ASTM D4839-03(2017) Standard Test Method for Total Carbon and Organic Carbon in Water by Ultraviolet, or Persulfate Oxidation, or Both, and Infrared Detection.pdf

1、Designation: D4839 03 (Reapproved 2017)Standard Test Method forTotal Carbon and Organic Carbon in Water by Ultraviolet, orPersulfate Oxidation, or Both, and Infrared Detection1This standard is issued under the fixed designation D4839; the number immediately following the designation indicates the ye

2、ar oforiginal adoption or, in the case of revision, 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 This test method covers the determination of totalcarb

3、on (TC), inorganic carbon (IC), and total organic carbon(TOC) in water, wastewater, and seawater in the range from 0.1mg/L to 4000 mg/L of carbon.1.2 This test method was used successfully with reagentwater spiked with sodium carbonate, acetic acid, and pyridine.It is the users responsibility to ens

4、ure the validity of this testmethod for waters of untested matrices.1.3 This test method is applicable only to carbonaceousmatter in the sample that can be introduced into the reactionzone. The syringe needle or injector opening size generallylimit the maximum size of particles that can be so introd

5、uced.1.4 In addition to laboratory analyses, this test method maybe applied to stream monitoring.1.5 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.6 This standard does not purport to address all of thesafety concerns, if any

6、, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.7 This international standard was developed in accor-dance with internationa

7、lly recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D1129 Termin

8、ology Relating to WaterD1192 Guide for Equipment for Sampling Water and Steamin Closed Conduits (Withdrawn 2003)3D1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3370 Practices for Sampling Water from Clos

9、ed ConduitsD4129 Test Method for Total and Organic Carbon in Waterby High Temperature Oxidation and by CoulometricDetectionD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water Analysis3. Terminology3.1 Definitions:3.1.1 For definitions of terms used in this st

10、andard, refer toTerminology D1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 inorganic carbon (IC), ncarbon in the form ofcarbon dioxide, carbonate ion, or bicarbonate ion.3.2.2 refractory material, nthat which cannot be oxidizedcompletely under the test method conditions.3.2.3 total c

11、arbon (TC), nthe sum of IC and TOC.3.2.4 total organic carbon (TOC), ncarbon in the form oforganic compounds.4. Summary of Test Method4.1 FundamentalsCarbon can occur in water as an inor-ganic and organic compound. This test method can be used to1This test method is under the jurisdiction of ASTM Co

12、mmittee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved Dec. 15, 2017. Published December 2017. Originallyapproved in 1988. Last previous edition approved in 2011 as D4839 03 (2011).DOI: 10.1520/D4839-

13、03R17.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard

14、is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principle

15、s for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1make independent measurements of IC, TOC, and TC, and canalso determine IC by the difference of TC and TOC, and TOCas the difference of TC a

16、nd IC.4.2 The essentials of this test method are: (a) removal of IC,if desired, by acidification of the sample and sparging bycarbon-free gas; (b) conversion of remaining carbon to CO2byaction of persulfate, aided either by elevated temperature orultraviolet (UV) radiation; (c) detection of CO2that

17、is sweptout of the reactor by a gas stream; and (d) conversion ofdetector signal to a display of carbon concentration in mg/L. Adiagram of suitable apparatus is given in Fig. 1.5. Significance and Use5.1 This test method is used for determination of the carboncontent of water from a variety of natur

18、al, domestic, andindustrial sources. In its most common form, this test methodis used to measure organic carbon as a means of monitoringorganic pollutants in industrial wastewater. These measure-ments are also used in monitoring waste treatment processes.5.2 The relationship of TOC to other water qu

19、ality param-eters such as chemical oxygen demand (COD) and total oxygendemand (TOD) is described in the literature.46. Interferences and Limitations6.1 The oxidation of dissolved carbon to CO2is broughtabout at relatively low temperatures by the chemical action ofreactive species produced by hot or

20、UV-irradiated persulfateions. Even if oxygen is used as the sparging gas, it makes amuch lower contribution to oxidation than in high-temperature(combustive) systems. Not all suspended or refractory materialmay be oxidized under these conditions; analysts should takesteps to determine what recovery

