mm 9009276 0031287 138 mm : qf Designation: D 4327-84 * AMERICAN SOCIETY FOR TESTING AND MATERIALS 1016 Race St., Philadelphia, Pa, 19103 Reprinted from the Annual Book of ASTM Standards, Copyright ASTM, If pt listed in the current combined Index, will appear in the next edition, Standard Test Method for ANIONS IN WATER BY ION CHROMATOGRAPHY'* ‘This standard is istued under the fixed designation D-4327; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A nurber in parentheses indicates the year of last reapproval ‘A superscript epsilon (¢) indiates an editorial change since the las revision or repproval, 1. Scope 1.1 This test method? covers the sequential determination of fluoride, chloride, nitrite, phos- phate, bromide, nitrate, and sulfate ions in water by ion chrdmatography. 1.2 This test method is applicable to drinking, ground and surface waters, boiler and cooling waters, domestic and industrial wastes, and at- mospheric precipitation samples. 1.3 Concentrations as low as 0.1 mg/L can be determined depending upon the anions to be quantitated. Utilizing a 100-1L sample volume and a sensitivity of 3 uS/em full scale, the follow- ing are approximate detection limits: Approximate ‘Detection Limit, ‘Anion mg/L Fluoride (>) on Chloride (Cr) ‘ 4 Nitrite (NO) 02 Phosphate (PO) o1 Bromide (BF) 02 Nitrate (NOS) 02 Sulfate (S007) 02 If lower detection levels are required, the sen- sitivity may be improved by using a lower scale setting (<3 S/cm) or a larger sample injection (100 BL). The analyst must assure optimum instrument performance to maintain a stable baseline at more sensitive conductivity full-scale settings, 1.4 The upper limit of this test method is dependent upon total anion concentration and may be determined experimentally as described in Annex Al. These limits may be extended by appropriate dilution. 1.5 It is the users’ responsibility to assure the validity of this test method to other matrices. 16 It is the analysts responsibility to assure the validity of the method for untested matrices. 1.7 This standard may involve hazardous ma- terials, operations, and equipment. This standard does not purport to address all of the safety prob- lems associated with its use, Iti the responsibil. ity of: whoever uses this standard to consult and establish appropriate safety and health practices and determine the applicability of regulatory limi- tations prior to use. 2. Applicable Documents 2.1 ASTM Standards: D 1066 Practic for Sampling Steam? D1129 Definitions of Terms Relating to Wate? D 1193 Specification for Reagent Water? D 2777 Practice for Determination of Preci- sion and Bias of Methods of Committee D- 19 on Water D 3370 Practices for Sampling Water? E 200 Preparation, Standardization, and Stor- age of Standard Solutions? E 260 Recommended Practice for General Gas Chromatography Procedures E 355 Recommended Practice for GC Terms and Relationships! ‘This test method is under the juridiction of ASTM Com- mittee D-19 on Water and isthe direc responsfblity of Subcom- mittee D19.05 on Inorganic Constituents in Water. josie elton approved Fe. 28, 198, Published March The following references may be consulted for additional information: Small, H, Steveas, T. S, and Bauman, W. C., “Novel Ton Exchange Chromatographic Method Using Conductimetric Detection.” Analytical Chemistry, Vol 47, 1975, p. 1801. Stevens, T.S, Turkeluon, V.T. and Alve, W. Rey=Determina- tion of Anions in Boiler Blow Down Water with lon Chro- ‘matopraphy,” Analytical Chemistry, Vol 49, 1977, p. 1176. Sawicki, E, Mulik, J.D, and Wigensein, E., Editors, Jon Chromatographic Analysis of Environmental Polbwants, AN Arbor Science Publishes, Ann Arbor, Mich, 1978. Mulik, J. D. and Sawicki, E, Editors, lon Chromatographic Avalbie from Dionex Cor, 1228 Tan Way, Sunayvale, Cali 94086, or an equivalent may be used.conductivity celf equipped with a itieter capable of reading from 0 to 1000 pS/cm on a linear scale. 