1、Designation: D 1688 07Standard Test Methods forCopper in Water1This standard is issued under the fixed designation D 1688; 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 indicates
2、 the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the Department of Defense.1. Scope1.1 These test methods cover the determination of copper inwater by atomic absorption sp
3、ectrophotometry. Three testmethods 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,Graphite Furnace5 to 100 g/L 25-331.2 Either dissolved or total recoverable coppe
4、r may bedetermined. Determination of dissolved copper requires filtra-tion through a 0.45-m (No. 325) membrane filter at the timeof collection. In-line membrane filtration is preferable.1.3 The values stated in SI units are to be regarded as thestandard. The values given in parentheses are provided
5、forinformation only.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to
6、 use. For specific hazardstatements, see Note 3, Note 5, Note 8, and Note 13.1.5 Three former photometric test methods were discontin-ued. Refer to Appendix X1 for historical information.2. Referenced Documents2.1 ASTM Standards:2D 858 Test Methods for Manganese in WaterD 1066 Practice for Sampling
7、SteamD 1068 Test Methods for Iron in WaterD 1129 Terminology Relating to WaterD 1192 Guide for Equipment for Sampling Water andSteam in Closed Conduits3D 1193 Specification for Reagent WaterD 1687 Test Methods for Chromium in WaterD 1691 Test Methods for Zinc in WaterD 1886 Test Methods for Nickel i
8、n WaterD 2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD 3370 Practices for Sampling Water from Closed ConduitsD 3557 Test Methods for Cadmium in WaterD 3558 Test Methods for Cobalt in WaterD 3559 Test Methods for Lead in WaterD 3919 Practic
9、e for Measuring Trace Elements in Water byGraphite Furnace Atomic Absorption SpectrophotometryD 4841 Practice for Estimation of Holding Time for WaterSamples Containing Organic and Inorganic ConstituentsD 5810 Guide for Spiking into Aqueous SamplesD 5847 Practice for Writing Quality Control Specific
10、ationsfor Standard Test Methods for Water Analysis3. Terminology3.1 Definitions: For definitions of terms used in these testmethods, refer to Terminology D 1129.4. Significance and Use4.1 Copper is found in naturally occurring minerals princi-pally as a sulfide, oxide, or carbonate. It makes up appr
11、oxi-mately 0.01 % of the earths crust and is obtained commer-cially from such ores as chalcopyrite (CuFeS2). Copper is alsofound in biological complexes such as hemocyanin.4.2 Copper enters water supplies through the natural processof dissolution of minerals, through industrial effluents, throughits
12、 use, as copper sulfate, to control biological growth in somereservoirs and distribution systems, and through corrosion ofcopper alloy water pipes. Industries whose wastewaters maycontain significant concentrations of copper include mining,ammunition production, and most metal plating and finishingo
13、perations. It may occur in simple ionic form or in one of manycomplexes with such groups as cyanide, chloride, ammonia, ororganic ligands.1These test methods are under the jurisdiction of ASTM Committee D19 onWater and are the direct responsibility of Subcommittee D19.05 on InorganicConstituents in
14、Water.Current edition approved Aug. 1, 2007. Published August 2007. Originallyapproved in 1959. Last previous edition approved in 2002 as D 1688 02.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandar
15、ds volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4.3 Although its salts, particularly copper sulfate, inhibitbiological growth such as s
16、ome algae and bacteria, copper isconsidered essential to human nutrition and is not considered atoxic chemical at concentrations normally found in watersupplies.5. Purity of Reagents5.1 Reagent grade chemicals shall be used in all tests.Unless otherwise indicated, it is intended that all reagents sh
17、allconform to the specifications of the Committee on AnalyticalReagents of the American Chemical Society, where suchspecifications are available.4Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy
18、ofthe determination.5.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Specification D 1193, Type I. Other reagent water types maybe used, provided it is first ascertained that the water is ofsufficiently high purity to permit its
19、 use without lessening thebias and precision of the determination. Type II water wasspecified at the time of round-robin testing of this test method.6. Sampling6.1 Collect the sample in accordance with Practices D 1066,Specification D 1192, and Practices D 3370, as applicable.6.2 Samples shall be pr
20、eserved with nitric acid (HNO3,spgr1.42) to a pH of 2 or less immediately at the time of collection,normally about 2 mL/L. If only dissolved copper is to bedetermined, the sample shall be filtered through a 0.45-m (No.325) membrane filter before acidification. The holding time forsamples may be calc
21、ulated in accordance with Practice D 4841.TEST METHOD AATOMIC ABSORPTION,DIRECT7. Scope7.1 This test method covers the determination of dissolvedand total recoverable copper in most waters and waste waters.7.2 This test method is applicable in the range from 0.05 to5 mg/L of copper. The range may be
22、 extended to concentra-tions greater 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, refineryprimary treated effluent, and two untreated waste waters. Theinformation on precision and bias may not apply
23、 to otherwaters.8. Summary of Test Method8.1 Copper is determined by atomic absorption spectropho-tometry. Dissolved copper in the filtered sample is aspirateddirectly with no pretreatment. Total recoverable copper in thesample is aspirated following hydrochloric-nitric acid digestionand filtration.
