ASTM D4129-05(2013)
(Test Method)Standard Test Method for Total and Organic Carbon in Water by High Temperature Oxidation and by Coulometric Detection
Standard Test Method for Total and Organic Carbon in Water by High Temperature Oxidation and by Coulometric Detection
SIGNIFICANCE AND USE
5.1 This test method is necessary because of the need for rapid reliable tests for carbonaceous material in waters and sediments.
5.2 It is used for determining the concentration of organic carbon in water that comes from a variety of natural, domestic, and industrial sources. Typically, these measurements are used to monitor organic pollutants in domestic and industrial waste water.
5.3 When a sample is homogenized so that particulate, immiscible phases, and dissolved carbon from both organic and inorganic sources is determined, the measurement is called total carbon (TC). When inorganic carbon response is eliminated by removing the dissolved CO2 prior to the analysis or the dissolved CO2 concentration subtracted from the total carbon concentration, the measurement is called total organic carbon (TOC). When particulates and immiscible phases are removed prior to analysis the measurement is called dissolved carbon (DC), or dissolved organic carbon (DOC) if inorganic carbon response has been eliminated.
5.4 Homogenizing or sparging of a sample, or both, may cause loss of volatile organics, thus yielding a negative error. The extent and significance of such losses must be evaluated on an individual basis. If significant quantities of volatile carbonaceous materials are present or may be present in samples organic carbon should be determined by the difference between the total carbon and the inorganic carbon concentrations. When organic carbon determined both by difference and by sparging agree it is acceptable to determine organic carbon by sparging for similar samples.
5.5 The relationship of TOC to other water quality parameters such as COD and BOD is described in the literature.5
SCOPE
1.1 This test method covers the determination of total and organic carbon in water and waste water, including brackish waters and brines in the range from 2 to 20 000 mg/L. This test method has the advantages of a wide range of concentration which may be determined without sample dilution and the provision for boat or capillary introduction of samples containing sediments and particulate matter where syringe injection is inappropriate.
1.2 This procedure is applicable only to that carbonaceous matter in the sample that can be introduced into the reaction zone. When syringe injection is used to introduce samples into the combustion zone, the syringe needle opening size limits the maximum size of particles that can be present in samples. Sludge and sediment samples must be homogenized prior to sampling with a micropipetor or other appropriate sampler and ladle introduction into the combustion zone is required.
1.3 The precision and bias information reported in this test method was obtained in collaborative testing that included waters of the following types: distilled, deionized, potable, natural, brine, municipal and industrial waste, and water derived from oil shale retorting. Since the precision and bias information reported may not apply to waters of all matrices, it is the user's responsibility to ensure the validity of this test method on samples of other matrices.
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific precautionary statements, see 9.1 and 10.2.1.
General Information
Relations
Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D4129 − 05 (Reapproved 2013)
Standard Test Method for
Total and Organic Carbon in Water by High Temperature
Oxidation and by Coulometric Detection
This standard is issued under the fixed designation D4129; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
1.1 This test method covers the determination of total and 2.1 ASTM Standards:
organic carbon in water and waste water, including brackish D513TestMethodsforTotalandDissolvedCarbonDioxide
watersandbrinesintherangefrom2to20 000mg/L.Thistest in Water
method has the advantages of a wide range of concentration D1129Terminology Relating to Water
which may be determined without sample dilution and the D1193Specification for Reagent Water
provisionforboatorcapillaryintroductionofsamplescontain- D3370Practices for Sampling Water from Closed Conduits
ing sediments and particulate matter where syringe injection is D3856Guide for Management Systems in Laboratories
inappropriate. Engaged in Analysis of Water
D4210Practice for Intralaboratory Quality Control Proce-
1.2 This procedure is applicable only to that carbonaceous
dures and a Discussion on Reporting Low-Level Data
matter in the sample that can be introduced into the reaction
(Withdrawn 2002)
zone.When syringe injection is used to introduce samples into
D5789Practice for Writing Quality Control Specifications
thecombustionzone,thesyringeneedleopeningsizelimitsthe
for Standard Test Methods for Organic Constituents
maximum size of particles that can be present in samples.
