INTERNATIONAL Iso STANDARD 11905-1 First edition 1987.06.04 re Water quality — Determination of nitrogen — Part 1: Method using oxidative digestion with peroxodisulfate Qualité de feau — Dosage de Parote — Partie 1: Méthode par minéralisation oxydante au peroxodisutfate Raference numberISO 11905- Contents a6 95 96 97 98 a9 0 0.1 102 a Scope. Normative reference: Flange of detection, Sensitivity Principle. Reagents. Apparatus. Sampling end samples, Procedure Test nortion.. Blank test... Verification of igcavery of organic nitrogen, Staring operation... Initiat sensi Calibretion Determination Expression of results. Method of calculation: Precision data . Test report © 1s017 {A righte resarved, Unlaes otrerwise specified, no part of thls publication may bo reprostueed of uilizod ny form of ky any mé 1 1 1 1 2 2 5 5 5 5 6 6 6 6 6 8 8 a 8 9 a a 2, oleetrenis or mechanical, Inclding photecapying end mierefilm, wkhout permission in wsiting from tho publisne, Intemational Organization for Standardization Gear postele 68.» CH-121% Gonave 20 « Switzariand errieeontrstiso.ch AQ] e=cl Net; palao; B=Is0es; Printod in Switzarsnd© 180 180 17905-1:1007(E) Annexes A g c D Precision data.... Recovery data for some nitragen-containing compounds... Determination of nitrate... Bibliagraphy. 10 n or] BISO 11905-1:1997(E) ® Iso FOREWORD ISO {the Intemational Organization for: Standardization) is a worldwide federation of netional standards bodies (ISO member bodias}, The work of preparing International Standards ie normatly 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, governnental and ran-gavarnmental, in liaison with ISO, also take part in the work, ISO collaborates closely with the International Electrotechnical Commission (IEC) ch all matters of elactrotechnical 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 11905-1 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physical, chemical and biashericel methods, |SC 11905 consists of the following parts, under the general tite Water quality — Determination of nitrogen: — Part 1: Method using oxidative digestion with peroxodisuifate — Part 2: Determination of bound nitrogen after oxidation and combustion to nitrogen dioxide using chemiluminescent detection Annexes A to D of this part of ISO 11908 are for information only.© 180 ISO 11905-1:1997(6) INTRODUCTION This part of ISO 11905 describes the peroxodisulfete oxidation: of nitrogen compounds in water to produce nitrate, Specific details of the determination of a.continuous flow method with initial raduetion of nitrate to nitrite by coppotized cadmium are then reported, The procedures referred to in the normative methed is the ieferance method. Annex C gives examples of alternative techniques suitable for the determination of nitrato in the cigest solution. While staying within the scope of this part of ISO 11905, itis permissible to use such altematives only provided that their performanse meets or is better than that given in table A.1, whan ‘aloutated using procaduras desorbed in I6O 5725-2, anc when the comparison of precisicn data between this Part of ISO 11905 and any altemative technique is carried out using the procedures dascribad in ISO 2854, All references to nitrogen concentrations are expressed in milligrams of nitragan per litre of solution imgf}.INTERNATIONAL STANDARD © iSO ISO 11908-1:1997(E) _— Water quality —- Determination of nitrogen — Part 1: Method using oxidative digestion with peroxodisulfate 1 Scope Thie part of 180 11905 specifies 2 method for the determination of nkrogen present in water, in the form of free ammonia, ammonium, nitrite, nitrate and organic nitrogan compounds capable of conversion to nitrate undor the oxidative conditians deserbad. Dissolved nitrogen ges is not determined by this method. Thi method is appticable to the analysis of natural fresh water, sea weter, drinking water, surface water and sweated sewago effluent. kis also applicable to the analysis of sewage and trade wastes in whieh the amount of organic mettar in the test portion can ba kept below 40 maf, expressed 2s carbon (C), wen measured ky Total Organic Carbon (TOC), oF 120 me, expressed as oxygen (O,), when measured by Chamical Oxygen Demand (COD) secording to the respeative International Standards. 