate out [for exam-
ple calcium carbonate, metals and metallic com- can in general be stored more effectively. In the case
pounds such as AI(O Mg&PO&] or be lost to of potable waters, the problem of storage can be
the vapour phase (for example oxygen, cyanides, solved more easily because these waters are less
mercury). susceptible to biological and chemical reactions.
Therefore, owing to these variations, which may af-
- The pH, conductivity, carbon dioxide content, etc.
fect the water samples, it may be necessary, in cer-
can be modified by the absorption of carbon diox-
tain determinations, to take individual samples rather
ide from the air.
than collective samples and to analyse them immedi-
- Metals dissolved or in a colloidal state as well as ately at the place of sampling. It should be remem-
certain organic compounds can be adsorbed or bered that the storage of samples for long periods is
absorbed irreversibly on the surface of containers only possible for the determination of a limited num-
or solid materials contained in the samples. ber of parameters.
In spite of numerous investigations which have been
- Polymerized products can depolymerize; con-
carried out in order to recommend methods which
versely, simple compounds can polymerize.
will enable water samples to be stored without
modification of their composition, it is impossible to
The extent of these reactions is a function of the
give absolute rules in this context which will cover all
chemical and biological nature of the sample, its
temperature, its exposure to light, the nature of the cases and all situations and which do not have ex-
container in which it i,s placed, the time between ceptions.
sampling and analysis, the conditions (for example
In every case, the method of storage should be com-
rest or agitation during transport) to which it is sub-
patible with the various analytical techniques for
mitted, etc.
which it will be used. One object of this part of
IS0 5667 is to describe the most commonly used
It follows that the variations relative to a particular
techniques.
constituent vary both in degree and rate, not only as
a function of the type of water, but also, for the same
type, as a function of seasonal conditions.
3.2 Feasible precautions
It must be emphasized moreover that these variations
are often sufficiently rapid to modify the sample con-
siderably in the space of several hours. In all cases, it
3.2.1 Filling the container
is therefore essential to take the necessary precau-
tions to minimize these reactions and, in ‘the case of
In the case of samples for the determination of
many parameters, to analyse the sample with a mini-
physico-chemical parameters, one simple precaution,
mum of delay.
which is not however adequate in all cases, is to fill
the flasks completely and stopper them in such a way
As the variations which take place in the water sam-
that there is no air above the sample.
ples are due to a large extent to biological processes,
it is generally necessary to choose, from the various
This limits interaction with the gas phase and agitation
possible methods of preservation, a method that does
during transport (thus avoiding modifications in carbon
not introduce unacceptable contamination.
dioxide content, and hence variations in pH; hydrogen
carbonates are not converted into precipitable car-
bonates; iron has less tendency to be oxidized, thus
Even the time for w hich the p
reserved sam ple can be
limiting colour variations; etc.).
stored before being analysed may change.
For microbiological examination, the sample container
As a guide, it can be said that methods of preserva-
should not be filled to the brim so that an air space is
tion tend to be less effective in the case of crude
left after insertion of the stopper. This aids mixing
sewage than in the case of purified sewage (effluents
before examination and avoidance of accidental con-
from biological treatment plants). It has also been ob-
tamination.
served that the behaviour of various waste water
Sample containers, whose contents are frozen as part
samples during storage is different depending on
of their preservation, should not be completely filled
whether the samples have been taken from municipal
(see 3.2.4).
or industrial sewage-treatment plants.
0 IS0
IS0 5667-3: 1994(E)
In general, new glassware should be rinsed with wa-
3.2.2 Use of appropriate containers
ter containing a detergent in order to remove dust and
The choice and preparation of a container can be of
residues of packing material, followed by thorough
major importance. IS0 5667-2 provides some guid-
rinsing with distilled or deionized water. For general
ance on this subject. trace analysis, the bottles should be filled with a
1 mol/l solution of nitric acid or hydrochloric acid and
However, it is essential that the container in which
left to soak for at least one day, followed by rinsing
the sample is stored and the stopper should not
with distilled or deionized water.
