1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN ISO 14403-1:2012Water quality Determinationof total cyanide and freecyanide using flow analysis(FIA and CFA)Part 1: Method using flow injection analysis(FIA) (ISO 14403-1:2
2、012)BS EN ISO 14403-1:2012 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN ISO14403-1:2012.The UK participation in its preparation was entrusted to TechnicalCommittee EH/3/2, Physical chemical and biochemical methods.A list of organizations represented on this c
3、ommittee can beobtained on request to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2012. Published by BSI StandardsLimited 2012ISBN 978 0 580 66025 2ICS 13.060
4、.50Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 July 2012.Amendments issued since publicationDate Text affectedEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE N
5、ORM EN ISO 14403-1 July 2012 ICS 13.060.50 English Version Water quality - Determination of total cyanide and free cyanide using flow analysis (FIA and CFA) - Part 1: Method using flow injection analysis (FIA) (ISO 14403-1:2012) Qualit de leau - Dosage des cyanures totaux et des cyanures libres par
6、analyse en flux continu (FIA et CFA) - Partie 1: Mthode par analyse avec injection de flux (FIA) (ISO 14403-1:2012) Wasserbeschaffenheit - Bestimmung von Gesamtcyanid und freiem Cyanid mittels Flieanalytik (FIA und CFA) - Teil1: Verfahren mittels Flieinjektionsanalyse (FIA) (ISO 14403-1:2012) This E
7、uropean Standard was approved by CEN on 13 July 2012. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references c
8、oncerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member
9、 into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, Franc
10、e, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOM
11、ITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 14403-1:2012: EBS EN ISO 14403-1:2012EN ISO 14403-1:2012 (E) 3 Foreword This document (EN ISO 14403-1:201
12、2) has been prepared by Technical Committee ISO/TC 147 “Water quality“ in collaboration with Technical Committee CEN/TC 230 “Water analysis” the secretariat of which is held by DIN. This European Standard shall be given the status of a national standard, either by publication of an identical text or
13、 by endorsement, at the latest by January 2013, and conflicting national standards shall be withdrawn at the latest by January 2013. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible
14、for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, For
15、mer Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. Endorsement notice The text of ISO 14403
16、-1:2012 has been approved by CEN as a EN ISO 14403-1:2012 without any modification. BS EN ISO 14403-1:2012ISO 14403-1:2012(E) ISO 2012 All rights reserved iiiContents PageForeword ivIntroduction v1 Scope 12 Normative references . 13 Terms and definitions . 14 Interferences . 24.1 Interferences by ox
17、idizing agents . 24.2 Interferences by sulfide, sulfite, nitrite, and carbonyl compounds . 24.3 Other interferences . 25 Principle . 25.1 Determination of total cyanide . 25.2 Determination of free cyanide 36 Reagents 37 Apparatus 58 Sampling and sample preparation 69 Procedure 79.1 Flow system set-
18、up . 79.2 Reagent blank measurement . 79.3 Checking the suitability of the flow system . 79.4 Calibration . 89.5 Sample measurement . 810 Calculation 911 Expression of results . 912 Test report . 9Annex A (informative) Examples of flow systems .10Annex B (normative) Determination of the real cyanide
19、 concentration in the potassium cyanide solution (6.18.1) 11Annex C (informative) Performance data .12Bibliography .14BS EN ISO 14403-1:2012ISO 14403-1:2012(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies).
20、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-g
21、overnmental, 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.International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
22、The main task of technical committees is to prepare International Standards. 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 vo
23、te.Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights.ISO 14403-1 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physi
24、cal, chemical and biochemical methods.ISO 14403 consists of the following parts, under the general title Water quality Determination of total cyanide and free cyanide using flow analysis (FIA and CFA): Part 1: Method using flow injection analysis (FIA) Part 2: Method using continuous flow analysis (
25、CFA)iv ISO 2012 All rights reservedBS EN ISO 14403-1:2012ISO 14403-1:2012(E)IntroductionMethods using flow analysis automate wet chemical procedures and are particularly suitable for the processing of many analytes in water in large series of samples at a high frequency of analysis.Analysis can be p
26、erformed by flow injection analysis (FIA) or continuous flow analysis (CFA). Both methods share the feature of an automatic introduction of the sample into a flow system (manifold) in which analytes in the sample react with reagent solutions on their way through the manifold. Sample preparation may
27、be integrated in the manifold. The reaction product is measured in a flow detector (e.g. flow photometer).See the foreword for a list of parts of this International Standard.It should be investigated whether and to what extent particular problems require the specification of additional marginal cond
28、itions. ISO 2012 All rights reserved vBS EN ISO 14403-1:2012BS EN ISO 14403-1:2012Water quality Determination of total cyanide and free cyanide using flow analysis (FIA and CFA) Part 1: Method using flow injection analysis (FIA)WARNING Persons using this part of ISO 14403 should be familiar with nor
29、mal laboratory practice. This part of ISO 14403 does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user to establish appropriate safety and health practices and to ensure compliance with any national regulatory conditions.IMPORTAN
