1、Designation: D5542 04 (Reapproved 2009)D5542 16Standard Test Methods forTrace Anions in High Purity Water by Ion Chromatography1This standard is issued under the fixed designation D5542; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revisi
2、on, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover the determination of trace (g/L) levels of fluoride, acetate, formate, chlori
3、de, phosphate, andsulfate in high purity water using ion chromatography in combination with sample preconcentration. Other anions, such asbromide, nitrite, nitrate, sulfite, and iodide can be determined by this method. However, since they are rarely present in significantconcentrations in high purit
4、y water, they are not included in this test method. Two test methods are presented and their ranges ofapplication, as determined by a collaborative study, are as follows:Range Tested(g/L Added)Limit of DetectionA(Single Operator)(g/L)SectionsTest Method A: 715Test Method A: 716Chloride 024 0.8Phosph
5、ate 039 BSulfate 055 1.8Test Method B: 1623Test Method B: 1724Fluoride 014 0.7Acetate 0414 6.8Formate 0346 5.6A Limit of detection is lowest measurable concentration not reportable as zero at 99 % level of confidence as per EPRI study as cited in Sections 1516 and 2324.B Insufficient data to calcula
6、te limit of detection.1.2 It is the users responsibility to ensure the validity of these test methods for waters of untested matrices.1.3 The common practical range of Test MethodAis as follows: chloride, 1 to 100 g/L, phosphate, 3 to 100 g/L, and sulfate,2 to 100 g/L.1.4 The common practical range
7、of Test Method B is as follows: fluoride, 1 to 100 g/L, acetate, 10 to 200 g/L, and formate,5 to 200 g/L.1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.6 This standard does not purport to address all of the safety conce
8、rns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1066 Practice for Sampling SteamD1129 Term
9、inology Relating to WaterD1192 Guide for Equipment for Sampling Water and Steam in Closed Conduits (Withdrawn 2003)3D1193 Specification for Reagent WaterD3370 Practices for Sampling Water from Closed ConduitsD3856 Guide for Management Systems in Laboratories Engaged in Analysis of Water1 These test
10、methods are under the jurisdiction of ASTM Committee D19 on Water and are the direct responsibility of Subcommittee D19.03 on Sampling Water andWater-Formed Deposits, Analysis of Water for Power Generation and Process Use, On-Line Water Analysis, and Surveillance of Water.Current edition approved Ma
11、y 1, 2009June 1, 2016. Published June 2009June 2016. Originally approved in 1994. Last previous edition approved in 20042009 asD554204. DOI: 10.1520/D5542-04R09. 04 (2009). DOI: 10.1520/D5542-16.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at s
12、erviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 The last approved version of this historical standard is referenced on www.astm.org.This document is not an ASTM standard and is intended only to provide the user o
13、f an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as pu
14、blished by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1D4210 Practice for Intralaboratory Quality Control Procedures and a Discussion on Reporting Low-Level Data (Withdrawn2002)3D4453
15、 Practice for Handling of High Purity Water SamplesD5810 Guide for Spiking into Aqueous SamplesD5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis3. Terminology3.1 Definitions:3.1.1 For definitions of terms used in these test methods this standard,
16、refer to Terminology D1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 analytical columnscolumns, na combination of one or more guard columns followed by one or more separatorcolumns used to separate the ions of interest. It should be remembered that all of the columns in series contrib
17、ute to the overallcapacity of the analytical column set.3.2.1.1 DiscussionIt should be remembered that all of the columns in series contribute to the overall capacity of the analytical column set.3.2.2 breakthrough volumevolume, nthe maximum sample volume that can be passed through a concentrator co
18、lumn beforethe least tightly bound ion of interest is eluted.3.2.3 concentrator columncolumn, nan ion exchange column used to concentrate the ions of interest and thereby increasemethod sensitivity.3.2.4 eluanteluant, nthe ionic mobile phase used to transport the sample through the exchange column.3
19、.2.5 guard columncolumn, na column used before the separator column to protect it from contaminants, such as particulatematter or irreversibly retained materials.3.2.6 ion chromatographychromatography, na form of liquid chromatography in which ionic constituents are separated byion exchange followed