- be a cause of contamination (for example borosili-
For the determination of phosphates, silicon, boron
cate or soda-lime glass containers may increase
and surfactants, detergents should not be used for
the content of silica or sodium);
cleaning purposes. For trace analysis of organic ma-
terial, special pretreatment of the bottles may be
- absorb or adsorb the constituents to be deter-
necessary and reference should be made to the rel-
mined (for example hydrocarbons may be ab-
evant International Standard (also see 3.2.3.2).
sorbed in a polyethylene container, traces of
metals may be adsorbed on the surface of a glass
3.2.3.2 For samples for determination of
container, which can be prevented by acidifying
pesticides, herbicides and their residues
the sample);
In general, glass (preferably brown) containers should
- react with certain constituents in the sample (for
be used because plastics, except polytetra-
example fluorides reacting with glass).
fluoroethylene (PTFE), may introduce interferents
which can be significant if trace analyses are to be
It should be remembered that the use of opaque
performed.
containers or brown (non-actinic) glass containers can
reduce the photosensitive activities to a considerable
All containers should be cleaned with water and de-
extent.
tergent, followed by thorough rinsing with distilled or
deionized water, then oven dried at 105 “C for 2 h and
It is preferable to reserve a set of containers for a
cooled before being rinsed with the extraction solvent
particular determinand, thereby minimizing risks of
used during the analysis. Finally they should be dried
cross-contamination. However, care is necessary in
with a stream of carefully purified air or nitrogen.
any case to prevent bottles which formerly held a high
concentration of a determinand from contaminating
In addition, for containers that have already been
subsequent low contamination samples. Disposable
used, an extraction with acetone for 12 h, followed
containers should be considered, if economic, to pre-
by a hexane rinse and drying as described in the pre-
vent this type of contamination, but they are not suit-
vious paragraph, should also be used.
able for such specific parameters as organochlorine
pesticides.
3.2.3.3 For samples for microbiological analysis
Blank samples containing distilled water should al-
The containers should be able to withstand a
ways be taken, preserved and analysed as a check on
sterilization temperature of 175 “C for 1 h and should
the suitability of the choice of container and cleaning
not produce or release at this temperature any
procedure.
chemicals which would either inhibit biological activ-
ity, induce mortality or encourage growth.
When sampling solid or semi-solid samples, jars or
wide-mouthed bottles should be used.
When lower sterilization temperatures are used (e.g.
steam sterilization), polycarbonate and heat-resistant
polypropylene containers may be used. Caps or other
3.2.3 Preparation of containers
stoppers should withstand the same sterilization
temperatures as the containers.
3.2.3.1 For samples for chemical analysis
It is essential that the containers be free of acidic,
For analysis of trace quantities of chemical constitu- alkaline and toxic compounds. Glass containers
ents of surface or waste water, it is usual to clean should be cleaned with water and detergent, followed
new containers thoroughly in order to minimize poss- by thorough rinsing with distilled water. They should
ible contamination of the sample; the type of cleaner also be rinsed with nitric acid (HNO,) 10 % (V/v) fol-
used and the container material vary according to the lowed by thorough rinsing with distilled water in order
constituents to be analysed. to remove any heavy metals or chromate residues.
0 IS0
IS0 5667-3: 1994(E)
If the samples contain chlorine, sodium thiosulfate
within the membrane can be leached out into the
(Na,S,O,) should be added, before sterilization (see sample.
table3). This is to eliminate inactivation of bacteria by
chlorine.
3.2.6 Addition of preservatives
Certain physical and chemical constituents can be
3.2.4 ‘Cooling or freezing of the samples
stabilized by the addition of chemical compounds, ei-
ther directly to the sample after taking it, or before-
The sample should be kept at a temperature lower
hand, to the container when it is still empty.
than that during filling. Containers should be almost,
but not completely, filled.
Various chemical compounds, at concentrations
equally varied, have been proposed.
It should be emphasized that cooling or freezing of
samples is only truly effective if it is applied immedi-
The most commonly used are
ately after the collection of the samples. When poss-
ible, this necessitates the use of cool-boxes or
- acids;
refrigerators in vehicles at the sampling site.
- basic solutions;
3.2.4.1 Simple cooling (in melting ice or in a
- biocides;
refrigerator between 2 “C and 5 “C) and storage of the
sample in the dark are, in most cases, sufficient to
- particular reagents, necessary for the specific
preserve the sample during transport to the laboratory
preservation of certain constituents [for example
and for a relatively short period of time before the
the determination of oxygen, total cyanides and
analysis. Cooling cannot be considered as a means
sulfides requires a previous fixation of the sample
of long-term storage, particularly in the case of waste
on site (see the relevant Internationa Standards
water samples (see table I).
on analysis)].