2 Normative references The following standards contain provisions which, through reference in this text, constitute provisions of this Part of ISC 11905. At the time of publication, the aditions indicated wera valid. All standards ara subject to revision, and parties to agreements baged on this port of ISO 11905 are encouraged to investigate the pessibiity of applying the most resent editions of the standards indicated below. Members of IEC and ISO maintain registers of current valid Internstional Standards. 150 3896:1987, Weter for analytical laboratory use —- Spocifiestion end test methods. 180 8728.2:1984, Accuracy ftruoness and precision) of measuroment mathods and results — Pat 2: Basic methods for the determination of repeatability and reproducibility of a standard measurement method. “3. Range of detection Using the maximum test portion spesitied in 9.1, nitrogen {N} cen be determined in the Tange up to 5 mg/. lich higher concentrations can be determined iicing srholler test portions. Using the maximum test portion, the lower limit of detection, expressed as N, is typically 0,02 maf. This dopende on the method usec to measure the nitrate concentration resulting trom the oxicetion. 4 Sensi Sonsitivity will depend upon the mathod used to measure the nitrate concentration resulting fram the oxidation.ISO 11905-1:19971E) 2180 The main potential interfarance affects arieo from dicsolved or suspended orgonia matter preaont in camptes, which compete for the oxidation eapacity of the peroxodisulfata reagen:. To quaraniee a sufficient excess cf the oxidation reagent, if the COD of the originsl eampie exceeds 120 mg/, expresced as O,, er tho TOC axesods 40mg, expressed as C, the sample needs to be diluted. Not all organic nitrogen compounds are quantitatively converted to nitrate by the oxidstion, Poo recoveries ean cccur with compounds containing double- and triple-bonded nitrogen atoms and also with thoss substances containing a >C=NH group. Cempounds with free amino groups give less than quantitative recovery, but in no case less than 87%: good recoveries of nitrogen are reported for several heterocyclic compounds, sea annex B, Overall, the method gives good recovery performance for organic nitrogen compounds and gives results not significantly different from those obtained by instrumental, high tamperature ‘exddation or redustion systems on @ wide range of real samples containing significant amounts of organic matter. 5 Prineiple Ammonia, nitrite and many organic nitrogen-containing compounds in the test sample ate oxidized to nitrate using peroxodisulfate in a buffered alkaline system by boiling at elevated pressure in a closed conisiner. Subsoquent reduction of nitrate to nitrite is carried out by pessage of the digest through a mixing coit containing copperized cadmium. The resulting nitrite is reacted with 4-aminobenzene sulfonamide and N-{i- naphthyll1,2-dismincothane dihydrochloride to procuse ¢ pink cofour. Photometric measurement is carried out at 846 nm. : 6 Reagents During the analysis, use water of purity crave 3 as specified in ISO 3696 and reagents of recognized analytical grace. 6.1 Sulfuric aeld, cH.S0) =4 mol/l Carefully mix {110 + 0,5} ml of concentrated sulfurie acid (H,SO,, p = 1,84 gim)) into about 350 mI of water. Allow to cool to room temperature and dilute with water to (500 + 10) ml, Store in a glass or plastics container. This reagent is stable indefinitaty. WARNING: This reagent can cause severe burns. Wear gloves and eye protection when handling or preparing ‘the acid, 6.2 Sodium hydroxide solution, NaOH) = 0,375 mol/l. Dissolve (15,0 + 0.5) g of sodium hydroxide in about 900 ml of water. Allow to enol to roam temperature and make up to (1009 + 10} mi with water, Store in @ polyethylene container. This reagent is stable for at least 9 months. WARNING: This reagent is corrosive. Wear gloves and eye protection when handling or preparing the solution, 6.3. Oxidizing solution. Dissolve (5:0 + 0,1 g of analytical reagent grade potassium peroxodisulfate (K,S,0,). containing not more than 8.001 % imm/imi nitrogen as impurity, and (3,00 4 0,03} g of boric aaid {H,80,) ‘in (100 + §} ml of sodium hydroxide solution (6.2), Score the solution in a polyethylene conteiner in the dark at roam temperature. This reagent is steble for up ta one woek.eiso Iso 11805- 1997(E} WARNING: This reagent is corrosive. Wear gloves and eye protection when handling or preparing the solution. 