7.1.5 Pump, capable of delivering a constant flow of approximately 2 to 5 mL/min throughout the test and tolerating a pressure of 200 to 700 psi (1.3 to 4.8 MPa). rd 7.2 Recorder, compatible with the detector output with a full-scale response time in 2 s or less. 7.3 Syringe, minimum capacity of 2 mL and equipped with a male pressue fitting. 1.4 Eluent and Regenerant Reservoirs—Suit- able containers for storing eluents and regener- ant. 7.5 Integrator—It may be desirable to inte- grate the area under the chromatogram, Different integrators can perform this task when compati- ble with the electronics of the detector meter or recorder. If an integrator is used, the maximum area measurement must be within the linear range of the integrator. 8. Reagents 8.1 Purity of Reagents—Reagent grade chem- icals shall be used in all tests. Unless otherwise indicated, it is intended that all reagents shall conform to the specification of the Committee on Analytical Reagents of the American Chemi- cal Society, where such specifications are avail able. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination. 8.2 Purity of Water—Unless otherwise indi- cated, references to water shall be understood to mean reagent water conforming to Specification D 3193, Type I. Column life may be extended by passing Type II water through a 0.22-m filter prior to use. 8.3 Anion Working “Solutions—Prepare_& blank and at least three different working solu- tions containing the following combinations of anions. The combination anion solutions must be prepared in volumetric flasks. See Table 1. 8.3.1 Prepare a high-range standard solution by diluting the volumes of each anion specified in Table | together to 1 L with water. 8.3.2 Prepare the intermediate-range standard solution by diluting 10.0 mL of the high-range standard solution (see 8.3.1) to 100 mL with water. wa yuutiess 4327 Uuab265 TOO mi 8.3.3 Prepare the low-range standard solution by diluting 20.0 mL of the intermediate-range standard solution (see 8.3.2) to 100 mL with water. 8.4 Eluent—Dissolve 1.0080 g of sodium bi- carbonate (0.003 M NaHCOs) and 1.0176 g of sodium carbonate (0.0024 Mf NaCOs) in water and dilute to 4 L with water. 8.5 Stock Solutions: 8.5.1 Bromide Stock Solution (1.00 mL=1.00 mg Br”)}—Dry approximately 2 g of sodium bro- mide (NaBr) for 6 h at 150°C and cool in a desiccator. Dissolve 1.2877 g of the dried salt in water and dilute to 1 L with water. 8.5.2 Chloride Stock Solution (1.00 mL = 1.00 mg Cl’)}—Dry sodium chloride (NaCl) for 1 hat 600°C and cool in a desiccator. Dissolve 1.6484 gof the dry salt in water and dilute to { L with water. 8.5.3 Fluoride Stock Solution (1.00 mL = 1.00 mg F-)—Dissolve 2.2160 g of sodium fluoride (NaF) in water and dilute to 1 L with water. Store in chemical resistant glass or polyethylene. 8.5.4 Nitrate Stock Solution (1.00 mL = 1.00 mg NO3")—Dry approximately 2 g of sodium. nitrate (NaNO;) at 105°C for 24 h. Dissolve exactly'1.3707 g of the dried salt in water and dilute to 1 L with water. 8.5.5. Nitrite Stock Solution (1.00 mL = 1.00 mg NOs)—Place approximately 2 g of sodium nitrite (NaNO,) in a 125-mL beaker and dry to constant weight (about 24 bh) in a desiccator containing concentrated H,S0, (sp gr 1.84). Dis- solve 1.4998 g of the dried salt in water and dilute to I L with water. Store in a sterilized glass bottle (Notes 1 and 2). Refrigerate and prepare monthly. Nore 1—Nitite is easily oxidized, especially in the presence of moisture, and only fresh reagents are to be used. (ore 2—-Prepare sterile bottles for storing nitrite solutions by heating for 1 h at 170°C in an air oven. 8.5.6 Phosphate Stock Solution (1.00 mL. = 1,00 mg PO,~")—Dissolve 1.4330 g of potassium dihydrogen phosphate (KH2PO,) in water and dilute to 1 L with water. 8.5.7 Sulfate Stock Solution (1.00 mL = 1.00 ‘Reagent Chemical, American Chemical Society Spei cations” Am. Chemica! Soe, Washinglon, De, For sues tions on the tesiog of agents not ied bythe Amenexs (Chemical Soccry, se “Reagent Chemicals and Stands,” bby oseph Rosin, D. Van Nostrand Co, lnc, New York, NY, nd the “United States Pharmacopeci) mg SO.)