3.2.4.2 In general, freezing (-- 20 “C) allows an in-
WARNING - The use of mercury(ll ) chloride
crease in the period of storage. Nevertheless, it is
and phenyl mercury( II) acetate
(HgCI,)
necessary to control the freezing and thawing tech-
(CH,CO,HgC,H,) should be avoided.
nique fully in order to return the sample to its initial
equilibrium after thawing. In this case, the use of
It should be remembered that certain preserv-
plastics containers (for example polyvinyl chloride) is
atives (for example acids, chloroform) need to be
strongly recommended.
used with caution, considering the danger in-
volved in their handling. Operators should be
Glass containers are not s uitable for freezi ng. Samples
warned of these dangers and the ways of pro-
for mi nalysi s should not be
crobiological a frozen.
tecting themselves from them.
3.2.5 Filtration or centrifuging of samples It is essential that the preservatives used do not in-
terfere during the determination; tests intended to
Suspended matter, sediment, algae and other micro-
check their compatibility are necessary in cases of
organisms may be removed, either at the time of
doubt. Any dilution of the sample with added pre-
taking the sample or immediately afterwards, by fil-
servatives should be taken into account during the
tration of the samples, through filter paper or mem- analysis and the calculation of results.
brane filter or by centrifuging. Filtration is, of course,
It is preferable that the addition of preservatives be
not applicable if the filter is likely to retain one or more
made using sufficiently concentrated solutions so that
of the constituents to be analysed. Equally, it is es-
only small volumes are necessary. This enables the
sential that the filter is not a cause of contamination
corresponding dilution to be disregarded in most
and is carefully washed before use, but in a manner
cases.
consistent with the final method of analysis.
The addition of these agents can also modify the
Alternatively, the reason for analysis may involve the
chemical or physical nature of the constituents and it
separation of soluble and insoluble forms (for example
is therefore necessary that these modifications are
of a metal) by filtration
not incompatible with the objects of later determi-
Membranes should be used with caution as various nations. (For example, acidification can solubilize
heavy metals and organic material may be adsorbed colloidal constituents or solids and should therefore
on the membrane surface, and soluble compounds only be used with caution if the aim of the measure-

0 IS0
IS0 5667-3: 1994(E)
ments is the determination of dissolved constituents.
4 Identification of samples
If the aim of the analysis is to determine the toxicity
to aquatic animals, the solubilization of certain com-
Containers holding the samples should be marked in
ponents, particularly heavy metals which are toxic in
a clear and durable manner in order to permit identifi-
ionic form, has to be avoided. Samples should there- cation without ambiguity in the laboratory.
fore be analysed as soon as possible.)
Additionally, it is generally necessary to note, at the
moment of sampling, numerous details which will
It is essential to carry out a blank test, particularly
permit a correct interpretation of the information ob-
determinations of trace elements, to take into account
tained (date and hour of sampling, name of person
possible introduction by the preservatives of an addi-
sampling, nature and amount of preservatives added,
tional amount of the elements to be determined (for
etc.). Various processes (labels, forms, etc.) allow the
example acids can introduce a not insignificant
practical attainment of these two objectives.
amount of arsenic, lead and mercury). In such a case,
samples of the preservatives used for the treatment
Special samples of anomalous material should be
of the water samples should be retained for use in the
clearly marked and accompanied by a description of
preparation of blank tests.
the observed anomaly. It is essential that samples
containing hazardous or potentially hazardous materi-
als, for example acids, are clearly identified as such.
5 Transport of samples
3.3 Recommendations
It is obvious that containers holding samples must be
As stated in 3.1, it is impossible to give absolute rules
protected and sealed in such a way that they do not
for preservation; the duration of preservation, the na-
deteriorate and do not lose any part of their contents
ture of the container and the efficiency of the preser-
during transport. Packaging should protect the con-
vation processes depend not only on the constituents
tainers from possible external contamination and
which have to be analysed and their levels, but also
breakage, particularly near the opening, and should
on the nature of the sample. The tables should
not itself be a source of contamination. During trans-
therefore be considered as giving reasonable sug-
portation, the samples should be kept as cool as
gestions only.
practicable and protected from light, with each sample
placed inside an individual waterproof container if
possible.
