DIN EN ISO 11206-2013 Water quality - Determination of dissolved bromate - Method using ion chromatography (IC) and post column reaction (PCR) (ISO 11206 2011) German version EN IS.pdf

1、May 2013 Translation by DIN-Sprachendienst.English price group 12No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 13

2、.060.50!%$*t“2010781www.din.deDDIN EN ISO 11206Water quality Determination of dissolved bromate Method using ion chromatography (IC) and post column reaction (PCR)(ISO 11206:2011);English version EN ISO 11206:2013,English translation of DIN EN ISO 11206:2013-05Wasserbeschaffenheit Bestimmung von gel

3、stem Bromat Verfahren mittels Ionenchromatographie (IC) und Nachsulenreaktion (PCR)(ISO 11206:2011);Englische Fassung EN ISO 11206:2013,Englische bersetzung von DIN EN ISO 11206:2013-05Qualit de leau Dtermination du bromate dissous Mthode utilisant la chromatographie ionique (IC) et la raction post-

4、colonne (PCR)(ISO 11206:2011);Version anglaise EN ISO 11206:2013,Traduction anglaise de DIN EN ISO 11206:2013-05www.beuth.deIn case of doubt, the German-language original shall be considered authoritative.Document comprises 22 pages04.13 DIN EN ISO 11206:2013-05 2 A comma is used as the decimal mark

5、er. National foreword The text of ISO 11206:2011 has been prepared by Technical Committee ISO/TC 147 “Water quality” and has been taken over as EN ISO 11206:2013 by Technical Committee CEN/TC 230 “Water analysis” (Secretariat: DIN, Germany). The responsible German body involved in its preparation wa

6、s the Normenausschuss Wasserwesen (Water Practice Standards Committee), Working Committee NA 119-01-03-01-12 AK Ionenchromatographische Verfahren of NA 119-01-03 AA Wasseruntersuchung. Designation of the method: Determination of dissolved bromate Method using ion chromatography (IC) and post column

7、reaction (PCR) (D 48): Method DIN EN ISO 11206 D 48 This standard has been published to implement the Water Framework Directive (WFD), Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy*). A

8、s a result of national implementation in Germany, the following action has been taken: in Subclause 5.13.3, the reference to 5.15 (original ISO version) has been corrected to 7.2. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 3696 DIN

9、 ISO 3696 ISO 5725-2 DIN ISO 5725-2 ISO 8466-1 DIN 38402-51 ISO 8466-2 DIN ISO 8466-2 ISO 10304-1 DIN EN ISO 10304-1 ISO 10304-4 DIN EN ISO 10304-4 ISO 15061 DIN EN ISO 15061 Expert assistance and specialized laboratories will be required to perform the analyses described in this standard. Existing

10、safety requirements are to be observed. Depending on the objective of the analysis, a check shall be made on a case-by-case basis as to whether and to what extent additional conditions will have to be specified. This standard has been prepared by the Normenausschuss Wasserwesen (Water Practice Stand

11、ards Committee) in collaboration with the Wasserchemische Gesellschaft Fachgruppe in der Gesellschaft Deutscher Chemiker (Water Chemistry Society Division of the German Chemical Society). It is part of the series Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung (German stand

12、ard methods for the examination of water, waste water and sludge): *) Registered in the DITR database of DIN Software GmbH, obtainable from: Beuth Verlag GmbH, 10772 Berlin. DIN EN ISO 11206:2013-05 3 Determination of dissolved bromate Method using ion chromatography (IC) and post column reaction (P

13、CR) (D 48). Standard methods published as DIN Standards are obtainable from Beuth Verlag GmbH, either individually or grouped in volumes. The standard methods included in the loose-leaf publication entitled Deutsche Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung will continue to be

14、 published by Wiley-VCH Verlag GmbH seek advice from the column supplier. The chosen combination of separator column and eluent shall conform to the resolution requirements specified in Clause 7. Use eluents as long as the requirements in Clause 7 and in 9.3 are met.A selection of reagents for commo