30、T It is absolutely essential that tests conducted according to this part of ISO 14403 be carried out by suitably trained staff.1 ScopeThis part of ISO 14403 specifies methods for the determination of cyanide in various types of water (such as ground, drinking, surface, leachate, and waste water) wit
31、h cyanide concentrations from 2 g/l to 500 g/l expressed as cyanide ions in the undiluted sample. The range of application can be changed by varying the operation conditions, e.g. by diluting the original sample or using a different injection volume.In this part of ISO 14403, a suitable mass concent
32、ration range from 20 g/l to 200 g/l is described.Seawater can be analysed with possible changes in sensitivity and adaptation of the reagent and calibration solutions to the salinity of the samples.2 Normative referencesThe following referenced documents are indispensable for the application of this
33、 document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies.ISO 3696, Water for analytical and laboratory use Specification and test methodsISO 5667-3, Water quality Sampling Part 3: Preserv
34、ation and handling of water samplesISO 8466-1, Water quality Calibration and evaluation of analytical methods and estimation of performance characteristics Part 1: Statistical evaluation of the linear calibration functionISO 8466-2, Water quality Calibration and evaluation of analytical methods and
35、estimation of performance characteristics Part 2: Calibration strategy for non-linear second-order calibration functions3 Terms and definitionsFor the purposes of this document, the following terms and definitions apply.3.1free cyanideeasily liberatable cyanidesum of cyanide ions and the cyanide bou
36、nd in weak metal cyanide complexes that liberate HCN at pH 3,83.2total cyanidefree cyanide (3.1), and in addition stronger metalcyanide complex compounds, with the exception of cyanide bound in gold, platinum, cobalt, ruthenium, and rhodium complexes from which recovery can be partialINTERNATIONAL S
37、TANDARD ISO 14403-1:2012(E) ISO 2012 All rights reserved 1BS EN ISO 14403-1:2012ISO 14403-1:2012(E)4 Interferences4.1 Interferences by oxidizing agentsOxidizing agents such as chlorine decompose most of the cyanides. If the presence of oxidizing agents cannot be excluded, treat the sample immediatel
38、y after sampling. Test a drop of the sample with potassium iodide-starch test paper (KI starch paper); a blue colour indicates the need for treatment. Add sodium thiosulfate, a few crystals at a time, until a drop of sample produces no colour on the indicator paper.Carry out a holding time study at
39、the sampling point in order to determine whether the sample is stable for the time period for preservation and whether the preservation is effective. If this preservation is ineffective, online measurement instrumentation may be required.4.2 Interferences by sulfide, sulfite, nitrite, and carbonyl c
40、ompoundsInterferences by sulfide start at 20 mg/l. If a drop of the sample on lead acetate test paper indicates the presence of sulfide, treat an additional 25 ml of the stabilized sample (pH 12) to that required for the cyanide determination with powdered lead carbonate.Lead sulfide precipitates if
41、 the sample contains sulfide.Repeat this operation until a drop of the treated sample solution does not darken the lead acetate test paper.Filter the solution through a dry filter paper into a dry beaker, and from the filtrate measure the sample to be used for analysis. Avoid a large excess of lead
42、and a long contact time in order to minimize loss by complexation or occlusion of cyanide on the precipitated material.Aldehydes and ketones can, under certain conditions, absorb cyanide by nucleophilic addition. To avoid this interference ethylenediamine can be added to the sample.Interference by n
43、itrite occurs above concentrations of 2 mg/l and can be avoided by addition of sulfamic acid (6.8) to the buffer (pH 3,8) for the gas diffusion method (6.20.1).Sulfite interferes above concentrations of 1 mg/l.4.3 Other interferencesParticulate matter in the sample can lead to clogging of the transp
44、ort tubes and interferes with the photometric measurement. Particles of diameter 0,1 mm should be removed by filtration.Thiocyanate can slightly interfere and lead to positive bias (9.3.2). Significant interferences can arise from cyanide impurities in thiocyanate (6.16).5 Principle5.1 Determination
45、 of total cyanideComplex-bound cyanide is decomposed by UV light at pH 3,8. A UV-B lamp (emission maximum 310 nm to 400 nm) and a digestion coil of perfluoro (ethylene/propylene) (FEP) or polytetrafluorethylene (PTFE) is used to filter off UV light with a wavelength 310 nm to 400 nm; a power of 8 W
46、to12 W; a digestion coil of FEP or PTFE, internal diameter 0,8 mm, length 5 000 mm, tube wall thickness at maximum 1 mm (e.g. 351 nm UV lamp with PTFE coil).The equipment shall be such that no UV light with a wavelength below 290 nm can reach the sample flow to avoid decomposition of thiocyanate to
47、cyanide.7.1.6 Thermoreactor 1: digestion coil of FEP with 0,8 mm 3 600 mm, tube wall thickness at maximum 1,5 mm with a temperature of 85 C for total cyanide and 40 C for free cyanide (see Figure A.1).7.1.7 Gas diffusion cell, with hydrophobic semipermeable membrane made from polypropylene or PTFE,
48、for example, typical thickness 90 m to 200 m, pore size 0,1 m to 1 m.7.1.8 Manifold with highly reproducible dosing of sample and reagents, with appropriate transport systems and connection assemblies of chemically inert polymer.7.1.9 Photometric detector, with flow cell, wavelength 600 nm 10 nm. An
49、 appropriate optical pathlength should be used to achieve a minimum absorbance (absolute value) of 0,005 for a 20 g/l cyanide solution.7.1.10 Recording unit (e.g. strip chart recorder, integrator, printer and plotter or a computer data system). In general, peak height signals are measured.7.1.11 Thermoreactor 2, 65 C, length 3 000 mm, internal diameter 0,8 mm (see Figure A.1).7.2 Additional apparatus.7.2.1 Lead acetate test paper, commercially available.7.2.2 Membrane filter assembly, with membrane filters having a por
