SIST EN ISO 10304-2:1998
(Main)Water quality - Determination of dissolved anions by liquid chromatography of ions - Part 2: Determination of bromide, chloride, nitrate, nitrite, orthophosphate and sulfate in waste water (ISO 10304-2:1995)
Water quality - Determination of dissolved anions by liquid chromatography of ions - Part 2: Determination of bromide, chloride, nitrate, nitrite, orthophosphate and sulfate in waste water (ISO 10304-2:1995)
The method is intended for monitoring waste water and the respective concentration of the anions mentioned in the title.
Wasserbeschaffenheit - Bestimmung der gelösten Anionen mittels Ionenchromatographie - Teil 2: Bestimmung von Bromid, Chlorid, Nitrat, Nitrit, Ortho-Phosphat und Sulfat in Abwasser (ISO 10304-2:1995)
Dieser Teil der ISO 10304 beschreibt ein Verfahren zur Bestimmung der gelösten Anionen Bromid, Chlorid, Nitrat, Nitrit, ortho-Phosphat und Sulfat in Abwasser. Die in Tabelle 1 angegebenen Arbeitsbereiche werden nach entsprechender Probenvorbereitung (z.B. Verdünnung) und mit einem Leitfähigkeitsdetektor (LF) oder einem UV-Detektor erreicht.
Qualité de l'eau - Dosage des anions dissous par chromatographie des ions en phase liquide - Partie 2: Dosage des ions bromure, chlorure, nitrate, nitrite, orthophosphate et sulfate, dans les eaux usées (ISO 10304-2:1995)
Kakovost vode - Določevanje raztopljenih anionov z ionsko kromatografijo - 2. del: Določevanje bromida, klorida, nitrata, nitrita, ortofosfata in sulfata v odpadni vodi (ISO 10304-2:1995)
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN ISO 10304-2:1998
01-januar-1998
1DGRPHãþD
SIST ISO 10304-2:1996
.DNRYRVWYRGH'RORþHYDQMHUD]WRSOMHQLKDQLRQRY]LRQVNRNURPDWRJUDILMRGHO
'RORþHYDQMHEURPLGDNORULGDQLWUDWDQLWULWDRUWRIRVIDWDLQVXOIDWDYRGSDGQLYRGL
,62
Water quality - Determination of dissolved anions by liquid chromatography of ions - Part
2: Determination of bromide, chloride, nitrate, nitrite, orthophosphate and sulfate in waste
water (ISO 10304-2:1995)
Wasserbeschaffenheit - Bestimmung der gelösten Anionen mittels
Ionenchromatographie - Teil 2: Bestimmung von Bromid, Chlorid, Nitrat, Nitrit, Ortho-
Phosphat und Sulfat in Abwasser (ISO 10304-2:1995)
Qualité de l'eau - Dosage des anions dissous par chromatographie des ions en phase
liquide - Partie 2: Dosage des ions bromure, chlorure, nitrate, nitrite, orthophosphate et
sulfate, dans les eaux usées (ISO 10304-2:1995)
Ta slovenski standard je istoveten z: EN ISO 10304-2:1996
ICS:
13.060.30 Odpadna voda Sewage water
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
SIST EN ISO 10304-2:1998 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST EN ISO 10304-2:1998
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SIST EN ISO 10304-2:1998
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SIST EN ISO 10304-2:1998
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SIST EN ISO 10304-2:1998
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SIST EN ISO 10304-2:1998
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SIST EN ISO 10304-2:1998
INTERNATIONAL ISO
STANDARD 10304-2
First edition
1995-04-01
Determination of
Water quality -
dissolved anions by liquid chromatography
of ions -
Part 2:
Determination of bromide, chloride, nitrate,
nitrite, orthophosphate and sulfate in waste
water
Quakt6 de I ’eau - Dosage des anions dissous par Chromatographie des
ions en Phase liquide -
Partie 2: Dosage des ions bromure, chlorure, nitrate, nitrite,
orthophosphate et sulfate dans les eaux us6es
Reference number
ISO 10304~2:1995(E)
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SIST EN ISO 10304-2:1998
Foreword
ISO (the International Organization for Standardization) is a worldwide
federation of national Standards bodies (ISO member bodies). The work
of preparing International Standards is normally carried out through ISO
technical committees. Esch 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 10304-2 was prepared by Technical Committee
ISO/TC 147, Water quality, Subcommittee SC 2, Physical, Chemical,
biochemical methods.