—Dry sodium sulfate’(Na;SO.) for 1 ‘h at 105°C and cool in a desiccator. Dissolve 1.4790 g of the dried salt in water and dilute to 1 L with water. 8.6 Suppressor Regenerant Solution—Cau- tiously add 111 mL of concentrated H:SOx (sp gx 1.84) to approximately 600 mL of water. Cool the solution and dilute to 4 L with water. 9. Sampling 9.1 Collect the sample in accordance with ap- plicable Practice D 1066 and Practices D 3370. 9.2 Analyze the samples as soon as possible after collection, Preservation by refrigeration at 4°C is required. 9.3 Filter the samples containing particulates through a prewashed 0.22-um filter prior to anal- ysis to avoid fouling or clogging the resin col- umns. 10. Calibration 10.1 Determination of Retention Times: 10.1.1 The retention time for each anion is determined by injecting a standard solution con- taining only the anion of interest and noting the time required for a peak to appear on the chro- matogram. Retention times vary with operating conditions and are influenced by the concentra- tion of ion(s) present. Prepare separate standard solutions in accordance with Table 2 by transfer- ring by pipet the designated aliquots of stock solutions prepared in Section 8 (8.5.1 through 8.5.7) into separate I-L volumetric flasks. Ana- lyze each standard of interest as defined in Sec- tion 11. Note the time in minutes for each peak to appear on the chromatogram. Note 3—Some operators have reported unvsually large shifis in retention time for nitrate with changes in concentration. If this occurs, care must be taken to ensure integration of the correct peak when integration is used for calculation. 10.1.2 Concentrations other than those listed in Table 2 may be used if they better approximate concentrations expected in the samples. Those concentrations listed will give about midscale response with a 1-V recorder input and a con- ductivity meter full-scale setting of 10 uS/cm. 10.1.3 Although retention times may vary from one column to another and are influenced bby such factors as temperature and eluent flow rates, the elution order of the anions is always as follows when (8.4) using the standard CO3"/ mE SUUSE /b UUSbeU eee Dasa HCO}" eluent: F, CI", NOy soe, : 10.2 Analyze the blank and each of the pre- pared calibration solutions described in 8.3 in accordance with the defined procedure (see Sec- tion 11). POL, Br, NO, Nore 4—Ifthe concentrations of the sample ions of interest are known or estimated, the concentration of standard solutions prepared for instrument calibration may be varied to better approximate or bracket the concentration range of interest. Anions of no interest ‘may be omitted Nore $—The intermediate-range combination anion standard (see 8.3.2) may be used to verify reso- lution of all seven anions. Nore 6—Each analytical curve should be established using only one scale setting. Changing the scale setting ‘may result in a slight change in the slope of the analyt- ical curve, : 10.3 Prepare analytical curves for each anion of interest by plotting on linear graph paper peak height or peak area versus the nominal concen- tration of the anion standard solution. Nore 7—Some operators have reported a shift ia slope of the phosphate calibration curve at approxi- rately 30 mg/L PO,,Ifsucha shiftin slope is observed, auditional standard solutions covering the entite range of corcentration should be prepared and analyzed in corder-to accurately define the slope of the curve. If an integrators being used, it may be necessary to manually calculate phosphate concentrations above 30 mg/L POs in order to oblain maximum accuracy. 11. Procedure 11.1 Set up the ion chromatograph in accord- anee with the manufacturer's instructions. See Annex Al for information concerning possible configurations for instrument set-up. Nore 8—The detector ranges are variable. Normal operating ranges are from 3 10 100 wS/cm full scale. ‘The range setting required for analysis will depend on the concentration of anions in the sample and should be chosen accordingly 11.2 Equilibrate the system by pumping eluent through all three columns until a stable baseline is obtained (approximately 15 to 20 min). This equilibration can normally be accom- plished while the samples and standards are being prepared. 