In any case in question, there needs to be no signif-
icant difference between the results of a determi-
If the time of travel exceeds the maximum recom-
nation carried out immediately and the result obtained
mended preservation time before analysis, then the
after preservation; each analyst should therefore ver-
samples should still be analysed, and the time be-
ify, taking into account particularly the method of
tween sampling and analysis reported, after consulta-
analysis which he intends to use, whether the sug-
tion with the scientist interpreting the analytical
gestions in tables 1 to 5 are suitable for the sample
results.
with which he is concerned.
6 Reception of samples in the laboratory
In addition, International Standards describing the
methods of analysis do, wherever possible, indicate
On their arrival in the laboratory, the samples should,
the recommended methods of preservation.
if their immediate analysis is impossible, be preserved
under conditions such that any contamination of the
Moreover, given that incompatibility can exist be-
outside of the containers is avoided and which pre-
tween the analyses to be carried out and the various
vent any change in their contents.
preservatives and containers possible, it is often
necessary to take several samples of the same water
The use, for this purpose, of refrigerated cabinets or
and to treat each of them in relation to the analyses
cool and dark places is highly recommended.
for which they are intended. This may result in a
ccmpromise between the techniques of preservation In all cases, and especially when a chain of custody
which would be most appropriate for each determi-
needs to be established, it is recommended that the
nation taken in isolation. The choice of sample pres-
count of sample containers received be verified
ervation procedure should always be the subject of
against the record of the number of sample bottles
consultation with the analyst.
sent for each sample.
0 IS0
IS0 5667=3:1994(E)
Table 1 - Techniques generally suitable for the preservation of samples - Physico-chemical and
chemical analysis
The information in table 1 is only a general guide to the preservation of samples. The complex nature of natural
and waste waters necessitates, before analysis, a verification of the stability of each type of sample treated ac-
cording to the methods proposed in table 1.
Maximum
recommended
Type of container
preservation time
International
before analysis
Standard
Parameter P = Plastics (e.g. (If a preservation period
Preservation Place of
to be polyethylene, is not specified, it is Comments
(The numbers
technique analysis
studied PTFE, PVC, generally unimportant.
refer to
PET) The indication
annex A.)
G = Glass ” 1 month” represents
BG = Borosilicate preservations without
glass particular difficulty.)
Acidity and P or G Cooling to be- Laboratory 24 h Samples should pref-
alkalinity tween 2 “C and erably be analysed at
5 “C the spot where the
sample is taken (par-
ticularly for samples
high in dissolved
gases).
Aluminium P Filtration at the Laboratory 1 month The dissolvedl) alu-
place of sam- minium and that ad-
dissolved 1)
pling and acidi- hering to suspended
matter can be deter-
fication of the
filtrate to mined from the
pH < 2 same sample.
total Acidification to Laboratory 1 month
pH < 2
Ammonia, P or G Acidification to Laboratory 24 h IS0 5664 121
free and pH < 2 with IS0 6778 [*s]
ionized H$O,, cooling IS0 7150 (261
WI
to between
2 “C and 5 “C
Cooling to be- Laboratory 6 h
tween 2 “C and
5 “C
AOX G Acidification to Laboratory 3 days IS0 9562 [%I
Analyse as soon as
(absorbable pH < 2 with possible. Refer to
organic hal- nitric acid, cool- relevant International
ides) ing to between Standard for details
2 “C and 5 “C, for particular types of
storage in the water.
dark
Arsenic P or G Acidification to Laboratory 1 month HCI should be used IS0 6595 [‘s]
pH < 2 if the hydride tech-
nique is used for
analysis.
Barium P or BG See aluminium Do not use H,SO,.
BOD P or G Cooling to be- Laboratory 24 h IS0 5815 [*I
(biochemical tween 2 “C and
5 oC and stor-
(Glass is preferable
oxygen de-
in the case of low
mand) age in the dark
BOD)
Boron and P Laboratory 1 month
IS0 9390 WI
borates
Q IS0 IS0 5667-3: 1994(E)
Maximum
recommended
Type of container
preservation time
International
before analysis
Standard
Parameter P = Plastics (e.g. (If a preservation period
Preservation Place of
Comments
polyethylene, is not specified, it is
to be
(The numbers
analysis
technique
generally unimportant.
studied PTFE, PVC,
refer to
PET) The indication
annex A.)