(Withdrawn 2002)
Sludge and sediment samples must be homogenized prior to
sampling with a micropipetor or other appropriate sampler and
3. Terminology
ladle introduction into the combustion zone is required.
3.1 Definitions—For definitions of terms used in this test
1.3 The precision and bias information reported in this test
method, refer to Terminology D1129.
method was obtained in collaborative testing that included
waters of the following types: distilled, deionized, potable,
4. Summary of Test Method
natural, brine, municipal and industrial waste, and water
4.1 The sample is homogenized or diluted, or both, as
derived from oil shale retorting. Since the precision and bias
necessary. If the sample does not contain suspended particles
informationreportedmaynotapplytowatersofallmatrices,it
or high-salt level a 0.200-mL portion is injected into the
is the user’s responsibility to ensure the validity of this test
reactionzone.Forsamplescontainingsolidsorhighsaltlevels,
method on samples of other matrices.
portions are placed in combustion boats containing tungsten
1.4 The values stated in SI units are to be regarded as
trioxide (WO ) or quartz capillaries and introduced into the
standard. No other units of measurement are included in this
reaction zone using a ladle. In the reaction zone the heat,
standard.
oxidation catalyst and oxygen atmosphere convert carbona-
ceous matter to carbon dioxide (CO ). The oxygen gas stream
1.5 This standard does not purport to address all of the
sweeps the gaseous reaction products through a series of
safety concerns, if any, associated with its use. It is the
scrubbers for potentially interfering gases and then to the
responsibility of the user of this standard to establish appro-
absorption/titration cell. The CO is determined by automatic
priate safety and health practices and determine the applica- 2
coulometric titration. Calibration by testing known carbon
bility of regulatory limitations prior to use. For specific
content standards is not required, however, standards are
precautionary statements, see 9.1 and 10.2.1.
analyzed periodically to confirm proper operation.
1 2
This test method is under the jurisdiction ofASTM Committee D19 on Water For referenced ASTM standards, visit the ASTM website, www.astm.org, or
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Organic Substances in Water. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved May 1, 2013. Published May 2013. Originally the ASTM website.
approved in 1982. Last previous edition approved in 2012 as D4129–05 (2012). The last approved version of this historical standard is referenced on
DOI: 10.1520/D4129-05R13. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4129 − 05 (2013)
4.2 Carbon dioxide is liberated from carbonates as well as thetotalcarbonandtheinorganiccarbonconcentrations.When
from organic matter under the reaction conditions. Organic organic carbon determined both by difference and by sparging
carbon is determined by difference between the total carbon agree it is acceptable to determine organic carbon by sparging
and the inorganic carbon determined separately or by acidify- for similar samples.
ing a portion of the sample to a pH of 2 or less and sparging
5.5 The relationship of TOC to other water quality param-
with carbon dioxide-free gas to remove carbonates,
eters such as COD and BOD is described in the literature.
bicarbonates, and dissolved carbon dioxide prior to total
6. Interferences
carbon determination. To determine organic carbon by differ-
ence the inorganic carbon is determined by acid release of
6.1 Any acidic or basic gas formed in the oxidation of the
carbon dioxide from a portion of the sample or other methods
sample and not removed by the scrubbers will interfere with
as given in Test Methods D513. For discussion of the limita-
the test. Potentially interfering gases that are removed by the
tions and guidelines for the use of the sparge technique see 5.4
scrubbers include hydrogen sulfide (H S), hydrogen chloride
and the paper by Van Hall.
(HCl), hydrogen bromide (HBr), hydrogen iodide (HI), sulfur
dioxide (SO ), sulfur trioxide (SO ) free halogens, halogen
4.3 Because of the various properties of carbon-containing
2 3
oxides, and nitrogen oxides. Hydrogen fluoride (HF) may be
compounds in water, any preliminary treatment of a sample
prior to injection dictates a definition of the carbon measured. removedbybubblingthegasstreamthroughwaterinthewater
vapor condenser.