11.3 Set up the instrument as directed by the manufacturer, Load 2 to 3 mL of sample into the sample entry port using a syringe (see Note 7). Inject the sample into the eluent stream and record the ion chromatogram (refer to Fig. 2). Note 9—Most plastic disposable syringes, if used, -cU come in packages that ae labeled “sterile,” but sterile does not necessarily imply clean of anions; and there- fore, all syringes should be flushed with’ water and sample or standard before use to mizimize contami- nation. 11.4 When the suppressor column becomes partially exhausted, regenerate with suppressor Tegenerant solution (8.6) in accordance with manufacturer's instructions. 12. Calculations 12.1 Refer the peak height or area noted for the anion(s) of interest to the appropriate analyt- ical curve(s) (see 10.3) to determine the anion concentration in milligrams per litre. Anion concentration, mg/L = Ax F where: A= milligrams per litre read from appropriate TABLE 1 Preparation of Standard Solutions for Instrument Calibratios 4327 calibration curve and F= dilution factor if sample was diluted prior to analysis, 13. Precision and Bias? 13.1 The collaborative test of this test method was performed in reagent water by 15 laborato- { ries, one operator each. Fourteen operators made uplicate determinations at each level for a total of 29 determinations at each level for each of seven anions, 13.2 The precision and bias of this test method for each anion in reagent water is ex- pressed in Tables 3 through 9. 13.3 These data may not apply to other water matrices * Supporting data has ben ied and are on loan from ASTM. Request RR:DI9-1105, Tigh Range Standard Gee 83.1) Milt of Each "termediate Range Low-Range Staid- Aion GaSe Sotasos, Anion Concenza. Sunda, m/L (see ar alle 4 fe 832) 533 1a) Diluted 12 = me _ 1000 mi. E Fuodde (F i 0 10 2 Ghieride (Cr) 10 10 10 02 Nitaite (NOP) 20 20 ° oa Phosphate (P00) 50 50 10 Bromide (BF) 0 0 a Nitrate (NOS) 30 20 06 Sule $0." 100 100 100 20} ‘TABLE 2 Preparation of Standard Soltions for ‘Determination of Retention Times Volume of —_ Stock Solution (1 mL = Stock Solution Anion Concea- 1.00 me) erie of “‘raton, me/t Wate mi Fioeide 3 3 Goride 4 4 Nivite 10 10 Phosphate 50 30 Bromide 10 wo Nite 30 30 Sulfate 50 50mm 5005275 9031252 STS mw qh 4327 TABLE 3. Foride ‘Amount Adéed, mg Amount Found, mg Ss s oe Bias, Signifcazt Le fo 95% Level 019 om ‘O08 ‘O02 +158 7 049 048 0.05 03 = 20 0 43 454 052 046 ra 0 212 aa 21 06 $09 10 130 142 9 2 =53 ys 322 30 86 33 =25 Bo TABLE 4 Chloride ‘Amount Added, mg Amount Found, mg S a i Statiscally i Bias, % Significant oe on 93% Lvl O17 026 010 008 4529 s 076 086 038 out 4132 0 110 172 oz 043 + 20 549 565 82 24 +29 20° 455 an 46 B +35 0 10% 1099 9 4a $24 20 TABLE 5 Nivite ‘Siatsically ‘Amount Added, mg Amount Found, mg si s i Bias, % Significant poe oe : 95% Level 04s 0.08 008 200 s 0.99 085 on ~s46 s 218 194 1 Hi10 ye 667 652 4s =23 sno 434 42 2 +18 20 937 952 4“ +16 0 TABLE 6 Bromide - Satatally ‘Amount Added, mg Amount Found, mg Ss s 5 ins, % Sigiscant ae BA 95% Level 025 025 008 002 00 20 046 045 0.04 0.04 22 20 137 29 10 06 =s8 ye 437 aa 39 25 35 20 63 63 3 " m7 20 750 139 3 uN +12 80 TABLE 7. Phosphate ‘Statistically ‘Amount Added, mg Amount Found, me Ss s. Fas, % ay POUL Poy 95% Level 018 010 ‘006 003 wa vs 049 om 0.15 017 =306 ye m2 23 Lt 08. =245 ye. 568 32 29 23 37 ye sit 6 m 3 =17 yes 3 63 n 9 06 ye4d 04327 (2) Bhoent reservoir @ Pump (@) Precolumn () Separator column (8) Suppressor column, (6) Detecor (2) Recorder or integrator, or both FIG. 1 Schematic of lon Chromatograph (Mandatory Information) Al. DETERMINATION OF RANGE OF METHOD AL The upper range of the method foran injected aliquot varies for each sample type and is limited by ‘the capacity of the separator column. If