20、 by a suitable detection means.3.2.7 resolutionresolution, nthe ability of an analytical column to separate constituents under specific test conditions.3.2.8 separator columncolumn, nthe ion exchange column used to separate the ions of interest according to their retentioncharacteristics prior to th
21、eir detection.3.2.9 suppressor devicedevice, na device that is placed between the analytical columns and the detector. Its purpose is toinhibit detector response to the ionic constituents in the eluant, so as to lower the detector background and at the same time enhancedetector response to the ions
22、of interest.3.2.9.1 DiscussionD5542 162Its purpose is to inhibit detector response to the ionic constituents in the eluant, so as to lower the detector background and at thesame time enhance detector response to the ions of interest.4. Significance and Use4.1 The anions fluoride, chloride, and sulfa
23、te have been identified as important contributors to corrosion of high pressure boilers,electric power turbines and their associated heat exchangers. Many electric power utilities attempt to reduce these contaminantsin their boiler feed water to less than 1 g/L.4.2 In the semiconductor manufacturing
24、 process these ions, among others, have been identified as a cause of low product yieldand, thus, must be monitored and controlled to levels similar to those required by the electric power industry.4.3 Low molecular weight organic acids, such as acetate and formate, have been found in many steam gen
25、erator feed watersand condensates.They are believed to come from the high temperature breakdown of organic matter found in boiler make up water.It is felt that these organic acids promote corrosion by lowering the pH of boiler waters and may even be corrosive themselves.4.4 Such low molecular weight
26、 organics may also be produced when ultraviolet light is used to produce bacteria-free water forsemiconductor processing. Such polar organic contaminants are suspected of causing reduced semiconductor yields.4.5 Phosphates are commonly added to drum boilers in the low mg/L level to precipitate calci
27、um and magnesium and therebyprevent scale formation. Ion chromatography can be used to monitor the concentration of such chemicals in boiler water, as wellas detect unwanted carry-over into the steam.5. Reagents5.1 Purity of ReagentsReagent grade chemicals shall be used in all tests. Unless otherwis
28、e indicated, it is intended that allreagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, wheresuch specifications are available. 45.1.1 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently hig
29、h purity to permit its usewithout lessening the accuracy of the determination.5.2 Purity of Water Unless otherwise indicated, references to water shall be understood to mean reagent water conformingto Specification D1193, Type I. Column life may be extended by passing Type I water through a 0.22 m f
30、ilter prior to use. Freshlyprepared water should be used for making the low level standards intended for calibration. The detection limits of this method willbe limited by the purity of the water and reagents used to make the standards. The purity of the water may be checked by use ofthis method. An
31、ion concentrations of less than 0.2 ppb each, is typical of Type I water.6. Sampling6.1 Collect samples in accordance with Practice D1066, SpecificationGuide D1192, PracticePractices D3370, and PracticeD4453, as applicable.6.2 Collect samples in polystyrene bottles that should be filled to overflow
32、and capped, so as to exclude air. Glass sample bottlesshould not be used, as they can contribute ionic contamination.6.3 Samples should be analyzed within 48 h of sampling. When acetate, formate or phosphate data are required, refrigerate at4C upon sampling.6.4 To prevent added ionic contamination,
33、no preservation or filtration of the sample shall be done.TEST METHOD ACHLORIDE, PHOSPHATE, AND SULFATE7. Scope7.1 This test method is optimized for the quantitative determination of trace levels of chloride, phosphate, and sulfate. Anionssuch as fluoride, acetate, and formate can be detected by thi
34、s method, but are not reliably resolved from each other. See Fig. 1 fora typical chromatogram.7.2 Using a concentrated sample volume of 20 mL, the test method is applicable in the range outlined in Section 1. The rangeof this test method may be extended by concentrating a smaller or a larger sample