G = Glass ” 1 month” represents
BG = Borosilicate preservations without
glass particular difficulty.)
Bromides P or G Cooling to be- Laboratory 24 h Samples should be
kept out of direct
and tween 2 “C and
5 “C sunlight.
bromine
compounds
IS0 5961 191
P or BG See aluminium
Cadmium
Laboratory 24 h 48 h may be possible IS0 6058 [‘o]
Calcium P or G
but exercise caution
for samples of con-
ductivity above
70 mS/m.
Acidif ication to Laboratory 1 month Acidification (do not IS0 6059 ~‘1
IS0 7980 (4’1
pH < 2 use H,SO,) permits
determination of the
calcium from the
same sample as the
other metals.
On site -
Carbon P or G
dioxide
Laboratory 1 week The preservation IS0 8245 1421
Carbon, Acidif ication to
pH < 2 with technique will de-
organic
H,SO,, cooling pend on the method
of analysis to be
to between
used. The test
2 “C and 5 “C
and storage in shotild be carried out
as soon as possible.
the dark
Freezing to Laboratory 1 month Freezing (- 20 “C)
may be used in cer-
- 20 “C
tain cases.
Chlorides P or G Laboratory 1 month IS0 9297 [501
Chlorine, P or G On site - Transport in dark. IS0 7393 [**I
1291 1301
residual The analysis should
be carried out as
soon as possible.
Chlorophyll P or G Cooling to 4 “C Laboratory 24 h Transport in dark.
After filtration Laboratory 1 month
and freezing of
the residue
Chro- P or BG Cooling to be- Laboratory 24 h
mium(VI) tween 2 “C and
5 “C
Chromium, P or BG See aluminium IS0 9174 [481
total
Cobalt P or BG See aluminium IS0 8288 I441

0 IS0
IS0 5667-3: 1994(E)
Maximum
recommended
Type of container
preservation time
International
before analysis
Standard
Parameter P = Plastics (e.g. (If a preservation period
Preservation Place of
is not specified, it is Comments
to be polyethylene,
(The numbers
technique analysis
studied PTFE, PVC, generally unimportant.
refer to
PET) The indication
annex A.)
= Glass ” 1 month” represents
G
BG = Borosilicate preservations without
glass particular difficulty.)
Acidif ication to Laboratory 5 days IS0 6060 [‘*I
COD (chem- P or G
pH < 2 with
ical oxygen
(Glass is preferable H,SO cooling
demand)
in the case of low
to be:&een
COD)
2 “C and 5 “C
and storage in
the dark
P Freezing to Laboratory 1 month
- 20 “C
Colour P or G On site - IS0 7887 1341
Cooling to be- Laboratory 24 h
tween 2 “C and
5 “C and stor-
age in the dark
24 h The test should pref- IS0 7888 (351
Conductiv- P or G Cooling to be- Laboratory
tween 2 “C and erably be carried out
ity
5 “C on site.
IS0 8288 [44]
Copper P or BG See aluminium
The preservation technique will depend on the method of analysis to be used. IS0 6703-Z [*‘I
Cyanides, P
easily liber-
ated
IS0 6703-I 1201
Cyanides, P The preservation technique will depend on the method of analysis to be used.
total
See surfactants
Detergents
See total residue
Dry residue
- 1 month
Fluorides P but not PTFE Laboratory
24 h IS0 10359-I
Greases, Glass washed with Extraction on Laboratory It is recommended
that, immediately af-
oils, hydro- solvent (e.g. site where
carbons pentane) used for practicable and ter sampling, the ex-
extraction cooling to be- traction agent used
in the method of
tween 2 “C and
5 “C analysis or extraction
be added, or the ex-
traction be carried
out, on site (but local
safety regulations
should be followed).
See aluminium IS0 8288 [44]
Heavy P or BG
metals
(except
mercury)
24 h
Hydrazine G Acidification Laboratory
with HCI to
1 mol/l (100 ml
per litre of
sample) and
storage in the
dark
See greases
Hydro-
carbons
Hydrogen- See alkalinity
carbonates
0 IS0
IS0 5667-3: 1994(E)
Maximum
recommended
Type of container
preservation time
International
before analysis
Standard
Parameter P = Plastics (e.g. (If a preservation period
Preservation
Place of
to be polyethylene, is not specified, it is Comments
technique analysis (The numbers
studied PTFE, PVC,
generally unimportant.
refer to
PET) The indication
annex A.)