24、 The same digestion procedure may be used todetermine total recoverable cadmium (Test Methods D 3557),chromium (Test Methods D 1687), cobalt (Test MethodsD 3558), iron (Test Methods D 1068), lead (Test MethodsD 3559), manganese (Test Methods D 858), nickel (Test Meth-ods D 1886), and zinc (Test Meth
25、ods D 1691).9. Interferences9.1 Sodium, potassium, sulfate, and chloride (8000 mg/Leach), calcium and magnesium (5000 mg/Leach), nitrate (2000mg/L), iron (1000 mg/L), and cadmium, lead, nickel, zinc,cobalt, manganese, and chromium (10 mg/L each) do notinterfere.9.2 Background correction or a chelati
26、on-extraction proce-dure (see Test Method B) may be necessary to determine lowlevels of copper in some waters.NOTE 1Instrument manufacturers instructions for use of the specificcorrection technique should be followed.10. Apparatus10.1 Atomic Absorption Spectrophotometer, for use at 324.7nm.NOTE 2The
27、 manufacturers instructions should be followed for allinstrumental parameters. A wavelength other than 324.7 nm may be usedif it has been determined to be equally suitable.10.1.1 Copper Hollow-Cathode LampMultielementhollow-cathode lamps are available and have been foundsatisfactory.10.2 OxidantSee
28、11.8.10.3 FuelSee 11.9.10.4 Pressure-Reducing ValvesThe supplies of fuel andoxidant shall be maintained at pressures somewhat higher thanthe controlled operating pressure of the instrument by suitablevalves.11. Reagents and Materials11.1 Copper Solution, Stock (1.0 mL = 1.0 mg Cu)Dissolve 1.000 g of
29、 electrolytic copper contained in a 250-mLbeaker in a mixture of 15 mL of HNO3(sp gr 1.42) and 15 mLof water. Slowly add 4 mL of H2SO4(1 + 1) and heat until SO3fumes evolve. Cool, wash down the beaker with water, anddilute to 1 Lwith water.Apurchased stock solution of adequatepurity is also acceptab
30、le.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 hydro-chloric acid (HCl).NOTE 3If a high reagent blank is obtained, distill the HCl or use aspectrograde acid. CautionWhen HCl is distilled
31、 an azeotropic mixtureis obtained (approximately 6 N HCl). Therefore, whenever concentratedHCl is specified for the preparation of a reagent or in the procedure, usedouble the volume specified if distilled HCl is used.11.4 Nitric Acid (sp gr 1.42)Concentrated nitric acid(HNO3).NOTE 4If a high reagen
32、t blank is obtained, distill the HNO3or use aspectrograde acid.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals,
33、BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D 1688 07211.5 Nitric Acid (1 + 499)Add 1 volume of HNO3(sp gr1.42) to 499 volumes of water.11.6 Sulfuric AcidConcentrated sulfuric acid (H2SO4).11.7 Sulf
34、uric Acid (1 + 1)Cautiously, and with constantstirring 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 toremove oil, water, and other foreign substances, is the usualoxidant.11.9
35、Fuel:11.9.1 AcetyleneStandard, commercially available acety-lene is the usual fuel. Acetone, always present in acetylenecylinders, can affect analytical results. The cylinder should bereplaced at 50 psig (345 kPa).NOTE 5Precaution: “Purified” grade acetylene containing a specialproprietary solvent r
36、ather than acetone should not be used with poly(vinylchloride) tubing as weakening of the tubing walls can cause a potentiallyhazardous situation.12. Standardization12.1 Prepare 100 mL each of a blank and at least fourstandard solutions to bracket the expected copper concentrationrange of the sample
37、s to be analyzed by diluting the standardcopper solution (11.2) with HNO3(1 + 499). Prepare the stan-dards each time the test is to be performed.12.2 When determining total recoverable copper add 0.5mL of HNO3(sp gr 1.42) and proceed as directed in 13.2-13.4.When determining dissolved copper proceed
