1、BRITISH STANDARD BS EN ISO 13395:1996 Water quality Determination of nitrite nitrogen and nitrate nitrogen and the sum of both by flow analysis (CFA and FIA) and spectrometric detection The European Standard EN ISO 13395:1996 has the status of a British Standard ICS 13.060BSENISO13395:1996 This Brit
2、ish Standard, having been prepared under the directionof the Health and Environment Sector Board, was published under the authority of the Standards Board and comes into effect on 15 November 1996 BSI 10-1998 The following BSI references relate to the work on this standard: Committee reference EH/3/
3、2 Draft for comment 94/501676 DC ISBN 0 580 26092 5 Committees responsible for this British Standard The preparation of this British Standard was entrusted by Technical Committee EH/3, Water quality, to Subcommittee EH/3/2, Physical, chemical and biochemical methods, upon which the following bodies
4、were represented: British Agrochemicals Association Ltd. British Ceramic Research British Gas plc British Soft Drinks Association Ltd. Chemical Industries Association Convention of Scottish Local Authorities Department of the Environment (Her Majestys Inspectorate of Pollution) Department of the Env
5、ironment (Water Directorate) Department of Trade and Industry (Laboratory of the Government Chemist) GAMBICA (BEAMA) Ltd. Industrial Water Society National Rivers Authority Royal Society of Chemistry Soap and Detergent Industry Association Society of Chemical Industry Swimming Pool and Allied Trades
6、 Association Ltd. Water Companies Association Water Research Centre Water Services Association of England and Wales Amendments issued since publication Amd. No. Date CommentsBSENISO13395:1996 BSI 10-1998 i Contents Page Committees responsible Inside front cover National foreword ii Foreword 2 1 Scop
7、e 3 2 Normative references 3 3 Principle 3 4 Reagents 3 5 Apparatus 6 6 Checking the flow system 7 7 Sampling and sample preparation 7 8 Interferences 7 9 Procedure 7 10 Evaluation 9 11 Expression of results 9 12 Precision 9 13 Test report 13 Annex A (informative) Examples of flow injection systems
8、(5.1) for the determination of nitrite(N) and nitrite/nitrate(N) 14 Annex B (informative) Examples of continuous flow systems (5.2) for the determination of nitrate(N) and nitrite/nitrate(N) 15 Annex C (informative) Example of a continuous flow system (so-called “macroflow”) (5.2) for the determinat
9、ion of 0,2 mg/l to 2 mg/l nitrite/nitrate(N) 16 Annex D (informative) Bibliography 17 Figure A.1 14 Figure B.1 15 Figure C.1 16 Table 1 Options for preparing the solutions C and B in Figure A.1, Figure B.1 and Figure C.1 4 Table 2 Preparation of the calibration solutions for nitrite(N) 5 Table 3 Pre
10、paration of the calibration solutions for nitrite/nitrate(N) 6 Table 4 Statistical data for the determination of nitrite(N) withflowinjectionanalysis (FIA) 10 Table 5 Statistical data for the determination of nitrite(N) with continuousflow analysis (CFA) 11 Table 6 Statistical data for the determina
11、tion of nitrite/nitrate(N) with flowinjection analysis (FIA) 12 Table 7 Statistical data for the determination of nitrite/nitrate(N) with continuous flow analysis (CFA) 13 List of references Inside back coverBSENISO13395:1996 ii BSI 10-1998 National foreword This British Standard has been prepared b
12、y Subcommittee EH/3/2 and is the English language version of EN ISO 13395:1996 Water quality Determination of nitrite nitrogen and nitrate nitrogen and the sum of both by flow analysis (CFA and FIA) and spectrometric detection published by the European Committee for Standardization (CEN). It is iden
13、tical with ISO 13395:1996 published by the International Organization for Standardization (ISO). NOTEThe tests described in this British Standard should only be carried out by suitably qualified persons with an appropriate level of chemical expertise. Standard chemical procedures should be followed
14、throughout. A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. Cross-references Publication
15、referred to Corresponding British Standard ISO 3696:1987 BS EN ISO 3696:1995 Water for analytical laboratory use. Specification and test methods BS EN 25667 Water quality. Sampling ISO 5667-1:1980 Part 1:1994 Guidance on the design of sampling programmes ISO 5667-2:1991 Part 2:1993 Guidance on sampl
16、ing techniques ISO 5667-3:1994 BS 6068 Water quality Part 6 Sampling Section 6.3:1996 Guidance on the preservation and handling of samples ISO 6777:1984 BS EN 26777:1993 Water quality. Physical, chemical and biochemical methods. Determination of nitrite: molecular absorption spectrometric method Sum