Filtration of the sample prior to injection will limit the carbon
measuredtodissolvedcarbonatesanddissolvedorganicmatter.
6.2 The capacity of the scrubbers for potentially interfering
Homogenizing permits determination of the carbon in in-
gasesmayvarywiththetypeofsamplesbeinganalyzed.Ifthe
soluble carbonates and insoluble organic materials.
scrubber capacity is exceeded it can be recognized by the
titrationcontinuingbeyondthenormalanalysistimeatahigher
5. Significance and Use
rate than the blank and high results for known carbon content
5.1 This test method is necessary because of the need for
standardsaswellasbyappearancechangesinthescrubbers.If
rapid reliable tests for carbonaceous material in waters and
the scrubber capacity is exceeded during an analysis the
sediments.
scrubbers should be replaced and the analysis repeated.
Samples containing all concentrations of the potentially inter-
5.2 It is used for determining the concentration of organic
fering species can be analyzed if the analyst uses great care to
carboninwaterthatcomesfromavarietyofnatural,domestic,
ensure that the scrubbers are and remain effective for his
and industrial sources. Typically, these measurements are used
samples.The frequency of replacing the scrubbers will depend
to monitor organic pollutants in domestic and industrial waste
on the nature of the samples.
water.
5.3 When a sample is homogenized so that particulate,
7. Apparatus
immiscible phases, and dissolved carbon from both organic
7.1 Apparatus for total carbon, organic carbon, and inor-
andinorganicsourcesisdetermined,themeasurementiscalled
ganic carbon determinations—combustion furnace with gas
total carbon (TC). When inorganic carbon response is elimi-
supply, gas purification train, flow control, acid reaction train,
nated by removing the dissolved CO prior to the analysis or
2 6
and carbon dioxide coulometer. Fig. 1 and Fig. 2 show block
the dissolved CO concentration subtracted from the total
diagrams of the apparatus.
carbon concentration, the measurement is called total organic
7.2 Sampling Devices—A spring-loaded .200-mL syringe
carbon (TOC). When particulates and immiscible phases are
(carbon analyzer syringe) having an all metal tip and a 50 mm
removed prior to analysis the measurement is called dissolved
long, 0.5-mm inside diameter needle with a square end is
carbon (DC), or dissolved organic carbon (DOC) if inorganic
recommendedforwatersamplescontaininglittleornoparticu-
carbon response has been eliminated.
late matter.
5.4 Homogenizing or sparging of a sample, or both, may
7.3 Homogenizing Apparatus—A household blender with
cause loss of volatile organics, thus yielding a negative error.
glass mixing chamber is generally satisfactory for homogeniz-
Theextentandsignificanceofsuchlossesmustbeevaluatedon
ing immiscible phases in water.
an individual basis. If significant quantities of volatile carbo-
naceous materials are present or may be present in samples
organiccarbonshouldbedeterminedbythedifferencebetween Handbook for Monitoring Industrial Wastewater, U.S. Environment Protection
Agency, August 1973, pp. 5–10 to 5–12.
InstrumentsmarketedbyCoulometrics,Inc.,asubsidiaryofUICInc.,P.O.Box
VanHall,C.E.,Barth,D.,andStenger,V.A.,“EliminationofCarbonatesfrom 563, Joliet, IL, 60434, or an equivalent, have been found satisfactory.
AqueousSolutionsPriortoOrganicCarbonDeterminations,” Analytical Chemistry, SyringesmanufacturedbyHamiltonCo.,P.O.Box10030,Reno,NV89510,or
Vol 37, 1965, pp. 769–771. an equivalent, have been found satisfactory for this purpose.