ISO 10304 consists of the following Parts, under the general title Water
quality - Determination of dissolved anions by liquid chroma tography of
ions:
- Part 2: Determination o f bromide, chloride, nitfa te, nitfite, orthophos-
pha te and sulfa te in waste wa ter
- Part 3: Determination of chromate, iodide, sulfite, thiocyanate and
thiosulfa te
- Part 4: Determination of chlorate, chloride and chlorite in water with
low con tamina tion
The title of ISO 10304-1 :1992 is Water quality - Determination of dis-
solved fluoride, chloride, nitrite, orthophosphate, bromide, nitra te and sul-
fate ions, using liquid chromatography of ions - Part 1: Method for wa ter
with Io w con tamina tion
Annex A of this part of ISO 10304 is for information only.
0 ISO 1995
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced
or utilized in any form or by any means, electronie or mechanical, including photocopying and
microfilm, without Permission in writing from the publisher.
International Organization for Standardization
Case Postale 56 l CH-l 211 Geneve 20 l Switzerland
Printed in Switzerland
ii
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SIST EN ISO 10304-2:1998
Q ISO
ISO 10304=2:1995(E
Introduction
The essential minimum requirements of an ion chromatographic System
to be applied within the scope of this part of ISO 10304 are the following:
Resolution power
It is essential that the peak resolution R does not fall below 1,3 for the
anion to be determined and the nearest peak (see clause 6 and figure3).
Method of detection
a) Measurement of the electrical conductivity with or without a sup-
pressor device, respectively.
b) Photometric measurement (UV/VlS), directly or indirectly.
Applicability of the method
Working ranges are according to table 1.
Calibration
Calibration and determination of the linear working range. Use of the
cases of application (see
method of Standard addition for specia
clause 9).
Quality control of the analytical method
Validity C heck of th e calibration function see 8.3). Replicate determi-
nations if necessary.
The diversity of the appropriate and suitable assemblies and the pro-
cedural Steps depending on them (e.g. composition of the mobile phases)
permit a global description only.
For further information on the analytical technique, refer to ISO 103044.
. . .
Ill
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SIST EN ISO 10304-2:1998
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SIST EN ISO 10304-2:1998
INTERNATIONAL STANDARD 0 ISO ISO 10304-2:4995(t
Water quality - Determination of dissolved anions by
liquid chromatography of ions -
Part 2:
Determination of bromide, chloride, nitrate, nitrite,
orthophosphate and sulfate in waste water
1.2 Interferences
1 Scope
1.1 General
1.2.1 Organic acids,
such as monocarboxylic or
This part of ISO 10304 specifies a method for the
dicarboxylic acids, tan interfere with the determi-
determination of the dissolved anions bromide, chlor-
nation of inorganic anions.
ide, nitrate, nitrite, orthophosphate and sulfate in
waste waters.
The working ranges listed in table 1 may be obtained
by an appropriate Sample pretreatment (e.g. dilution)
and by applying a conductivity detector (CD) or a
1.2.2 In a buffered eluent (e.g. carbonatelhydrogen
UV-detector.
carbonate), the determination will not be influenced
by the Sample pH in the range of pH 2 to pH 9.
Table 1 - Working ranges of the analytical
method
Working
Detection
range
Anion
1.2.3 Large concentration differentes between the
direct
w/l
anions Br-, Cl-, NO$ NOT, PO:- and SO:- may lead
UV-detection
to typical Cross-sensitivity interferences caused by an
Bromide (Br-) 0,05 to 20 CD or UV (200 nm
insufficient Separation. The respective concentrations
to 215 nm)
given in table 2 were typical for conductivity detectors
Chloride (Cl-) 0,l to 50 CD
and UV-detectors; no interferences could be observed
0,l to 50 CD or UV (200 nm
Nitrate (NO,)
to 215 nm) with a Sample volume of 50 ~1. The data given are
0,05 to 20 CD or UV (200 nm
Nitrite (NOT) valid only when the quality requirements specified for
to 215 nm)
the columns are met (sec clause 6). The determi-
Orthophosphate
nation of chloride may be subject to interference from
0,l to 20 CD
Po:-)
high fluoride concentrations.
Sulfate (SO:-> 0,l to 100 CD
NOTE - The working range is limited by the exchange
capacity of the columns.
1
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SIST EN ISO 10304-2:1998
ISO 10304~2:1995(E) 0 ISO
1.2.4 The determination of sulfate may be subject
to interference by high iodide or thiosulfate concen-
Table 2 - Cross-sensitivity of anions
trations.