G = Glass ” 1 month” represents
BG = Borosilicate
preservations without
glass particular difficulty.)
lodides Glass Cooling to be- Laboratory 24 h Samples should be
tween 2 “C and
kept out of direct
5 “C
sunlight.
Al kalization to Laboratory 1 month
pH 11
Iron( II) P or BG Acidification to On site or 24 h
pH < 2 with in labora-
HCI and exclu-
ton/
sion of atmos-
pheric oxygen
Iron, total P or BG See aluminium IS0 6332 (‘41
Kjeldahl P or BG Acidification to Laboratory 24 h Do not acidify if free IS0 5663 1’1
(nitrogen) pH < 2 with ammonia is to be
H2S0,,, cooling measured on same
to between sample.
2 “C and 5 “C
and storage in
the dark
Lead P or BG See aluminium
Do not use H2S0,. IS0 8288 Id41
Lithium P Laboratory 1 month
Acidification to Laboratory 1 month
Acidification permits
pH < 2
determination of the
lithium from the
same sample as the
other metals.
Magnesium P or BG
See calcium IS0 6059 [“I
IS0 7980 ~‘1
Manganese P or BG
See aluminium IS0 6333 [‘5]
Mercury, BG Acidif ication to
Laboratory 1 month Particular care is IS0 5666 131 141
(51
total pH < 2 with
needed to ensure
HNO, and addi- that the sample con-
tion of K&O, tainers are free from
[0,05 % (m/m)
contamination.
final concen-
tration]
Nickel P or BG
See aluminium IS0 8288 ~41
Nitrate P or G Acidif ication to Laboratory 24 h
IS0 7890 ~1
[371 Ml
pH < 2 or cool-
ing to between
2 “C and 5 “C
On-site filtra-
Laboratory 48 h For ground and sur-
tion with a
face waters
membrane fil-
ter of pore size
0,45 pm and
cooling to be-
tween 2 “C and
5 “C
Nitrite
P or G Cooling to be- Laboratory 24 h
IS0 6777 [2z]
tween 2 “C and
5 “C
. .
0 IS0
IS0 5667=3:1994(E)
Maximum
recommended
Type of container
preservation time
International
before analysis
Standard
Parameter P = Plastics (e.g. (If a preservation period
Preservation Place of
to be polyethylene, is not specified, it is
Comments
(The numbers
technique analysis
PTFE, PVC,
studied generally unimportant.
refer to
PET) The indication
annex A.)
G = Glass ” 1 month” represents
BG = Borosilicate
preservations without
glass particular difficulty.)
Odour G Cooling to be- Laboratory 6 h The test can be car-
tween 2 “C and (for quanti- ried out on site (qual-
5 “C tative itative analysis).
analysis)
Organic See AOX
chlorine
Orthophos- B or G Cooling to be- Laboratory 24 h The analysis should IS0 6878-l ~41
tween 2 “C and
phates, be carried out as
total 5 “C soon as possible.
Otihophos- B or G The sample Laboratory 24 h The analysis should IS0 6878-l [24]
phates, dis- should be fil- be carried out as
solved tered on site at soon as possible.
the time of
sampling. Cool-
ing to between
2 “C and 5 “C
Oxygen P or G On site - IS0 5813 [a]
’ IS0 5814171
G Fixing of the Laboratory 4 days at most Fix the oxygen in ac-
oxygen on site
cordance with the
and storage in method of analysis
the dark used.
Ozone - On site -
Permang- G Acidif ication to Laboratory 2 days Analyse as soon as IS0 8467 [47]
anate index pH < 2 with possible. Acidifi-
H,SO,, cooling
cation in accordance
to between with the start of the
2 “C and 5 “C analytical method
and storage in can be a useful pres-
the dark ervation technique.
P Freezing to Laboratory 1 month
-20 “C
Pesticides, G (washed with Cooling to be- Laboratory 24 h
It is recommended
organo- solvent) tween 2 “C and that, immediately af-
chlorine 5 “C and stor- ter sampling, the ex-
age in the dark traction agent used
in the method of
analysis be added, or
that extraction be
carried out on site.