17、mary of pages This document comprises a front cover, an inside front cover, pages i and ii, theENtitlepage, pages2 to 18, an inside back cover and a back cover. This standard has been updated (see copyright date) and may have had amendments incorporated. This will be indicated in the amendment table
18、 on theinside front cover.EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 13395 July 1996 ICS:13.060.00 Descriptors: Water, quality, water pollution, water tests, chemical analysis, determination of content, nitrogen, nitrates, nitrites. English version Water quality Determination of nitrit
19、e nitrogen and nitrate nitrogen and the sum of both by flow analysis (CFAand FIA) and spectrometric detection Qualit de leau Dtermination de lazote nitreaux et de lazote nitrique et de la somme des deux par analyse en flux (CFA et FIA) et dtection spectromtrique (ISO 13395:1996) This European Standa
20、rd was approved by CEN on 1996-06-09. 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 concerning such n
21、ational standards may be obtained on application to the Central Secretariat 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 into its own language and
22、 notified to the Central Secretariat has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United K
23、ingdom. CEN European Committee for Standardization Comit Europen de Normalisation Europisches Komitee fr Normung Central Secretariat: rue de Stassart 36, B-1050 Brussels 1996 Copyright reserved to CEN members Ref. No. EN ISO 13395:1996 EENISO13395:1996 BSI 10-1998 2 Foreword The text of the Internat
24、ional Standard ISO13395:1996 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 publicati
25、on of an identical text or by endorsement, at the latest by January 1997 and conflicting national standards shall be withdrawn at the latest by January 1997. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this
26、 European Standard: Austria, Belgium, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom.ENISO13395:1996 BSI 10-1998 3 1 Scope This International Standard specifies a method for the determinatio
27、n of nitrite(N) (see note 2), nitrate(N) or the sum of both nitrite/nitrate(N), in various types of waters (such as ground, drinking, surface, and waste waters) in mass concentrations ranging from 0,01 mg/l to 1 mg/l for nitrite(N) and from 0,2 mg/l to 20 mg/l for nitrite/nitrate(N), both in the und
28、iluted sample. The range of application can be changed by varying the operating conditions. NOTE 1Seawater may be analysed with changes in respect to sensitivity and adaptation of the carrier solution and calibration solutions to the salinity of the samples. NOTE 2The following concise terms are use
29、d in the text of this International Standard: 2 Normative references The following standards contain provisions which, through reference in this text, constitute provisions of this International Standard. At the time of publication, the editions indicated were valid. All standards are subject to rev
30、ision, and parties to agreements based on this International Standard are encouraged to investigate the possibility of applying the most recent editions of the standards indicated below. Members of IEC and ISO maintain registers of currently valid International Standards. ISO 3696:1987, Water for an
31、alytical laboratory use Specification and test methods. ISO 5667-1:1980, Water quality Sampling Part1: Guidance on the design of sampling programmes. ISO 5667-2:1991, Water quality Sampling Part2: Guidance on sampling techniques. ISO 5667-3:1994, Water quality Sampling Part3: Guidance on the preserv
32、ation and handling of samples. ISO 6777:1984, Water quality Determination of nitrite Molecular absorption spectrometric method. 3 Principle 3.1 Sum of nitrite(N) and nitrate(N), nitrite/nitrate(N) With flow injection analysis (FIA), the sample is fed into a continuously flowing buffer solution (carr
33、ier stream) by means of an injection valve, or, with continuous flow analysis (CFA) being applied, it is continuously mixed with this buffer solution. Nitrate in the sample is reduced with metallic cadmium to nitrite 4 . Then, a phosphoric acid reagent solution that is also flowing continuously is a
34、dmixed. Nitrite that is initially present and nitrite resulting from the reduction of nitrate will diazotize sulfanilamide in acid solution to the diazonium salt which is then coupled with N-(1-naphthyl)ethylenediamine to form a red dye 567 . Waste containing cadmium in liquid or solid form shall be