21、is being obtained. This maybe done by several methods: (a) by monitoring reactionprogress to verify that oxidation has been completed; (b)byrerunning the sample under more vigorous reaction conditions;(c) by analyzing the sample by an alternative method, such asTest Method D4129, known to result in

22、full recovery; or (d)byspiking samples with known refractories and determiningrecovery.6.2 Chloride ion tends to interfere with oxidative reactionmechanisms in this test method, prolonging oxidation timesand sometimes preventing full recovery. Follow manufactur-ers instructions for dealing with this

23、 problem. See AppendixX1 for supporting data.6.3 Homogenizing or sparging of a sample, or both, maycause loss of purgeable organic compounds, thus yielding avalue lower than the true TOC level. (For this reason, suchmeasurements are sometimes known as nonpurgeable organiccarbon (NPOC). The extent an

24、d significance of such lossesmust be evaluated on an individual basis. This may be done bycomparing the TOC by difference (TC-IC) with the direct TOCfigure, that is, that obtained from a sparged sample. Thedifference, if any, between these TOC figures representspurgeable organic carbon (POC) lost du

25、ring sparging.Alternatively, direct measurement of POC can be made duringsparging, using optional capabilities of the analyzer.6.4 Note that error will be introduced when the method ofdifference is used to derive a relatively small level from twolarge levels. For example, a ground water high in IC a

26、nd lowin TOC will give a poorer TOC value as (TC-IC) than by directmeasurement.7. Apparatus7.1 Homogenizing ApparatusA household blender is gen-erally satisfactory for homogenizing immiscible phases inwater.7.2 Sampling DevicesMicrolitre-to-millilitre syringes aretypically required for this test met

27、hod. Alternatives includemanually operated or automatically operated sampling valves.Sampling devices with inside diameters as small as 0.15 mmmay be used with samples containing little or no particulatematter. Larger inside dimensions such as 0.4 mm will berequired for samples with particulate matt

28、er.NOTE 1See 6.1 concerning oxidation of particulate matter.7.3 Apparatus for Carbon DeterminationThis instrumentconsists of reagent and sample introduction mechanism, agas-sparged reaction vessel, a gas demister or dryer, or both, anoptional CO2trap, a CO2-specific infrared detector, a controlsyste

29、m, and a display. Fig. 1 shows a diagram of such anarrangement.7.3.1 Sparging requires an inert vessel with a capacity of atleast double the sample size with provision for sparging with50 to 100 mL/min of carbon free gas. This procedure willremove essentially all IC in 2 to 10 min, depending on desi

30、gn.7.3.2 OxidationThe reaction assembly contains reagentand sample introduction devices, and a reactor vessel withsparging flow of carbon-free gas. The vessel may be heated byan external source, and may contain a UV lamp. The reactionvessel and sparging vessel (see 6.3) may be combined.7.3.3 Gas Con

31、ditioningThe gas passing from the reactoris dried, and the CO2produced is either trapped and later4Handbook for Monitoring Industrial Wastewater, Section 5.3, U.S. Environ-ment Protection Agency, August 1973, pp. 512.FIG. 1 Diagram of ApparatusD4839 03 (2017)2released to the detector, or routed dire

32、ctly to the detectorthrough a chlorine-removing scrubber.7.3.4 DetectorThe CO2in the gas stream is detected by aCO2-specific nondispersive infrared (NDIR) detector.7.3.5 Presentation of ResultsThe NDIR detector output isrelated to stored calibration data and then displayed as milli-grams of carbon p

33、er litre.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of the Committee onAnalytical Reagents of theAmerican Chemical Society,5wheresuch specifications are av

34、ailable. Other grades may be used,provided it is first ascertained that the reagent is of sufficientpurity to permit its use without lessening the accuracy of thedetermination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Spe

35、cification D1193, Type I or Type II. The indicatedspecification does not actually specify inorganic carbon ororganic carbon levels. These levels can affect the results of thistest method, especially at progressively lower levels of thecarbon content in the samples to be measured. Where inorganiccarb