Pesticides, G (washed with Cooling to be- Laboratory 24 h Extraction should be
organo- solvent) tween 2 “C and commenced as soon
phosphorus
5 “C and stor- as possible after
age in the dark sampling, preferably
within 24 h.
See greases, oils and hydrocarbons
Petroleum
and deriva-
tives
On site
P or G The test should be
PH
carried out as soon
Laboratory
Transportation
.6h
as possible and pref-
at a lower tem-
erably immediately
perature than
on site after sam-
the initial one
pling.
0 IS0 IS0 5667=3:1994(E)
Maximum
recommended
Type of container
preservation time
International
before analysis
Standard
(If a preservation period
Parameter P = Plastics (e.g.
Preservation Place of
polyethylene, is not specified, it is Comments
to be
(The numbers
technique analysis
PTFE, PVC, generally unimportant.
studied
refer to
PET) The indication
annex A.)
= Glass ” 1 month” represents
G
BG = Borosilicate preservations without
glass particular difficulty.)
BG Inhibition of Laboratory 24 h The preservation IS0 6439 [‘a]
Phenol
index biochemical technique will de-
pend on the method
oxidation by
CuSO, and of analysis to be
acidification used.
with H3POd to
pH < 2
Cooling to be- Laboratory 24 h The extraction should
Phenols BG
tween 2 “C and be carried out as
5 “C and stor- soon as possible.
age in the dark
The use of iodized IS0 6878-l 1241
Phosphorus, BG or G Cooling to be- Laboratory 24 h
tween 2 “C and glass containers for
dissolved
5 “C. Immedi- samples is recom-
ate on-site fil- mended when low
tration concentrations are
necessary. being examined. (A
bottle can be iodized
by placing a few
crystals of iodine into
the sealed container,
which is then heated
to 60 “C for 8 h.) It
should be noted that
the iodine can leach
back into the sample,
thus becoming an
interferent in the
analysis. It is recom-
mended that consul-
tation with the
analyst be carried out
prior to using this
preservation tech-
nique.
Phosphorus, BG or G Cooling to be- Laboratory 24 h See above
total tween 2 “C and
5 “C
Acidif ication to Laboratory 1 month See above
pH < 2 with
l-Go4
Potassium See lithium IS0 9964-2 [60]
IS0 9964-3 16’1
Selenium G or BG Acidification to Laboratory 1 month IS0 9965 [a21
pH < 1, except
if selenides are
present. If
present, al ka-
lize to pH > 11
with NaOH.
0 IS0
IS0 5667=3:1994(E)
Maximum
recommended
Type of container
preservation time
International
before analysis
Standard
Parameter P = Plastics (e.g. (If a preservation period
Preservation Place of
is not specified, it is Comments
to be polyethylene,
(The numbers
technique analysis
generally unimportant.
studied PTFE, PVC,
refer to
PET) The indication
annex A.)
G = Glass ” 1 month” represents
preservations without
BG = Borosilicate
glass particular difficulty.)
Silicates, P Filtration at the Laboratory 24 h
dissolved place of sam-
pling, acidifi-
cation to
pH < 2 with
H2S0, and
cooling to be-
tween 2 “C and
5 “C
As for dis- Laboratory 24 h
Silicates, P
total solved silicates
Silver P or BG See aluminium Do not use HCI.
Some forms of silver
need addition of
cyanide for stabil-
ization.
IS0 9964-l 1591
Sodium See lithium
IS0 9964-3 [a’]
With waste water IS0 9280 [da]
Sulfates P or G Cooling to be- Laboratory 1 week
note that hydrogen
tween 2 “C and
5 “C sulfide may be
formed; therefore
hydrogen peroxide
should be added to
the sample. For sam-
ples with high BOD
(e.g. > 200 mg/l)
hydrochloric acid
should be added in-
stead, noting the
possible hazard of
released hydrogen
sulfide.
Sulfides P or G Fix samples im- Laboratory 24 h Stabilize according to
mediately on the relevant Inter-
(easily lib-
site by alkaliz- national Standard.
erated)
ation, if
necessary, with
sodium
carbonate fol-
lowed by addi-
tion of zinc
acetate.