6.4 Hydrachloricacid, c{HC} =5 mols. Cautiously add (450 + 10) ml of concentrated hydrochloric acid |HCI, p= 1,18 gimi) to {500 « 70} ml of water with constant stirring. Maks up to {1000 + 10} mi with water. Store in a glass or polyethylene bottle, This solution ie stable for ot least six months. WARNING: This reagent can cause severe bums. Wear gloves and eye protection when handfing or preparing theadid, 8.5 Hydrochloric acid, (HC) 0,1 mol/l. Add (10,0 & 0,5) m1 of sencentrated frydrochtorie acid (HCI, 6 = 1.18 gimll to about 960 ml of water. Mix and make up to (1000 + 10) mi with water, Store in @ glese or polyethylene bottle. This reagent is stable indefinitely. WARNING: This reagent can cause severe bums, Wear gloves and eye protectian when handfing or preparing, the acid, 8.8 Glycine sotution, 200 mo/, expressed as N. Dissalve (1,072 = 0,001) g of glycine, HjNCH,COOH, in about 809 ml of water and cifute to one litre with water Ina calibrated flask. Store in a gless container. If stored in a refrigerator at 6 °C te 6 °C this reagent is stable for at least one month. 6.7 Glycine solution, 2 mg/l, expressed es N, Pipette (10,00 « 9,97) mi of glycine solution {6.5} into = one-itre calibrated flack and make up to volume with ‘wator. Propere freah sclution for each batch of analyses. NOTE — The concontiation of this stenderd glycine solution should be chosen to match the expected range of conceatrations of niragen to De determined: for axample, if lower nitrocen results are expested then the concentration of tha standerd alycine solution should he reduced, (See aleo 8.5). 6.8 Reagent blank. : Corry out at least one biank test using the proosdure described but replacing the test portion with water. 6.5 Coppor sulfate solution. Dissolve (20 + 0,2! g of copporit) sulfate pentahydrate (CuSO, -5 11,0) in (1000 + 10} ml of water. Store in a glass or polyethylene bottle. ‘This solution is stable for at least six months, 6.10 Copperized cadmium granules WARNING: Cadmium is toxic by inhalation, by contact with skin orby ingestion. Wash (10:+.0,1) 9 of eadmium granules {250 jim to 425 ym) in (50 0,5) ml of hydrochloric acid (6.4), Rinse the grerules three times in water by decantation, Add (100 # 1) mil of copper li} sulfate solution (6.81 and swirl the granules foF 5 min or until the blue colour partially fares. Decant off the solution ond repest the procedure with fresh coppertl}) sulfate solution (6.9) until a brown colloidal precipitate iorms. Finally, wash the ‘coppertted cecimium granules with water until all precipitated copper is removed. Carry out a minimum of 10 weahes. Store tho cepperized grenules under water until equlied. Avoid contact with air. 611 Buffer eolution, Dissolve (85,0 = 0,5} g of ammonium chforide (NH.CIi in about 800 mt of watar. Add (1,0 a 0,11 9 of wotting agant (6.13). Make up.to (1000 10} ml with water and store in a glass bottle. This solution is stable for at least one month.ISO 11905-1:1997(E) © 180 6.12 Colour reagent. Dissolve (40 = O.5t 9 of 4-aminobenrens sulfonamide (NH.C,H.SO.NHJ in a mixture of (500 2 1) mi of orthophasphoric acid (HPO, o= 1,71 g/mi and (600 50) ral of water In ¢ heaker. Dissolve {2,00 = 0,2) g of (-raphthyf-1,2-diaminosthane eihydrachioride (C,H,NHCH,CH,NH, » 2HCI) in the resulting solution. Transfer toa 1090 ml calibreted flask and dilute to the mark with water, Mix wall, Store in an amber glass bottle, The solution is stable for 1 month if stored at2*C to 5 °C. WARNING: N-(1-naphihy!)-1,2-diaminoethane tihydrechloride is toxic by inhalation, by contact with skin or by ingestion. 