1、Designation: D1688 12D1688 17Standard Test Methods forCopper in Water1This standard is issued under the fixed designation D1688; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses ind
2、icates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the U.S. Department of Defense.1. Scope*1.1 These test methods cover the determination of copper in water by atomic a
3、bsorption spectrophotometry. Section 34 onQuality Control pertains to these test methods. Three test methods are included as follows:Test Method ConcentrationRange SectionsAAtomic Absorption,Direct0.05 to 5 mg/L 7 15BAtomic Absorption,Chelation-Extraction50 to 500 g/L 16 24CAtomic Absorption,Graphit
4、e Furnace5 to 100 g/L 25 33Test Method ConcentrationRange SectionsAAtomic Absorption,Direct0.05 to 5 mg/L 7 15BAtomic Absorption,Chelation-Extraction50 to 500 g/L 16 24CAtomic Absorption,Graphite Furnace5 to 100 g/L 25 331.2 Either dissolved or total recoverable copper may be determined. Determinati
5、on of dissolved copper requires filtrationthrough a 0.45-m (No.(11.10 325) ) membrane filter at the time of collection. In-line membrane filtration is preferable.1.3 The values stated in either SI units or inch-pound units are to be regarded separately as standard. The values statedgivenin each syst
6、em are mathematical conversions and may not be exact equivalents; therefore, each system shall be used independentlyof the other.parentheses are mathematical conversion to inch-pound units that are provided for information only and are notconsidered standard.1.4 Three former photometric test methods
7、 were discontinued. Refer to Appendix X1 for historical information.1.5 This standard does not purport to address all of the safety concerns, 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 a
8、pplicability of regulatorylimitations prior to use. For specific hazard statements, see Note 411.3, Note 611.9.1, Note 1020.10, and Note 1622.11.1.5 Three former photometric test methods were discontinued. Refer to Appendix X1 for historical information.1.6 This international standard was developed
9、in accordance with internationally recognized principles on standardizationestablished in the Decision on Principles for the Development of International Standards, Guides and Recommendations issuedby the World Trade Organization Technical Barriers to Trade (TBT) Committee.2. Referenced Documents2.1
10、 ASTM Standards:2D858 Test Methods for Manganese in WaterD1066 Practice for Sampling SteamD1068 Test Methods for Iron in Water1 These test methods are under the jurisdiction of ASTM Committee D19 on Water and are the direct responsibility of Subcommittee D19.05 on Inorganic Constituentsin Water.Curr
11、ent edition approved Sept. 1, 2012June 1, 2017. Published September 2012July 2017. Originally approved in 1959. Last previous edition approved in 20072012 asD1688 07.D1688 12. DOI: 10.1520/D1688-12.10.1520/D1688-17.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM C
12、ustomer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to
13、 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 published by ASTM is to be considered the official document.*A Summa
14、ry of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD1687 Test Methods for Chromium in WaterD1691 Test Method
15、s for Zinc in WaterD1886 Test Methods for Nickel in WaterD1976 Test Method for Elements in Water by Inductively-Coupled Argon Plasma Atomic Emission SpectroscopyD2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling Wat
16、er from Closed ConduitsD3557 Test Methods for Cadmium in WaterD3558 Test Methods for Cobalt in WaterD3559 Test Methods for Lead in WaterD3919 Practice for Measuring Trace Elements in Water by Graphite Furnace Atomic Absorption SpectrophotometryD4841 Practice for Estimation of Holding Time for Water
17、Samples Containing Organic and Inorganic ConstituentsD5673 Test Method for Elements in Water by Inductively Coupled PlasmaMass SpectrometryD5810 Guide for Spiking into Aqueous SamplesD5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis3. Terminology3
18、.1 DefinitionsDefinitions: For definitions of terms used in these test methods, refer to Terminology D1129.3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 continuing calibration blank, na solution containing no
19、 analytes (of interest) which is used to verify blank response andfreedom from carryover.3.2.2 continuing calibration verification, na solution (or set of solutions) of known concentration used to verify freedom fromexcessive instrumental drift; the concentration is to cover the range of calibration