D4129 − 05 (2013)
FIG. 1 Total Carbon and TOC Apparatus
FIG. 2 CO Evolution Apparatus
replacement air should be passed through a drying tube filled with equal
8. Reagents
parts of 8 to 20-mesh soda lime, oxalic acid, and 4 to 8-mesh anhydrous
8.1 Purity of Reagents—Reagent grade chemicals shall be
calcium chloride, each product being separated from the other by a
used in all tests. Unless otherwise indicated, it is intended that glass-wool plug.
all reagents shall conform to the specifications of the commit-
8.3 Gas Supply—Use oxygen of at least 99.6% purity.
teeonAnalyticalReagentsoftheAmericanChemicalSociety.
8.4 Scrubber Tubes and Catalyst Packings as well as
Other grades may be used provided it is first ascertained that
instructions for their preparation are available from the equip-
the reagent is of sufficiently high purity to permit its use
ment manufacturer. Fig. 1 illustrates the flow diagram and
without lessening the accuracy of the determination.
names the reagents used.
8.2 Purity of Water—Unless otherwise indicated, reference
towatershallbeunderstoodtomeanreagentwaterconforming 8.5 Carbon Dioxide Coulometer Reagents—Cell solutions
to the Specification D1193, Type I. Other reagent water types toabsorbCO fromthegasstreamandconvertittoatitratable
may be used, provided it is first ascertained that the water is of acid and permit 100% efficient coulometric titration.
sufficiently high purity to permit its use without adversely
8.6 Acid—Various acids may be used for acidification of
affecting the precision and bias of the test method. Type II
samples. Hydrochloric acid is recommended. Phosphoric and
water was specified at the time of round robin testing of this
sulfuric acids are suitable if they do not cause materials to
test method. If necessary, carbon dioxide-free water is to be
precipitate from the sample. Nitric acid is not recommended
preparedbyboilingdistilledwaterinaconicalflaskfor20min.
because it may cause premature oxidation of organics in the
The boiled water is cooled in the flask stoppered with a
sample.
one-hole rubber stopper fitted to a soda lime-Ascarite drying
8.7 Organic Carbon Standard Solutions—Although the
tube. For large (10 to 20 L) volumes of carbon dioxide-free
water, the absorbed carbon dioxide may be removed by method does not require sample standardization, proper opera-
tion of the instrument should be confirmed by injection of
insertingafritted-glassgas-dispersiontubetothebottomofthe
standards of similar composition and concentration to the
container and vigorously bubbling nitrogen through the water
for at least 1 h. Carbon dioxide-free water may be stored if unknown.Standardsshouldbestablewatersolublecompounds
such as KHP or benzoic acid of suitable purity.
properly protected from atmospheric contamination.
NOTE1—Glasscontainersarepreferredforthestorageofreagentwater
9. Hazards
and most standard solutions. It is necessary to provide protection against
changes in quality due to the absorption of gases or water vapor from the
9.1 Injectionofsamplescontainingover25 000mg/LTOC
laboratory air.As volumes of fluid are withdrawn from the container, the
or 0.5 mL water may cause explosion of the combustion tube.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory Satisfactory reagents available from Coulometrics, Inc., a subsidiary of UIC
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia Inc., P.O. Box 563, Joliet, IL, 60434 use ethanolamine to absorb CO forming
and National Formulary,U.S.PharmaceuticalConvention,Inc.(USPC),Rockville, hydroxethylcarbamic acid that is titrated coulometrically using a color indicator for
MD. end-point detection.
D4129 − 05 (2013)
10. Sampling 12.4 Ladle Introduction of Samples:
12.4.1 When a micropipet can be used with the sample,
10.1 CollectthesampleinaccordancewithPracticesD3370
place 0.200 mL of the sample into a platinum boat or a
or other applicable ASTM method(s).
capillary tube containing approximately 20 mg of WO .
10.2 Preservation:
Position the boat (capillary) in the ladle and place the ladle in
10.2.1 To preserve samples for this analysis, store or ship
the cool portion of the combustion tube through the introduc-
samplesinglassatorbelow4°C. Caution—Headspaceinthe
tionport.Afterclosingtheintroductionport,allow60sforthe
samplebottleorfreezingthesamplemaycontributetotheloss
oxygen gas stream to sweep out air that ent
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