6.13 Wetting agent. NOTE — The presence of a wetting egent in a continuous-flow system is desirable In order to promote smooth hycraulie flow. Use a nonionic surfartant of the polyoxyethylene alnohol type er the alkyIphenoxypolyethoxy ethanol type. 8.14 Nitrate solution, containing 1000 mg/l, exprassed as N. Dissolve (7,215 + 0,001} g of potassium nitrate {KNO,) {previously dried at 105 °C for at least 2 hh in about 750 ml of water. Quantitatively transfer to a one-litre calibrated flask and make up to volurne with water. Store ina. glass container. This solution is stable for two months. 6.45 Nitrate solution, containing 190 mg/, expressed as N, Pipatte (50,00 + 0.05) ml of nitrate solution (6.14) into 2 500 mi celiarated flask and make up to volume with water. Store ina glass contoiner. This soluticn is stable for one month. 6.16. Nitrite solution, containing 160 mg/|, expressed es N. Dissolve (0,492 + 0,002) g of sodium nitrite INaNO,) Idried at 105 °C for at least 2 hp in about 730 ml of water, Transfer quantitatively to a 1000 ml one-mare volumetric flask and dilute to the mork with water. Store ina stoppered amber glass boitle at 2°C to 5°C. This salution is stable for at least one month. 6.17 Nitrite solution, containing 4 mail, expressed as N. Pipatte (2,00 « 0,01) ml of nitrite eohstion (8.16) into a 60 mt calibrated flak and make up to volure with wator. Prepare fresh solution as required.180 7 Apparatus Orcinary laboratory epparatus end: 7A Homogenizer. 72 Digestion vessels. Battles of polytetrafluoroethene {PTFE} or other suitable materials with screw caps, nominal capacity in the range 100 mi to 125 mi, capable of withstanding prossures of up to 200 KPa. Gee 9.3. 7.3 Autoclave, suitabis for pressures up to 200 kPa and operation at 120 °C. Ses also note in annex C. 7.4 Continuous-flow analysis equipment, comprising: ~ sample presentation unit (sampler): — multichannel peristaltic pump: —anelyticel cartridge {manifold} including pump tubes, mixing coils, rechuction column (5.5) and dialyser unit; — epectromoter, incorporating 9 flow coll and capabla of measuremont over a wavelength rango botweon 520 nm and 850 nm; —recordor. 775 Reduction column. Constructed from glass or plasties tubing with an intemal diameter fdentical to that of the mixing coils used elcowhere in the system. Fill the colurnn with copperized cadrnium granules 48.10} HAZARD). Tha volume, in militres, oscupied by the granules shall be as close as possible to the total liquid Towrate, Hi miliiftres per minute, aassing through the column, 8 Sampling and samples Collect laboratory samples in plastics or glass bottles. Analyse them as quickly as possible, of store them at benween 2 °Gand 5 °C for up 7048. NOTE — Aciaification with suifuris acid (9.1) to pH 2 cam also be used! as an ald to samafe preservation, pravided any ossible contamination of the acidified sample by absorption cf atmospheric ammonia is prevented. In this case, te sample can be stared for up to 8 ays. 9 Procedure 9:1 Tost portion ‘Ths maximum test portion, enabling the determination of nitrogen cencentratione in samples of up to 5 mg/l, is 50 ml. Use smaller test portions as appropstate to determine higher nitrogen concentrations. In all cases, the test portion shall be controlled such that its TOC contont does not exceed 2mg as cerbon, or auch thet ite COD dozs not excead 6 mg as oxygen {see 1.3), Before taking the test portion, ensure that the laboratory sample is thoroughly mixed. If the sample is inhomogeneous, the homogerizer {7.1} ean be used. If laboretery samples are strangly acid (pH < 2) ensure that, alter addition of the oxidizing solution {6.3) to tho test gortion, a pH cf 8,7 is attained by carefully adjusting the pH with sadium hydroxide olution (8.2)($0 11905- :1987(E) e180 982 Blank test Carry out et least one blank test with every batch of digestions, using (50 1) ml of water in place of the test portion. 