36、on in reagent water is significant, CO2-free water may beprepared from reagent water by acidifying to pH 2, thensparging with fritted-glass sparger using CO2-free gas (timewill depend on volume and gas flow rate, and should bedetermined by test). Alternatively, if the carbon contribution ofthe reage

37、nt water is known accurately, its effect may beallowed for in preparation of standards and other solutions.CO2-free water should be protected from atmospheric contami-nation. Glass containers are required for storage of water andstandard solutions.8.3 AcidVarious concentrated acids may be used forac

38、idification of samples and of the oxidizing reagent. Acidssuch as phosphoric (sp gr 1.69), nitric (sp gr 1.42), or sulfuric(sp gr 1.84) are suitable for most applications. Sulfuric acidshould be used in the form of a 1 + 1 dilution, for safetyreasons. Hydrochloric acid is not recommended.8.4 Organic

39、 Carbon, Standard Solution (2000 mg/L)Choose a water-soluble, stable reagent grade compound, suchas benzoic acid or anhydrous potassium hydrogen phthalate(KHC8H4O4). Calculate the weight of compound required tomake 1 L of organic carbon standard solution; for example,KHC8H4O4= 0.471 g of carbon per

40、gram, so one litre of 2 g/Lof standard requires 2/0.471, or 4.25, grams of KHP. Dissolvethe required amount of standard in some CO2-free water in a1-L volumetric flask, add 1 mL of acid, and dilute to volume.This stock solution, or dilutions of it, may be used to calibrateand test performance of the

41、 carbon analyzer.8.5 Persulfate SolutionPrepare by dissolving the appro-priate weight of potassium or sodium persulfate in 1 Lof water,to produce the concentration specified by the instrumentmanufacturer. If specified, add 1 mL of phosphoric acid (sp gr1.69) and mix well. Store in a cool, dark place

42、. Recipes for thisreagent solution may be modified by manufacturers to meet theneeds of specific applications, for example, high chloridesamples.8.6 Gas SupplyA gas free of CO2and of organic matter isrequired. Use a purity as specified by the equipment manufac-turer. The use of oxygen is preferred f

43、or the UV-persulfatemethod, and nitrogen or helium is preferred if a CO2trap isused between reactor and detector.9. Sampling and Sample Preservation9.1 Collect the sample in accordance with Guide D1192 andPractices D3370.9.2 To preserve samples for this analysis, store samples inglass at 4C. To aid

44、preservation, acidify the samples to a pHof 2. It should be noted that acidification will enhance loss ofinorganic carbon. If the purgeable organic fraction is important,fill the sample bottles to overflowing with a minimum ofturbulence and cap them using a fluoropolymer-lined cap,without headspace.

45、9.3 For monitoring of waters containing solids or immis-cible liquids that are to be injected into the reaction zone, usea mechanical homogenizer or ultrasonic disintegrator. Filteringor screening may be necessary after homogenization to rejectparticle sizes that are too large for injection. Volatil

46、e organicsmay be lost. See 6.3.9.4 For wastewater streams where carbon concentrations aregreater than the desired range of instrument operation, dilutethe samples as necessary.10. Instrument Operation10.1 Follow the manufacturers instructions for instrumentwarm-up, gas flows, and liquid flows.11. Ca

47、libration11.1 Use the stock solution of 2000 mg/L of carbon, andvarious dilutions of it, for calibration.NOTE 2Dilutions should be made with CO2-free water (see 8.2).11.2 Calibration protocols may vary with equipment manu-facturers. However, in general, calibrate the instrument inaccordance with the

48、 manufacturers instructions, and usestandards to verify such calibration in the specific range ofinterest for actual measurements. Plots of standard concentra-tion versus instrument reading may be used for calibration or toverify linearity of response.11.3 Establish instrument blank according to the

49、 manufac-turers instructions.12. Procedure12.1 Mix or blend each sample thoroughly and carry out anynecessary dilution to bring the carbon content within range ofthe instrument.5Reagent 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, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Roc