15、n eluents is presented in 5.2 to 5.6. Examples for appropriate eluents are given in 5.13.2 and 5.13.3.5DIN EN ISO 11206:2013-05 EN ISO 11206:2013 (E) 5.13.1 Sodium carbonate concentrate, null(Na2CO3) null 0,09 mol/l.The addition of the following eluent concentrate is appropriate for the eluent prepa

16、ration (5.13.2):Dissolve 9,54 g of sodium carbonate (5.2) in water (5.1) in a 1 000 ml volumetric flask and dilute to volume with water (5.1).The solution is stable for 6 months if stored at 2 C to 8 C.5.13.2 Sodium carbonate eluent, null(Na2CO3) null 0,009 mol/l.The following eluent is applicable f

17、or the determination of bromate:Place 100 ml of the sodium carbonate concentrate (5.13.1) in a 1 000 ml volumetric flask and dilute to volume with water (5.1).5.13.3 Sulfuric acid eluent, null(H2SO4) null 0,1 mol/l.Place 100 ml of sulfuric acid (5.3) in a 1 000 ml volumetric flask and dilute to volu

18、me with water (5.1).NOTE Ammonium heptamolybdate tetrahydrate (5.7) can be added to the eluent provided the composition meets the resulting concentration of the PCR reagent in the PCR unit (7.2).5.14 Ammonium heptamolybdate solution, null(NH ) Mo O 4 6 7 24null 0,002 mol/l.Dissolve 0,25 g of ammoniu

19、m heptamolybdate tetrahydrate (5.7) in 100 ml of water (5.1).The solution is stable for 1 month if stored in a light impervious bottle at ambient temperature.5.15 Post column reaction (PCR) reagent.Degas all water used for the preparation of the PCR reagent. Take steps to avoid any renewed air pick-

20、up during operation (e.g. by helium sparging).Dissolve 45 g of potassium iodide (5.8) in approximately 500 ml of water (5.1), add 25 ml of the ammonium heptamolybdate solution (5.14) in a 1 000 ml volumetric flask and dilute to volume with water (5.1).Sparge the solution with helium for 20 min to re

21、move all traces of dissolved oxygen, and immediately place it in the PCR module and pressurize it with helium.The solution contains 0,27 mol/l potassium iodide and 0,05 mmol/l of ammonium heptamolybdate. Prepare the solution on the day of use. Store the solution in light-impervious bottles (e.g. wra

22、pped with aluminium foil) and protect the solution from light exposure.NOTE Since potassium iodide is photosensitive, the solution can develop a light yellow colour with time, even when stored under helium. This can be avoided by the addition of sodium hydroxide (5.4) with a resulting concentration

23、of 0,001 mol/l of sodium hydroxide.5.16 Iron(II) solution, null(Fe2+) null 1 000 mg/l.Place 6 l of nitric acid (5.9) in approximately 15 ml water (5.1) in a 25 ml volumetric flask, dissolve 0,124 g of iron(II) sulfate heptahydrate (5.10) and dilute to volume with water (5.1).The resulting pH value i

24、s about 2. The solution is stable for 2 d.5.17 Bromate stock standard solution, null(BrO3) null 1 000 mg/l.Dry approximately 1,5 g of potassium bromate (5.11) for at least 1 h at 105 C null 5 C. Store the dried solid in a desiccator.6DIN EN ISO 11206:2013-05 EN ISO 11206:2013 (E) Dissolve 1,306 g nu

25、ll 0,001 g of the dried potassium bromate in approximately 800 ml of water (5.1) in a 1 000 ml volumetric flask and dilute to volume with water (5.1). Store the solution at 2 C to 8 C in polyethene or glass bottles and renew it every 12 months.Alternatively, use commercially available stock solution

26、s of the required concentration.5.18 Bromate standard solution.Depending on the concentrations expected, prepare the following standard solutions of different bromate concentrations from the stock standard solution (5.17). Note the possible risk of changes in concentration caused by interaction with