[Detection: conductivity (CD) and direct UV]
Relations: SO:-/l- or SOi-is,O$- or l-/S,Oz- =
tolerable absolute
Ratio sf the mass
1: > 500
concentration of
concentrations
interfering ionsl)
solute/interfering ion
Cross-sensitivities to other anions, such as Br-, Cl-,
NO;, NO,, PO:- and SO:-, may occur, especially in
the presence of sulfite ions whose retention strongly
depends on the selectivity of the separating column
used. Inorganic anions such as fluoroborate or chlorite
tan interfere with the determination of the named in-
organic anions.
NOTE 1 The identification of some anions (e.g. nitrite) or
the detection of interferences (e.g. fatty acids) tan be fa-
cilitated by using a conductivity detector and UV-detector
placed in series.
Anion combinations (e.g. Cl-/l-) which are not listed
in table 2 will not interfere in the specified range of
application.
Solid particles and organic compounds (such as min-
eral oils, detergents and humic acids) shorten the
lifetime of the separating column and are therefore
eliminated before the analysis
is started (sec
clause 7).
Sulfide ions tan Cause errors during the determination
of sulfate; they are eliminated according to clause 7.
NO,INO, 1:500 NO; 500
NO,/SO;- 1:500 (CD) so;- 500
1:1 000 (UV) so;- 500
2 Normative references
PO:-/Br- 1:lOO Br- 100
The following Standards contain provisions which,
1:500 Cl- 500
Po;-/cI-
through reference in this text, constitute provisions
1:500 NO; 400
PO;-/NO,
of this part of ISO 10304. At the time of publication,
PO;-/NO, 1:lOO NO; 100
the editions indicated were valid. All Standards are
subject to revision, and Parties to agreements based
1:500 so;- 500
po;-/so:-
on this part of ISO 10304 are encouraged to investi-
po;-/so;- 1:5o*)
gate the possibility of applying the most recent edi-
tions of the Standards indicated below. Members of
so;-/cr 1:500 Cl- 500
IEC and ISO maintain registers of currently valid
SO;-/NO3 1:500 NO3 400
International Standards.
sog-po;- 1:50*,
1:500
so;-/s,o;-
ISO 5667-1 :1980, Water quality - Sampling -
Part 1: Guidance on the design of sampling pro-
so;-/r 1:500
grammes.
1) Dilute the Sample if the interfering concentration is
exceeded.
ISO 5667-2:1991, Watet- quality - Sampling -
2) When it is present, SO:- will always interfere, Part 2: Guidance on sampling techniques.
ISO 5667-3:1994, Water quality - Sampling -
Part 3: Guidance on the preservation and handling of
samples.
2
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SIST EN ISO 10304-2:1998
0 ISO ISO 10304-2:1995(~
ISO 8466-1: 1990, Wa ter quality - Calibration and 4.2 Sodium carbonate (Na,CO,).
evaluation of analytical methods and estimation of
Performance characteristics - Part 1: Statistical
4.3 Potassium hydrogenphthalate (CaH,O,K).
evaluation of the linear calibration function.
4.4 Sodium tetraborate (Na,B,O,.l OH,O).
ISO 10304-1 :1992, Water quality - Determination of
dissolved fluoride, chloride, nitrite, orthophospha te,
4.5 Gluconic acid, w(C~H,,O,) = 50 % (VW),
bromide, nitrate and sulfate ions, using liquid chro-
aqueous Solution.
matography of ions - Part 1: Me thod for wa ter with
low con tamina tion.
4.6 Methanol (CH,OH).
3 Principle
4.7 Lithium hydroxide (LiOH).
Liquid chromatographic Separation of ions by means
4.8 Glycerol (C, -I,O,).
of a separating column. Use of an anion exchanger as
the stationary Phase, and usually, aqueous solutions
of salts of weak monobasic and dibasic acids as mo-
4.9 Acetonitrile (CH,CN).
bile phases (eluent, see 4.17). Conductivity and
UV-detectors are used within this part of ISO 10304.
4.10 Potassium hydroxide (KOH).
When using conductivity detectors, it is essential that
the eluents have a sufficiently low conductivity. For
4.11 Sodium bromide (NaBr).
this reason, conductivity detectors are often com-
bined with a suppressor device (e.g. a cation
4.12 Sodium chloride (NaCI).
exchanger) which decreases the conductivity of the
eluent and converts the separated anions into their
corresponding acids. 4.13 Sodium nitrate (NaNO,).