Sulfides P or G Fix samples im- Laboratory - Analyse as soon as
possible. Stabilize ac-
mediately on
cording to the rel-
site by alkaliz-
ation, if evant International
necessary, with Standard.
sodium
carbonate fol-
lowed by addi-
tion of zinc
acetate. Fill
sample bottle
to exclude air
completely.
0 IS0
IS0 5667-3: 1994(E)
Maximum
recommended
Type of container
preservation time
International
before analysis
Standard
Parameter P = Plastics (e.g. (If a preservation period
Preservation Place of
is not specified, it is
to be polyethylene, Comments
(The numbers
analysis
technique
generally unimportant.
studied PTFE, PVC,
refer to
PET) The indication
annex A.)
G = Glass ” 1 month ” represents
BG = Borosilicate preservations without
glass ’ particular difficulty.)
Sulfites P or G Fixing on site Laboratory 48 h
by addition of
1 mlofa
2’5 % (m/m)
solution of
EDTA per
100 ml of sam-
ple
Cooling to be- Laboratory 48 h
Surfac- G Rinse glass contain-
tween 2 “C and ers as described in
tants,
cationic 5 “C IS0 7875-l and
IS0 7875-2. Analyse
samples as soon as
possible. To prevent
adsorption on the
container wall, add
on site 5 mg/l of a
linear alkylethoxyl-
ated nonionic
surfactant.
Surfac- G Acidif ication to Laboratory 48 h Rinse glass contain- IS0 7875-l 132)
tants, pH < 2 with ers as described in
IS0 7875-l. Analyse
anionic H,SO, and
cooling to be- samples as soon as
tween 2 “C and possible.
5 “C
IS0 7875-2 [ss]
Surfac- G Addition of Laboratory 1 month Rinse glass contain-
40 % (Vi+ ers as described in
tants,
nonionic formaldehyde IS0 7875-2. Analyse
to give a samples as soon as
possible.
1 % (WV) sol-
ution; cool to
between 2 “C
and 5 “C and
ensure sam-
pling container
is completely
filled.
Suspended P or G Laboratory 24 h The test should be
carried out as soon
and
sedimentary as possible and pref-
matter erably on site.
Tin P or BG See aluminium Do not use HNO,. If
organo-tin is present,
use acetic acid for
preservation for total
tin analysis, but if
speciation is required
then freeze and anal-
yse as soon as poss-
ible.
See calcium
Total hard-
ness
0 IS0
IS0 5667-3: 1994(E)
Maximum
recommended
Type of container
preservation time
International
before analysis
Standard
(If a preservation period
Parameter P = Plastics (e.g.
Preservation Place of
Comments
polyethylene, is not specified, it is
to be
(The numbers
analysis
technique
generally unimportant.
PTFE, PVC,
studied
refer to
The indication
PET)
annex A.)
” 1 month” represents
G = Glass
preservations without
BG = Borosilicate
particular difficulty.)
glass
Cooling to be- Laboratory 24 h
Total resi- P or G
tween 2 “C and
due (dry ex-
tract) 5 “C
IS0 7027 (251
Laboratory 24 h The test should pref-
Turbidity P or G
erably be carried out
on site.
P or BG See aluminium
Uranium
IS0 8288 [44]
See aluminium
Zinc P or BG
I) Dissolved: Denotes that which passes through a filter of pore size 0,45 pm.
Allocation of parameters to the types of preservation (annex to
Table 2 -
table 1)
Allocating the corresponding parameters to one of the non-specific types of pres-
ervation given in table 2 is intended to help the user to select a type of preservation
which is effective for several parameters simultaneously, if necessary. However,
limited applicability should be checked in each individual case on the basis of the
data for individual materials. Parameters not listed in table2 should not normally be
preserved using these methods.
Suitable for Not suitable for
Preservation by
Acidification to pH < 2 Alkaline metals Cyanides
Sulfides
Aluminium
Ammonia (but not if separate free Carbonates, bicarbonates, carbon
dioxide
and total ammonia analyses are
required)
Sulfites, sulfur dioxide
Arsenic
Thiosulfates
Alkaline earth metals
Nitrites
Nitrate
Phosphonates (if speciation is re-
Total hardness quired)
Soaps and esters ,
Phosphorus, total
Hexamethylenetetramine
Heavy metals
Do not use sulfuric acid for
calcium, strontium, barium,
radium, lead.
Do not us
...