27、 the vessel material, which increases with decreasing bromate concentration. Store the standard solutions in polyethene or glass bottles.5.18.1 Bromate standard solution I, null(BrO3) null 100 mg/l.Pipette 10,0 ml of bromate stock standard solution (5.17) into a 100 ml volumetric flask and dilute to

28、 volume with water (5.1).Store the solution at 2 C to 8 C in polyethene or glass bottles. The solution is stable for 6 months.5.18.2 Bromate standard solution II, null(BrO3) null 1 mg/l.Pipette 1,0 ml of standard solution I (5.18.1) into a 100 ml volumetric flask and dilute to volume with water (5.1

29、).Store the solution at 2 C to 8 C in polyethene or glass bottles. The solution is stable for 3 months.5.19 Bromate calibration solutions.Depending on the bromate concentration expected in the sample, use the bromate standard solution I (5.18.1) or II (5.18.2) to prepare 5 to 10 calibration solution

30、s, distributed over the expected working range as evenly as possible.For example, proceed as follows for the range 0,5 g/l to 5 g/l bromate.Pipette, into a series of 100 ml volumetric flasks, the following volumes: 50 l, 100 l, 150 l, 200 l, 250 l, 300 l, 350 l, 400 l, 450 l and 500 l of the bromate

31、 standard solution II (5.18.2) and dilute to volume with water (5.1).The concentrations of bromate in these calibration solutions are: 0,5 g/l, 1,0 g/l, 1,5 g/l, 2,0 g/l, 2,5 g/l, 3,0 g/l, 3,5 g/l, 4,0 g/l, 4,5 g/l and 5,0 g/l respectively.Prepare the calibration solutions on the day of use.5.20 Bla

32、nk solution.Fill a volumetric flask, e.g. 100 ml, with water (5.1).6 ApparatusUsual laboratory apparatus and, in particular, the following.6.1 IC system, complying with the quality requirements specified in Clause 7, i.e. resolution. In general, it shall consist of the following components (see Figu

33、re 1).6.1.1 Eluent reservoir, and a degassing unit.6.1.2 IC pump, suitable for isocratic or gradient technique.6.1.3 Sample delivery device, e.g. sample pump, including a sample injection system incorporating a sample loop of appropriate volume (e.g. 0,1 ml to 1 ml) or autosampler device.7DIN EN ISO

34、 11206:2013-05 EN ISO 11206:2013 (E) 6.1.4 Recording device, e.g. PC with software for data acquisition and evaluation.6.1.5 Post column reaction (PCR) unit, consisting of the following:6.1.5.1 PCR reagent reservoir.6.1.5.2 Hnulldelivery unit, e.g. H2SO4reservoir, suppressor unit.6.1.5.3 Reagent del

35、ivery system, e.g. peristaltic pump.6.1.5.4 Reaction coil, of e.g. 500 l internal volume.6.1.5.5 Reaction coil heater, capable of maintaining a temperature of 80 C.6.1.6 UV detector, e.g. spectrophotometer: 190 nm to 400 nm.KeyCD conductivity detectoraOptional.Figure 1 Schematic representation of an

36、 ion chromatographic system including an in-line PCR system6.2 Cartridges.6.2.1 Cation exchanger in the Na form (cartridge).6.2.2 Cartridges, with non-polar phases to be used for sample preparation (e.g. polyvinylpyrrolidone).7 Quality requirements7.1 Separator columnIn chromatograms of samples and

37、standard solutions of bromate, the peak resolution, null, between bromate and the nearest peak shall not fall below 1,3 see Equation (1) and Figure 2. Adjust the separation conditions accordingly.8DIN EN ISO 11206:2013-05 EN ISO 11206:2013 (E) Keynull1width of peak 1null2width of peak 2nullRretentio

38、n timenull signal1 peak 12 peak 2Figure 2 Graphical representation of the parameters to calculate the peak resolution, nullNOTE 1 Within the scope of this International Standard, the calculation of resolution, null, is appropriate for both isocratic and gradient elution.Calculate the peak resolution