35、volume. Be sure not to exceed concentratorcolumn breakthrough volume (see annex).4 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For Suggestions on the testing of reagents not listed bythe American Chemical Society, see Annual Standards for L
36、aboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.FIG. 1 Anions by Test Method AD5542 1638. Quality Control8.1 Before this test is applied to analyzing unknown samples, the analyst s
37、hall establish quality control procedures asrecommended in Practices D4210 and D5847, and Guide D3856. In order to be certain that analytical values obtained by this testmethod are valid and accurate within the confidence limits of the tests, the QC procedures described in this section must befollow
38、ed.8.2 The laboratory using this test shall perform an initial demonstration of laboratory capability.Analyze seven replicates of anInitial Demonstration of Performance (IDP) solution. The IDPsolution contains method analytes of known concentration, preparedfrom a different source to the calibration
39、 standards, used to fortify reagent water. Ideally, the IPD solution should be prepared byan independent source from reference materials.8.2.1 The mean and standard deviation of seven values for each test method analyte shall then be calculated and compared,according to Practice D5847, to the single
40、 operator precision and recovery established for this test method.8.2.2 If the values obtained for the IDP precision and recovery do not meet the criteria described above, initial demonstrationof performance must be repeated until the results fall within these criteria.8.3 When beginning use of this
41、 method, a Calibration Verification Standard (CVS) containing each test method analyte shallbe analyzed to verify the calibration standards and acceptable instrument performance. This verification should be performed oneach analysis day or whenever fresh eluent has been prepared. The CVS is a soluti
42、on of method analytes of known concentration(mid-calibration range) used to fortify reagent water. The CVS must be prepared from a different source than the calibrationstandards. If the determined CVS concentrations are not within 615 % of the known values, the analyst shall reanalyze the CVS.If the
43、 values still fall outside acceptable limits, a new calibration curve is required which must be confirmed by a successful CVSbefore continuing with on-going analyses.8.4 One continuing CVS shall be analyzed with each sample batch (maximum of 20 samples) to verify the previouslyestablished calibratio
44、n curves. If the determined analyte concentrations fall outside acceptable limits (615 %) that analyte isjudged out of control, and the source of the problem must be identified before continuing with on-going analyses. All samplesfollowing the last acceptable CVS should be reanalyzed.8.5 One Laborat
45、ory Control Sample (LCS) shall be analyzed with each sample batch (maximum of 20 samples) to ensure thetest method is in control. The LCS is a solution of the test method analytes spiked at concentration levels of the IDPsolution addedto a matrix that sufficiently challenges the test method. The LCS
46、 must be taken through all of the steps of this analytical methodincluding sample preservation and pretreatment.The analyte recoveries for the LCS must fall within the control limits listed below:Upper Control Limit5x13S (1)Lower Control Limit5x23S (2)where:x = percent mean recovery, andS = standard
47、 deviation of the mean recovery, as determined from historical values for the equivalent concentration and matrix.8.5.1 If the results do not fall within these limits, analysis of samples is halted until the problem is corrected. Either all samplesin the batch must be reanalyzed so as to pass these
48、performance criteria, or the results must be qualified with an indication thatthey do not fall within the performance criteria of the test method.8.6 A reagent blank shall be analyzed as part of the initial generation of calibration curves. A reagent blank shall also beanalyzed with each sample batc
49、h (maximum of 20 samples) to check for contamination introduced by the laboratory or use of thetest method.8.7 One matrix spike (MS) shall be analyzed with each sample batch (maximum of 20 samples) to test method recovery. Spikea portion of one sample from each batch with a known concentration of the method analytes. The MS shall be prepared inaccordance with that outlined in Guide D5810 and section 11.11 of Guide D3856. The % recovery of the spike must fall within% recovery 6 analyst % RSD for an equivalent spike concentration and