the ionic strength of the sample to be analyzed exceeds column capacity, the ions of interest will not be separated as shown in Fig. 2. Retention times will also decrease 2s the ionic strength of the sample increases. The upper range of the method for the ion(s) of interest in the sample matrix may be determined by the followis procedure. The procedure is defined for currently av able separator coturans supplied by the appropsiate manufactarer. ALLL Bypass the separator column (only the sup- pressor column is on line) and inject 100 ul of a 5.8- B/L (0.01 meq) solution of sodium chloride (NaCI). ‘This represents 10 % of the separator column capacity, that is 0.1 meq. Note the conductivity response. AJ.1.2 Inject 100 pL of the sample of interest (sep- arator column bypassed). Note the conductivity re- sponse. AL.L3 Ifthe conductivity response noted in AI1.2 is less than or equal to the conductivity response noted in the sodium chloride solution in Al.1.1, column capacity has not been exceeded.mm 9009276 003i-94 378 Ml q) 04327 ALLA If the conductivity response noted in Al1.2 must be diluted prior to injection into the ion chro- is greater than the conductivity response noted for the matograph. ‘ sodium chloride solution in ALLt-1, the test sample A2. CONFIGURATIONS FOR SETTING UP AN ION CHROMATOGRAPH A2.L Table A2.1 lists various configurations for set-; Configurations other than those listed may be used if ting up an ion chromatograph, Choice of configuratién’, they successfully resolve all anions of interest, as de- depends primarily upon which ions are of interest. scribed in 7.1.2 of this test method. TABLE A21 Configurations for Setting Up 2 fon Chromatograph low Rat, Separtor Column SuppressorColumn! Flow Rat Comment 4xR0mme 4x 100mm? 23 extrolation of all anions 9x 100 mm 4x smn 4x 250mme OOM? AB wl ale 6 anions in about ne 9x 100 mat of 1) but wll ot eave NO and ae : ()4xS0mm* 4x SO-mme 4x 100mm? 23 wilreselve NO} and SO¥ ony 9 100 mm? @)sxsommt 4x S0mm 4x 100mm? 46 will eolve SOF only 9% 100 mmé & : “In all cass, either suppresior column i suitable The 4 x 100 man will give a smaller waterdip, but the 9% 100 rom wil last longer between regenerations. a Dionex Part No, 30825 or equivalent. Dionex Part No, 30827 or equivalent. Dionex Par No. 30829 or equivalent * Dionex Part No. 30828 or equivalent APPENDIX (Nonmandatory Information) ‘XL. TECHNIQUES.FOR ELIMINATING WATER DIP X11 A method of eliminating the water dip is to eluent concentrate (solution that is 100 times more introduce concentrations of carbonate and bicarbonate _concentraved than the eluent used for analysis) per 100 into the sample that closely approximate that of the ml of sample. eluent used for analysis. Adjustment of sample back- X12 Standard solutions must be prepared as di- ground may be accomplished in two different ways: rected in X1.1.2. It is important to prepare a blank XI.L.1 Dilute the sample with eluent ifsample di- using reagent water and eluent (100:1) to compensate lution is required prior to analysis. for any anionic impurities present. ‘XI.L2 Aéd an equivalent of 1.0 mL of a prepared ‘The American Society for Teuting and Materials toked no postion respecting the validity of any patent rights asserted in connection with one item mentioned inthis standard. Users ofthis standard are expresly advised that determination of the validity of any sich _nutont rights, andthe risk of infringement of such rights, are entirely their own responsibilty. This standard is subject to revision at any time bythe responsible technica committee and must be reviewed every five years and If not revised. eter reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards and should be address 19 ASTM Headquarters. Your comments will receive cargul consideration at a meeting of the responsible technical commitee, which you may attend. Ifyou feel that your comments have not received a fair hearing you should ‘make your views known to the ASTM Committe on Standards, 1916 Race S., Philadelphia, Po. 19103.