38、 with 13.5.12.3 Aspirate the blank and standards and record the instru-ment readings. Aspirate HNO3(1 + 499) between each stan-dard.12.4 Prepare an analytical curve by plotting the absorbanceversus standard concentration for each standard. Alternatively,read directly in concentration from the instru
39、ment.13. Procedure13.1 Measure 100.0 mL of a well-mixed acidified sampleinto a 125-mL beaker or flask.NOTE 6If only dissolved copper is to be determined, start with 13.5.13.2 Add 5 mL of HCl (sp gr 1.19) to each sample.13.3 Heat the samples on a steam bath or hotplate in awell-ventilated hood until
40、the volume has been reduced to 15to 20 mL, making certain that the samples do not boil.NOTE 7When analyzing samples containing appreciable amounts ofsuspended matter, the amount of reduction in volume is left to thediscretion of the analyst.13.4 Cool and filter the samples through a suitable filter,
41、such as fine-textured, acid washed, ashless paper, into 100-mLvolumetric flasks. Wash the filter paper two or three times withwater and adjust to volume.13.5 Aspirate each filtered and acidified sample and deter-mine its absorbance or concentration at 324.7 nm. AspirateHNO3(1 + 499) between each sam
42、ple.14. Calculation14.1 Calculate the concentration of copper in each sample,in milligrams per L, using an analytical curve or alternatively,read directly in concentration (see 12.4).15. Precision and Bias515.1 The collaborative test of this test method was per-formed by ten laboratories, five of wh
43、ich supplied two opera-tors each. Each of the 15 operators made determinations atthree levels on three different days in samples of reagent waterand water of choice for a total of 270 determinations.15.2 These collaborative test data were obtained on reagentgrade water, river water, tap water, groun
44、d water, lake water,refinery primary treated effluent, and two untreated wastewaters. For other matrices, these data may not apply.15.3 Precision and bias for this test method conform toPractice D 2777-77, which was in place at the time ofcollaborative testing. Under the allowances made in 1.4 ofPra
45、ctice D 2777-06, these precision and bias data do meetexisting requirements for interlaboratory studies of CommitteeD19 test methods.15.4 PrecisionThe single-operator and overall precisionof this test method within its designated range may beexpressed as follows:In reagent water, Type II:SO5 0.020X
46、1 0.035ST5 0.052X 1 0.123In water or waste water:SO5 0.016X 1 0.033ST5 0.060X 1 0.039where:SO= single-operator precision,ST= overall precision, andX = determined concentration of copper, mg/L.15.5 BiasRecoveries of known amounts of copper wereas shown in Table 1.TEST METHOD BATOMIC ABSORPTION,CHELAT
47、ION-EXTRACTION16. Scope16.1 This test method covers the determination of dissolvedand total recoverable copper in most waters and brines.5Supporting data are available from ASTM International Headquarters. RequestRR: D19-1037.TABLE 1 Determination of Bias for Test Method AAmount Added,mg Cu/LAmount
48、Found, mgCu/LBias, %StatisticallySignificant, 95 %LevelReagent Water4.0 4.11 + 2.75 no2.0 2.06 + 3.0 no0.4 0.46 + 15.0 yesWater or Waste Water4.0 4.03 + 0.75 no2.0 2.02 + 1.0 no0.4 0.41 + 2.5 noD 1688 07316.2 This test method is applicable in the range from 50 to500 g/L of copper. The range may be e
49、xtended to concentra-tions greater than 500 g/L by dilution of the sample.16.3 Collaborative test data were obtained on reagent water,river water, tap water, 50 % artificial sea water, and syntheticNaCl brine (50 000 mg/L). The information on precision andbias may not apply to other waters.17. Summary of Test Method17.1 Copper is determined by atomic absorption spectro-photometry. The element, either dissolved or total recoverable,is chelated with pyrrolidine dithiocarbamic acid and extractedwith chloroform. The extract is evaporated to dryness,