35、 removed appropriately. 3.2 Nitrite(N) Nitrite(N) is determined, omitting the cadmium reduction, directly by the above-mentioned diazotization and coupling reaction 8 . The chemical reactions of the nitrite are identical with those in the manual procedure (see ISO 6777). 3.3 Nitrate(N) The mass conc
36、entration of nitrate(N) is given by the difference: nitrite/nitrate(N) nitrite(N). 4 Reagents If not stated otherwise, only reagents of recognized analytical grade and water according to grade 1 of ISO 3696 shall be used. The blank value of the reagents shall be checked regularly (see 9.3). 4.1 Phos
37、phoric acid (H 3 PO 4 ), r = 1,71 g/ml. 4.2 Sulfanilamide (4-aminobenzenesulfonamide, C 6 H 8 N 2 O 2 S). 4.3 N-(1-naphthyl)ethylenediaminedihydrochloride N-(1-naphthyl)-1,2- diaminoethanedihydrochloride), C 12 H 16 N 2 Cl 2 . 4.4 Sodium nitrite (NaNO 2 ), dried to constant mass at, for example, 150
38、 C. 4.5 Potassium nitrate (KNO 3 ), dried to constant mass at, for example, 150 C. 4.6 Imidazole (C 3 H 4 N 2 ), for synthesis, or alternatively ammonium chloride (NH 4 Cl), dried to constant mass at 105 C (see note 3). 4.7 Hydrochloric acid I (HCl) concentrated, w = 37 %. nitrite(N): (mass concentr
39、ation of) nitrite, expressed as nitrogen nitrate(N): (mass concentration of) nitrate, expressed as nitrogen nitrite(N)/nitrate(N): (mass concentration of) the sum of nitrite(N) and nitrate(N)ENISO13395:1996 4 BSI 10-1998 4.8 Hydrochloric acid II, c(HCl) = 1 mol/l. 4.9 Copper sulfate solution I, r(Cu
40、SO 4 5H 2 O) = 2,5 g/l; this solution is stable. 4.10 Copper sulfate solution II, r(CuSO 4 5H 2 O) = 20 g/l; this solution is stable. 4.11 Polyethyleneglycol dodecyl ether HO (CH 2 CH 2 O) n C 12 H 21 , surfactant, u = 33 C to 41 C, solution, w = 30 %. The solution is stable for approximately 4 week
41、s. 4.12 Cadmium granulate (Cd), grain size, for example 0,3 mm to 1,5 mm (a minimum reduction capacity of 90 % shall be reached; see 5.1 and 5.2). 4.13 Imidazole stock solution, c = 0,25 mol/l. Dissolve, in a beaker of nominal capacity1litre,17,0 g of imidazole (4.6) inapproximately 900 ml of water.
42、 While stirring with a magnetic stirrer, add hydrochloric acid I (4.7) and adjust, with the help of a pH electrode, the pH to 7.5. Transfer to a volumetric flask, of nominal capacity1000 ml, and dilute to volume with water. The solution is stable for 4 weeks if kept in a brown glass bottle at room t
43、emperature. 4.14 Buffer solution Mix 100 ml of the imidazole stock solution (4.13) with 100 l of copper sulfate solution I (4.9). Prepare the solution freshly before use. NOTE 3Alternatively an ammonium buffer solution can be used, for example: 85 g of ammonium chloride (NH 4 Cl) should be dissolved
44、 in water and diluted to a volume of1000ml, and the pH should be adjusted to approximately7,5. 4.15 Carrier or dilution solutions, C and B in Figure A.1, Figure B.1 and Figure C.1. Table 1 shows some well-known options for preparing these solutions. Prepare the solutions, containing the surfactant(4
45、.11), freshly before use. Prior to use, solutions C and B for FIA shall be degassed, for example by membrane filtration (vacuum). Table 1 Options for preparing the solution C and B in Figure A.1, Figure B.1 and Figure C.1 4.16 Buffered copper sulphate solution Mix 20 ml of the copper sulfate solutio
46、n II (4.10) and20 ml of the imidazole stock solution (4.13) in a beaker of nominal capacity 50 ml. Prepare the solution freshly before use. 4.17 Reagent solution, R 1(in Figure A.1, Figure B.1 and Figure C.1). Dissolve, in a volumetric flask of nominal capacity500 ml, 5 g of sulfanilamide (4.2), 0,5
47、 g of N-(1-naphthyl)ethylenediaminedihydrochloride (4.3) in water, add 50 ml of phosphoric acid (4.1), and dilute to volume. Stored in a brown glass bottle, the solution is stable for at least one week. NOTE 4For the preparation of this reagent solution, hydrochloric acid (4.7, 4.8) may be used inst
48、ead of phosphoric acid, provided equivalent performance characteristics are obtained. The solutions of sulfanilamide (4.2) and N-(1-naphthyl)ethylenediaminedihydrochloride (4.3) can also be made separately and dosed into the equipment by different lines. Prior to use, solution R 1for FIA shall be de
49、gassed, for example by membrane filtration (vacuum). Method Parameter Content of solution C (see Figure A.1, Figure B.1 and Figure C.1) Contents of solution B (seeFigure A.1, Figure B.1and Figure C.1) FIA Nitrite Water Water aBuffer (4.14) aNo solutionB a Nitrite/nitrate Buffer (4.14) Buffer (4.14) CFA Nitrite “C” is not necessary Water a,bBuffer (4.14) a,b No solutionB a,b Nitrite/nitrate “C” is not necessary Buffer (4.14) b a Three different alternatives. b If, in the case of CFA, water or buff