39、 for the peak pair 2,1, null2,1, using Equation (1):Rttww2121212,=()+RR(1)wherenullR1is the retention time, in seconds, of the first peak;nullR2is the retention time, in seconds, of the second peak;null1is the peak width, in seconds, on the time axis of the first peak;null2is the peak width, in seco

40、nds, on the time axis of the second peak.NOTE 2 The values null1and null2are the base widths of the isosceles triangles constructed over each Gaussian peak.7.2 PCR conditionsTypical analytical conditions are described in 7.3 and 7.4.Adjust the ammonium heptamolybdate concentration to between 11 mol/

41、l and 15 mol/l and the potassium iodide concentration to between 55 mmol/l and 65 mmol/l.9DIN EN ISO 11206:2013-05 EN ISO 11206:2013 (E) Alterations of the procedural parameters (e.g. flow rates, potassium iodide concentration or ammonium heptamolybdate concentration in eluent or PCR reagent) are al

42、lowed. If applied, calculate using Equation (2):nullnull1null null1null nullnull2null null2null (nullnull1null nullnull2) null null3(2)wherenullnull1is the eluent flow rate, in millilitre per minute;null1is the concentration, in mole per litre, of ammonium heptamolybdate solution in the eluent;nulln

43、ull2is the flow rate, in millilitre per minute, of the PCR pump;null2is the concentration, in mole per litre, of ammonium heptamolybdate or potassium iodide solution in the PCR reagent;null3is the concentration, in mole per litre, of ammonium heptamolybdate or potassium iodide solution after the mix

44、ing procedure in the PCR unit.EXAMPLE Example for the calculation of the ammonium heptamolybdate concentration in the PCR moduleEluent flow: nullnull1null 0,7 ml/minAmmonium heptamolybdate concentration in the eluent: null1null 0 mol/lPCR flow: nullnull2null 0,2 ml/minAmmonium heptamolybdate concent

45、ration in the PCR reagent: null2null 50 mol/l0,7 ml/min null 0 mol/l null 0,2 ml/min null 50 mol/l null (0,7 ml/min null 0,2 ml/min) null null3Ammonium heptamolybdate concentration in the PCR module: null3= 11,1 mol/lNOTE Solutions with a pH value null1 can require heating of the reaction solution i

46、n the PCR unit.7.3 Chromatographic and PCR conditions for the chromatogram shown in Figure 3Column: Ion exchangerEluent: 100 mmol/l sulfuric acidSample injection volume: 1 000 lEluent flow rate: 0,7 ml/minPCR reagent: 0,27 mol/l potassium iodide nullnull50 mol/l ammonium heptamolybdatePCR reagent fl

47、ow: 0,2 ml/minConditions at PCR reaction coil: Volume: 400 lTemperature: ambient temperature11,1 mol/l ammonium heptamolybdate60 mmol/l potassium iodideDetection: UV, null null 352 nm10DIN EN ISO 11206:2013-05 EN ISO 11206:2013 (E) Keynull absorbancenullRretention timePeak Ion Concentration1 bromate

48、 1,0 g/lFigure 3 Example of a chromatogram of a standard solution conforming to this International Standard7.4 Chromatographic and PCR conditions for the chromatogram shown in Figure 4Precolumn: Ion exchangerColumn: Ion exchangerEluent: 9 mmol/l Na2CO3Sample injection volume: 225 lEluent flow rate:

49、1,3 ml/minPCR reagent: 0,27 mol/l potassium iodide nullnull50 mol/l ammonium heptamolybdatePCR reagent flow: 0,4 ml/minConditions at PCR reaction coil: Volume: 375 lTemperature: 80 C12 mol/l ammonium heptamolybdate64 mmol/l KlDetection: UV, null null 352 nm11DIN EN ISO 11206:2013-05 EN ISO 11206:2013 (E) Keynull conductivitynull absorbancenullRretention timePeak Ion Concentration1 bromate 8 g/l2 chloride 14 mg/l3 sulfate 1