9.3. Cleaning digestion vessels Before use in analysis for the first time, add to each naw digestion vessel {7.2} about {60 + “) ml af oxidizing solution 16.3). Close the vessel end heat itn the autoclave {7.3} for {30 = 5} min. Remove the vessel, allow it to 00) to Foor temperature and discard the contents. Rinse the vessel thoroughly with water, fil to the brim with hydrochloric acid {6.6}, stopper and store until required ia the analytical procedure, Immediately before use, empty the veseel and rinse with water. After cleening for the first time by the procedure described above, rinse the digestion vesssls with water. If significant contemination is known or suspected, clean the digestion flesks again by the procedure described above. Wherever possibia, reserve cleaned digestion vassals for the deter-mination of nitrogen. 8.4 Digestion Pipette @ suitable test portion (9.1) of up to 50 ml, {V mb, Inte a clean digestion vessel (7.2) and if necessary. add water from a burotte or moasuring eylindar to give a total volume of (69 « 1) mi. Pipette {10.0 0,1} ml of the oxidizing solution (6.3) into the digestion vesset and immediately close the vessel. Mix thoraughly. Digest for (20. 5) min at (120 5) °C, Some digestions require additional time for complate oxidetion, for exemple €0 min, Remove the digestion vessel from the source of heat and allow to coal to room temperature, Shake the digestion vessel in order to dissolve any precipkate which may form, end quantitatively transfer the solution to a 100 ml calibrated flask. Make up to volume with water. NOTE 1 If any particulate mattor remains undissolved in the digest, it should be filtered through a prarinsed glass fibre {itor paper into the 100 m’ colrated flask, The fier should be rinsed with watur te ensure quantitative irensfer. NOTE 2 If necossary. the digest may be kept for up ta several wwaekt In the unopense digestion vassal bofors completing the analytical procedure. Hewever, avoid contamination from abserpiion of etmesphaic ammonia, 95 Verification of recovery of organic nitrogen With ovary katch of digestions, include at lonst one recovery test using (60,00 2 0,05} ml of glycine solution {6.71 in place of the test portion. If the standard glysine solution specified in 6.7 is used, the nitragen concentration measured shall not diffor from 2,00 mail by more than + 0.20 mal. If greater percentage differences for this or other standard solutions are found, the overell method shall be examined and results ‘rom the associated batch of samples chell nat bo reported. 9.6 Starting operation Conneot the systam 2s illustrated in figure 1, but omitting tha reduction eclumn, Fallow the manufacturers? instructions where appropriate. With the sample probe al rest in the reagent blank (68), place all the reagent lines in their respective reagents and start the pump. When ail reagent lines and coils have bsen filled, stop the pump and insart the reduction column into the system. This procedure avoids alr entrapment in the cotarnn.eso Pump tabs, (law estes (mm) waste os ving cit turns) [ 23 2 a 03 Redaction eotunn tS} Maing cot sO turnsh [ i 08 f 03 Uebabbler — vaste oa Floweat, Recordar-Calavineler $40 rt tL Figure ISO 11905-1:1997(E) Extast ale ‘mmontumcteri (11 Sample ale Colour rezgent 6.121 ExtastISO 11905-1:1997(E) 2180 Allow tha aystem to equilibrate and during this period, chock that the bubble patter and hydraulic behaviour of the system are operating te the manufacturer's instructions, if not, eliminate difficulties before procesding 109.7. 97 Initial sonsitivity satting ‘When a baseline response given at the recorder is stable, adjust to about 6% of tha full-scale doflaction; transfer the sample probe into the 4,0 mg/l;siandaré nitrate solution (9.8). When there is a postive stable respense at the recorder due to the colour produced from thie £,0 mg standard nitrate solution (9.8), adjust this response to read about 95% of full-ecele deflection. NOTE 1 The semple probe need remain In the standard sclution only for sufticient ime to glve a staady reading. Roturn the semple probe to rest in the wash position, first removing teces ef stenderd aclution from the outside of the probe by rinsing with weter and cleaning with a clean tissue. NOTE 2 Periodically, tne response from the 4,0 mg/l stancard nitrate solution |98) end the 40 mail standard nitrite solution. (8.17) should ba campared to check effciancy of reduction. The respanse from the nitrate solution shaule be at east 90% of thet from the nitrite solution, Lower reduction efficiencies should be investigated and attention to the eduction system wil usually be required 9.8. Calibration ‘Choose the calibration range te match the expected range of concentrations to be determined. (See also 9.5). For example, to @ series of five 50 ml calibrated flasks, add, by moans of a micraburatte or calibrated micropipettes, 1,0; 0,8; 0,6; 0,4 and 0,2 ml of nitrate solution {6.15). Make up to volume with water. These flasks new respectively contain the equivalent of 4,0. 