UV-detection either measures the absorption directly
4.14 Sodium nitrite (NaNO,).
(see table 1) or, in the case of anions which are
transparent in the UV-range, measures the decrease
4.15 Potassium dihydr Bgenphosphate (KH,PO,).
in the background absorption caused by a
UV-absorbing eluent (indirect measurement). If in-
4.16 Sodium sulfate (r\
direct UV-detection is used, the measuring wave-
length depends on the composition of the eluent.
4.17 Eluents
The concentration of the respective anions is deter-
mined by a calibration of the Overall procedure. Par-
Different eluents are usec 1, their choice depending on
ticular cases may require calibration by means of
the type of separating column and detector. There-
Standard addition (spiking).
fore, follow the column manufacturer ’s instructions
for the exact composition of the eluent. The eluent
If no suppressor device is used, it is essential that the
compositions described in 4.17.1 and the last two
conductivity of the eluent be as low as possible.
Paragraphs of 4.17.2.2 are examples only. A choice
of reagents commonly used as eluents is given in 4.1
NOTE 2 References covering this analytical technique are
summarized in annex A of ISO 10304-1 :1992. to 4.10.
Degas all the eluents or prepare eluents using
4 Reagents
degassed water. Take Steps to avoid any renewed gas
pick-up during Operation (e.g. by helium sparging). In
Use only reagents of recognized analytical grade.
Order to avoid the growth of bacteria or algae, store
Weigh with an accuracy of 1 % of the nominal mass.
the eluents in the dark and renew every 2 d to 3 d.
The water shall have an electrical conductivity of
< 0,Ol mS/m and shall be free of particulate matter
4.17.1 Examples of eluents for ion
with diameter > 0,45 Pm. The increase of the elec-
chromatography using the suppressor technique
trical conductivity due to an uptake of carbon dioxide
does not interfere with the determination.
For the application of the suppressor technique,
sodium hydroxide and salt solutions of weakly
dissociated acids, such as sodium carbonate/sodium
4.1 Sodium hydrogencarbonate (NaHCO,).
3
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SIST EN ISO 10304-2:1998
0 ISO
ISO 10304=2:1995(E)
hydrogencarbonate, sodium hydrogencarbonate and 4.17.2.1.1 Potassium hydrogenphthalate
sodium tetraborate tan be used. concentrate
The addition of the following eluent concentrate to the
4.17.1.1 Sodium carbonate/sodium
Sample has proved to be helpful for Sample pretreat-
hydrogencarbonate concentrate
ment and eluent preparation (4.17.2.1.2).
The addition of the following eluent concentrate to the
Place 20,5 g of potassium hydrogenphthalate (4.3) in
Sample has proved to be successful for Sample pre-
a volumetric flask of nominal capacity 1 000 ml, dis-
treatment and eluent preparation (see 4.17.1.2).
solve in water and dilute to volume.
Place 25,4 g of sodium carbonate (4.2) and 25,5 g of
The Solution contains 0,l mol/1 of potassium hydro-
sodium hydrogencarbonate (4.1), in a volumetric flask
genphthalate and is stable for a longer period of time
of nominal capacity 1 000 ml, dissolve in water (see
if stored at 4 “C to 6 “C.
first Paragraph of this clause) and dilute to volume.
4.17.2.1.2 Potassium hydrogenphthalate eluent
The Solution contains 0,24 mol/1 of sodium carbonate
and 0,3 mol/1 of sodium hydrogencarbonate and is
For the determination of chloride, nitrate, nitrite,
stable for several months if stored at 4 “C to 6 “C.
orthophosphate and sulfate in a Single determination,
the following eluent has proved to be successful.
4.17.1.2 Sodium carbonate/sodium
hydrogencarbonate eluent Place 100 ml of the concentrate (4.17.2.1 .l) in a
volumetric flask of nominal capacity 5 000 ml. Add
The following eluent is applicable for the determi-
500 ml of methanol (4.6), dilute with water (see first
nation of bromide, chloride, nitrite, orthophosphate, Paragraph of this clause), adjust to pH 5 with potass-
and sulfate in a Single determination. ium hydroxide (4.10) and dilute to volume.
Place 50 ml of the concentrate (4.17.1 .l) in a The Solution contains 0,002 mol/1 of potassium hy-
volumetric flask of nominal capacity 5 000 ml, and di- drogenphthalate and 10 % (WV) of methanol.
lute to volume with water (see first Paragraph of this
clause). 4.17.2.2 Eluents for an anion exchanger on a
polymer base
The Solution contains 0,002 4 mol/1 of sodium car-
bonate and 0,003 mol/1 of sodium hydrogencarbonate.
Acidic as well as basic eluents may be used for ion
chromatography with an anion exchanger on a poly-
mer base.