20、 curve.3.2.3 total recoverable copper, na descriptive term relating to the forms of copper recovered in the acid-digestion procedurespecified in this test standard.4. Significance and Use4.1 Copper is found in naturally occurring minerals principally as a sulfide, oxide, or carbonate. It makes up ap
21、proximately0.01 % of the earths crust and is obtained commercially from such ores as chalcopyrite (CuFeS2). Copper is also found inbiological complexes such as hemocyanin.4.2 Copper enters water supplies through the natural process of dissolution of minerals, through industrial effluents, through it
22、suse, as copper sulfate, to control biological growth in some reservoirs and distribution systems, and through corrosion of copperalloy water pipes. Industries whose wastewaters may contain significant concentrations of copper include mining, ammunitionproduction, and most metal plating and finishin
23、g operations. It may occur in simple ionic form or in one of many complexes withsuch groups as cyanide, chloride, ammonia, or organic ligands.4.3 Although its salts, particularly copper sulfate, inhibit biological growth such as some algae and bacteria, copper isconsidered essential to human nutriti
24、on and is not considered a toxic chemical at concentrations normally found in water supplies.4.4 ICP-MS or ICP-AES may also be appropriate but at a higher instrument cost. See Test Methods D5673 and D1976.5. Purity of Reagents5.1 Reagent grade chemicals shall be used in all tests. Unless otherwise i
25、ndicated, it is intended that all reagents shall conformto the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications areavailable. available.3 Other grades may be used, provided it is first ascertained that the reagent is of sufficiently h
26、igh purity topermit its use without lessening the accuracy of the determination.5.2 Purity of WaterUnless otherwise indicated, references to water shall be understood to mean reagent water conforming toSpecification D1193, Type I. Other reagent water types may be used, provided it is first ascertain
27、ed that the water is of sufficientlyhigh purity to permit its use without lessening the bias and precision of the determination. Type II water was specified at the timeof round-robin testing of this test method.6. Sampling6.1 Collect the sample in accordance with Practices D1066 and D3370, as applic
28、able.3 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 Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Ph
29、armacopeia and NationalFormulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, MD.D1688 1726.2 Samples shall be preserved with nitric acid (HNO3, sp gr 1.42) to a pH of 2 or less immediately at the time of collection,normally about 2 mL/L. If only dissolved copper is to be determined, the
30、sample shall be filtered through a 0.45-m (No.(11.10325) ) membrane filter before acidification. The holding time for samples may be calculated in accordance with Practice D4841.NOTE 1Alternatively, the pH may be adjusted in the laboratory if the sample is returned within 14 days. within 14 days of
31、collection. However, acidmust be added at least 24 hours before analysis to dissolve any metals that adsorb to the container walls. This could reduce hazards of working with acidsin the field when appropriate.TEST METHOD AATOMIC ABSORPTION, DIRECT7. Scope7.1 This test method covers the determination
32、 of dissolved and total recoverable copper in most waters and waste waters.7.2 This test method is applicable in the range from 0.05 to 5 mg/L of copper. The range may be extended to concentrationsgreater than 5 mg/L by dilution of the sample.7.3 Collaborative test data were obtained on reagent wate
33、r, river water, tap water, ground water, lake water, refinery primarytreated effluent, and two untreated waste waters. The information on precision and bias may not apply to other waters.7. Scope7.1 This test method covers the determination of dissolved and total recoverable copper in most waters an
34、d waste waters.7.2 This test method is applicable in the range from 0.05 to 5 mg/L of copper. The range may be extended to concentrationsgreater than 5 mg/L by dilution of the sample.7.3 Collaborative test data were obtained on reagent water, river water, tap water, ground water, lake water, refiner
35、y primarytreated effluent, and two untreated waste waters. The information on precision and bias may not apply to other waters.8. Summary of Test Method8.1 Copper is determined by atomic absorption spectrophotometry. Dissolved copper in the filtered sample is aspirated directlywith no pretreatment.