3,2; 2.4; 7,8 and 8 mg/l, expressed a5 N, in the original {est.portion of 50 ml (8.1), These concentrations afe In tum equivalent to 0.2; 0,16; 0,12; 0,08 and 0,04 mg of N in the test portion itself. Run the five calibration standards as indicated in 9.9. At the end of the determination, measure the system response to the calibration standards from the rerorcar ‘race, taking the beseline trace obtained during initial sensitivity setting {9.7| os the blank response value. Plot a graph of response against concentration of nitrogen in milligrams per litre. The graph shall be linear ‘and pass through the origin. If nat, check procedures to ansure that the graph is linear. 99. Determination Rinse and fil each sample container used in the instrument with a portion of the test solution, calitration standard or blank es sporopriate. Load the turntable with the filled containers in accerdance with the manufacturer's instructions, NOTE — if cross-contamination occurs between iva sam™pias (visible on the recorder trace as incomplete separation of consecutive sample responses), bath samples should he reanalysed, eaparated by # lank eolution, When a stable baseline is obtained on the recorder, ra-adjust, if necessary, to ahout 5% of full-seala ceflection and start the sampling unit. When all the system responses due to the prosessed solutions heve appeared on the recorder and a final baseline has been obtained, remove the reduction column from.the systern, and switeh off the recorder end spectrometer. Transfer all reagent lines to water end pump for at loast 15 min ar a time recommended in the manufacturer's instructions.©1s0 11905-1:1997(E) 10 Exprassion of results 10.1 Method of calcufetion Meesure the system response to the samples or standards 96 appropriete from the recorder trace, taking the baseline trace obtained during initial sensitivity setting (6.7) as the blank response value. Read off the corresponding nitrogen concentration, in miligrams per litre, from the calibration greph. These concentrations correspond to ritrogen in the original sample when the full 5(-ml test portion 18.1] hes been used in the digestion. Multiply the concontratione by 50/¥ when emallar test portions, af volume Vml, have besn taken. Date-hendling facilities may also be used. 10,2 Precision date Precision data obtained in various international laboratories sre prasented in table A.1 In annex A, Data were calculated using precocuras described i ISO 5725-2. 11 Test report The test report shall incfuds the following information: 9) a reference to this part of ISO £1905; b) all Information necessary for complete Identifstion of the sample; 2) the results and the methad of expression used; d} a statement of the comparison of data obtained using this part of [SO 1180S and the’performance dete obtained using any altamative technicute: 2) the chemical exygan demand and/or the total organic carbon concentration in the sample; 8) the volume of test portion used; g)_ details of eny operations not included in this part of ISO 11805, together with any circumstances that may have affected the results,ISO 11905-1:1997(E) Iso Annex A (informative) Precision data Table A.1 ~ Precision data of the results of the total nitrogen international collaborative trial Ss} tas | wo, | nap Mean se ow, 5 wv, Mean 2 a 4 veoovery at 2 1 % el om | 2 1,989) 071 3558 ana? 2,588 100 of 7 | a6 1 99,26 5,692 5734 2776 2,796 99 ml ow | a4 ° 7401 0,595, 1,228 0,166 ama Ri ow | a6 1 15,002 0,588, 3,808 0318 2,118 98 ni} ow [| as ° 7179 0463 6497 ont +960 s| wv | 34 0 16.9641 0.800 5313 0,202 11195 98 e| a | 34 2 7222 0,291 4031 Tt 2373 ol 17 | a ° 22,287 1.938 5.17 0801 2,252 99 AB — Numbor of laboretoriog = Stance 2 mg/l © = Standart 100 mgf M = Settiottsmvege R= Settled sewage sped wth Bg NV = Finatemuant S = Final ofluont spi wth 10 rg P =Bstary = Estiery spied wit 15 gy No = Nurnberofrestts NAP = Namber of cutierlaboratorias 4, = Standard devistion of reprodusibitty GY, = Beproauetoitty caemetent oF variation 4, ~ Starclard devietion of repeattility CY, = Repentabitty coeficientofvaratlone1so Annex B informative ISO 11905-1:1997(E} Recovery data for some ‘nitrogen-containing compounds. Compound Maes of | Diveston time Recovery nitrogen. min ° maf iene chioride 4 2 29-701 Meth! orange ‘ » 18-38 Serie 4 » ra ntrophero| 08 » 10207 3 B eo. ‘eniroentine 08 @ te 28 O68 a 85488 3 B 19.32 3 # 982 Adenotin tiphoephats as = 12-87 3 a 1oo04 ‘Dimethylformamide 5 30 92-98 3 2 9-702 Pring os a 94-36 3 = 6-87 counicacia 7 2 s9-108 EDTA disodium sat zs = 87-98 Powrslan ferrocyenle 2 = 04-90 Urea za 30 e102 Chowne 2 20 17-36 ‘Faminoentivaquinone-2-suFonie acid 24 x 06-38 Thiovrea 05-3 30 78-107ISO 11905-1:1997(E) ®1S0 Annex C informative} Determination of nitrate CA General ‘There are several techniques, outlined in the following paragraphs, aveilable for the determination of nitrate ions in the digest solution. All the techniques ara widely usad for tha analysis of waters but only the method described in this relerence method has precision data associated with the analysis of the digest solution. Any technique can he tised provided the precision data show it to be eal to or hatter than the precision data reported in table A.1. NOTE — Microwave digestion apparatus can be suiteble for use In the reference methad and in sltemative methods. Operating procedures appropriate to particular instruments should be validated end the precision obtained sheuld be ‘equal 10 of better than the precision reported in table A.1. €.2 Automatic continuous-flow spectrometric method with reduction of nitrate to nitrite by hydrazine Such methods are similar to that given in the reference method but 2 solution of hydrazine sulfate should be used, added before the colour reagent, in place of the copperized cadmium reducticn call. €.3 ‘Reduction of nitrate to nitrite by passage of the digest through a celumn sont: copperized cadmium, fallowed by reaction and spectrometric measurement ‘This is @ manual version of the continuous-flow method, giver the reference method, with similar reagents: end reactions. The acid digest solution should be neutralized with sodium hydroxide solution before making upto TCO ml at step 9.4, ing C4 Direct spectrophotometric method using UV absorbance measuremenis This method iavoivee the measurement of the UV absorbance of the digest solution at a wavelength of 210 nm, This is a rapid method, but it is necessary to check the abscrbance at 210 nm for any rasidual organic material that may be suspected; if the absorbance at 275 nm exceeds 5% of that at 210 nm {in cells of the sane pathlength}, ha method should de considered invalid. €.5. Liquid chromatographic methods Methods using liquid chromatographic separation of fons using low-capacity anion exchange resins as ihe stationary ‘phase and aqueous salt solutions of weak mono- of dibasic acids 2s the mobile phase. Detection can be carried out by conductivity measurement or UY detection. See [SO 10304-1,@180 1SO 11905-1:1997 (E! Annex D Unformative! Bibliography [1 Nydahl. On the percxodisulfate oxidation of totel nitrogen in waters to nitrate, Water Research, 12,1978, p. 1128. 121 F Koroleff, Methods of Seawater Analysis. Edited by K Grasshoff, M Ehrhardt and K Kremling, second edition, Verlag Cherie, Weinheim, 1983. {31 180 208471976, Statistical interpretation of data Techniques of estimation and tests retating to meens and variances. (4) 180 6060:1989, Water quality. Determination of the chemical axygen demand, Is] ISO 10304-11992, Water quality - Determination of dissolved fluoride, chloride, nitrite, erthophasphate, bromide, nitrate end sulfate, using liquid chramatographiy of ions - Part 1; Method for water with low concentration, [6] EN 1484:1994, Water analysis - Guidelines for the determination ai total organis carbon (TOO),