4.17.2 Examples of eluents for ion
chromatography without using the suppressor
Examples of typical acidic eluents are solutions con-
technique
taining potassium hydrogenphthalate. Examples of
typical basic eluents are solutions containing
For ion chromatography techniques which do not util-
p-hydroxybenzoate or sodium borate/sodium glucon-
ize suppressor devices, salt solutions (e.g. potassium
ate.
hydrogenphthalate, p-hydroxybenzoic acid, sodium
borate/sodium gluconate and sodium benzoate) are
For the determination of chloride, nitrate, orthophos-
used. The solutions may contain various additions,
phate and sulfate in a Single determination, the
e.g. alcohols. The concentration of the salts is usually
sodium borate/sodium gluconate eluent has proved to
in the range of 0,000 5 mol/1 to 0,Ol mol/l. Concen-
be successful. lt is prepared in the following way.
trate and eluent solutions are prepared as described
in 4.17.2.1.1 and 4.17.2.1.2. Note that some alkaline Place 0,85 g of sodium tetraborate (4.4) and 0,22 g
concentrate solutions of the cited salts are not stable.
of lithium hydroxide (4.7) in a volumetric flask of
Adjust the pH of the eluent after the dilution of the
nominal capacity 5 000 ml. Add 0,6 ml of gluconic
concentrate.
acid (4.5), 3,1 ml of glycerol (4.8), and 600 ml of
acetonitrile (4.9). Dilute to volume with water.
4.17.2.1 Mobile phases for anion exchanger on a
silica gel base 4.18 Stock solutions
For ion chromatography using anion exchanger col- Prepare stock solutions with mass concentration p of
umns on a silica gel base, use only eluents in the pH 1 000 mg/1 for each of the anions: bromide, chloride,
range of 1,5 to 6,5. nitrate, nitrite, orthophosphate and sulfate.
4
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SIST EN ISO 10304-2:1998
0 ISO ISO 10304-2:1995(.
Dissolve the appropriate mass of each of the sub-
stances, prepared as stated in table3, in a small
Table 4 - Volumes of stock solutions for the
quantity of water in volumetric flasks of nominal ca-
preparation of the mixed Standard Solution I
pacity 1 000 ml. Dilute to volume with water. The
Stock solution Anion concentration
solutions are stable for several months if stored at
Anion
ml
4 “C to 6 “C. mg/1
10
Br- 1
Alternatively, use commercially available solutions of
Cl- 10 100
the required concentration.
NO3 10 100
NOTE 3 Nitrite is easily oxidized to nitrate and therefore
NO; 1 10
nitrite Standard solutions should be prepared on the day of
use. po;- 1 10
100
so;- 10
Table 3 - Mass of Portion and pretreatment for
4.19.2 Mixed Standard Solution II
stock solutions
Pretreatment by
I
The mass concentrations of this Solution are as fol-
d fing l)
lows:
Mass of
Anion Salt Duration Temperature
Portion
p(Br-, NOT, PO:-) = 1 mg/1
h “C
g
p(Cl-, NO;, SO:-) = 10 mg/1
Bromide NaBr 1,287 7 6
Chloride NaCI 1,648 4 2
Pipette 10 ml of the mixed Standard Solution I
24
Nitrate NaNO, 1,370 7
(4.19.1) into a volumetric flask of nominal capacity
Nitrite NaNO, 1,499 8 1
100 ml, and dilute to volume with water.
Ortho-
KH,PO, 1,433 0 1
Phosphate
Store these solutions in polyethylene bottles.
1,479 0 1
Sulfate Na,SO,
The Solution is stable for 2 d only, even if stored at
1) Let the substance cool in a desiccator after drying.
4 “C to 6 “C.
4.19.3 Mixed Standard Solution Ill
The mass concentrations of this Solution are as fol-
lows:
4.19 Mixed Standard solutions
p(Br-, NOT, PO:-) = 0,l mg/1
p(CI-, NO;, SO:-) = 1,0 mg/1
4.19.1 Mixed Standard Solution I
Pipette 1 ml of the mixed Standard Solution I (4.19.1)
into a volumetric flask of nominal capacity 100 ml, and
The mass concentrations of this Solution are as fol- dilute to volume with water.
lows:
If possible, store these solutions in polytetrafluoro-
r-, NO;, PO:) = 10 mg/1
ethylene-hexafluoropropylene (FEP) bottles or high
dB
density polyethylene (PE-HD) bottles.
p(CI. NO;, SO:-) = 100 mg/1
The Solution is not stable. Prepare it on the day of
use.
Pip
...
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