36、Total recoverable copper in the sample is aspirated following hydrochloric-nitric acid digestion and filtration.The same digestion procedure may be used to determine total recoverable cadmium (Test Methods D3557), chromium (TestMethods D1687), cobalt (Test Methods D3558), iron (Test Methods D1068),
37、lead (Test Methods D3559), manganese (TestMethods D858), nickel (Test Methods D1886), and zinc (Test Methods D1691).9. Interferences9.1 Sodium, potassium, sulfate, and chloride (8000 mg/Leach), calcium and magnesium (5000 mg/Leach), nitrate (2000 mg/L),iron (1000 mg/L), and cadmium, lead, nickel, zi
38、nc, cobalt, manganese, and chromium (10 mg/L each) do not interfere.9.2 Background correction or a chelation-extraction procedure (see Test Method B) may be necessary to determine low levelsof copper in some waters.NOTE 2Instrument manufacturers instructions for use of the specific correction techni
39、que should be followed.10. Apparatus10.1 Atomic Absorption Spectrophotometer, for use at 324.7 nm.NOTE 3The manufacturers instructions should be followed for all instrumental parameters. A wavelength other than 324.7 nm may be used if it hasbeen determined to be equally suitable.10.1.1 Copper Hollow
40、-Cathode LampMultielement hollow-cathode lamps are available and have been found satisfactory.10.2 OxidantSee 11.8.10.3 FuelSee 11.9.10.2 Pressure-Reducing ValvesThe supplies of fuel and oxidant shall be maintained at pressures somewhat higher than thecontrolled operating pressure of the instrument
41、by suitable valves.11. Reagents and Materials11.1 Copper Solution, Stock (1.0 mL = 1.0 mg Cu)Dissolve 1.000 g of electrolytic copper contained in a 250-mL beaker ina mixture of 15 mLof HNO3 (sp gr 1.42) and 15 mLof water. Slowly add 4 mLof H2SO4 (1 + 1) and heat until SO3 fumes evolve.Cool, wash dow
42、n the beaker with water, and dilute to 1 L with water. A purchased copper stock solution of appropriate knownpurity is also acceptable.11.2 Copper Solution, Standard (1.0 mL = 0.1 mg Cu)Dilute 100.0 mL of copper stock solution to 1 L with water.11.3 Hydrochloric Acid (sp gr 1.19)Concentrated hydroch
43、loric acid (HCl).D1688 173NOTE 4If a high reagent blank is obtained, distill the HCl or use a spectrograde acid.CautionWhen HCl is distilled an azeotropic mixture is obtained(approximately 6 N HCl). Therefore, whenever concentrated HCl is specified for the preparation of a reagent or in the procedur
44、e, use double the volumespecified if distilled HCl is used.(WarningWhen HCl is distilled an azeotropic mixture is obtained (approximately 6 N HCl). Therefore, wheneverconcentrated HCl is specified for the preparation of a reagent or in the procedure, use double the volume specified if distilled HCli
45、s used.)11.4 Nitric Acid (sp gr 1.42)Concentrated nitric acid (HNO3).NOTE 5If a high reagent blank is obtained, distill the HNO3 or use a spectrograde acid.11.5 Nitric Acid (1 + 499)Add 1 volume of HNO3 (sp gr 1.42) to 499 volumes of water.11.6 Sulfuric AcidConcentrated sulfuric acid (H2SO4).11.7 Su
46、lfuric Acid (1 + 1)Cautiously, and with constant stirring and cooling, add 1 volume of concentrated sulfuric acid(H2SO4, sp gr 1.84) to 1 volume of water.11.8 Oxidant:11.8.1 Air, which has been passed through a suitable filter to remove oil, water, and other foreign substances, is the usualoxidant.1
47、1.9 Fuel:11.9.1 AcetyleneStandard, commercially available acetylene is the usual fuel.Acetone, always present in acetylene cylinders,can affect analytical results.The cylinder should be replaced at 345 kPa (50 psi). (Warning“Purified” grade acetylene containinga special proprietary solvent rather th
48、an acetone should not be used with poly(vinyl chloride) tubing as weakening of the tubingwalls can cause a potentially hazardous situation.)NOTE 6Precaution: “Purified” grade acetylene containing a special proprietary solvent rather than acetone should not be used with poly(vinylchloride) tubing as
49、weakening of the tubing walls can cause a potentially hazardous situation.11.10 Filter PaperPurchase suitable filter paper. Typically the filter papers have a pore size of 0.45-m membrane. Materialsuch as fine-textured, acid-washed, ashless paper, or glass fiber paper are acceptable. The user must first ascertain that the filterpaper is of sufficient purity to use without adversely affecting the bias and precision of the test method.12. Standardization12.1 Prepare 100 mL each of a blank and at least four standard solutio
