ASTM D4129-98(2003)
(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
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 20000 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 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.
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An American National Standard
Designation:D 4129–98 (Reapproved 2003)
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 D 4129; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope D 513 Test Methods for Total and Dissolved Carbon Diox-
ide in Water
1.1 This test method covers the determination of total and
D 1129 Terminology Relating to Water
organic carbon in water and waste water, including brackish
D 1193 Specification for Reagent Water
watersandbrinesintherangefrom2to20 000mg/L.Thistest
D 3370 Practices for SamplingWater from Closed Conduits
method has the advantages of a wide range of concentration
D 3856 Guide for Good Laboratory Practices in Laborato-
which may be determined without sample dilution and the
ries Engaged in the Sampling and Analysis of Water
provision for boat or capillary introduction of samples contain-
D 4210 Practice for Interlaboratory Quality Control Proce-
ing sediments and particulate matter where syringe injection is
dures and a Discussion on Reporting Low-Level Data
inappropriate.
D 5789 Practice for Writing Quality Control Specifications
1.2 This procedure is applicable only to that carbonaceous
for Standard Test Methods for Organic Constituents
matter in the sample that can be introduced into the reaction
zone. When syringe injection is used to introduce samples into
3. Terminology
thecombustionzone,thesyringeneedleopeningsizelimitsthe
3.1 Definitions—For definitions of terms used in this test
maximum size of particles that can be present in samples.
method, refer to Terminology D 1129.
Sludge and sediment samples must be homogenized prior to
sampling with a micropipetor or other appropriate sampler and
4. Summary of Test Method
ladle introduction into the combustion zone is required.
4.1 The sample is homogenized or diluted, or both, as
1.3 The precision and bias information reported in this test
necessary. If the sample does not contain suspended particles
method was obtained in collaborative testing that included
or high-salt level a 0.200-mL portion is injected into the
waters of the following types: distilled, deionized, potable,
reactionzone.Forsamplescontainingsolidsorhighsaltlevels,
natural, brine, municipal and industrial waste, and water
portions are placed in combustion boats containing tungsten
derived from oil shale retorting. Since the precision and bias
trioxide (WO ) or quartz capillaries and introduced into the
information reported may not apply to waters of all matrices, it
reaction zone using a ladle. In the reaction zone the heat,
is the user’s responsibility to ensure the validity of this test
oxidation catalyst and oxygen atmosphere convert carbon-
method on samples of other matrices.
aceous matter to carbon dioxide (CO ).The oxygen gas stream
1.4 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-
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.
4.2 Carbon dioxide is liberated from carbonates as well as
2. Referenced Documents
from organic matter under the reaction conditions. Organic
2.1 ASTM Standards:
carbon is determined by difference between the total carbon
and the inorganic carbon determined separately or by acidify-
ing a portion of the sample to a pH of 2 or less and sparging
This test method is under the jurisdiction of ASTM Committee D19 on Water
with carbon dioxide-free gas to remove carbonates, bicarbon-
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
Organic Substances in Water. ates, and dissolved carbon dioxide prior to total carbon
Current edition approved Dec. 10, 1998. Published March 1999. Originally
determination. To determine organic carbon by difference the
approved in 1982. Last previous edition approved in 1988 as D 4129 – 88 (1993).
inorganic carbon is determined by acid release of carbon
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. Withdrawn.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D 4129–98 (2003)
FIG. 1 Total Carbon and TOC Apparatus
dioxide from a portion of the sample or other methods as given 5.5 The relationship of TOC to other water quality param-
in Test Methods D 513. For discussion of the limitations and eters such as COD and BOD is described in the literature.
guidelines for the use of the sparge technique see 5.4 and the
6. Interferences
paper by Van Hall.
6.1 Any acidic or basic gas formed in the oxidation of the
4.3 Because of the various properties of carbon-containing
sample and not removed by the scrubbers will interfere with
compounds in water, any preliminary treatment of a sample
the test. Potentially interfering gases that are removed by the
prior to injection dictates a definition of the carbon measured.
scrubbers include hydrogen sulfide (H S), hydrogen chloride
Filtration of the sample prior to injection will limit the carbon 2
(HCl), hydrogen bromide (HBr), hydrogen iodide (HI), sulfur
measuredtodissolvedcarbonatesanddissolvedorganicmatter.
dioxide (SO ), sulfur trioxide (SO ) free halogens, halogen
2 3
Homogenizing permits determination of the carbon in in-
oxides, and nitrogen oxides. Hydrogen fluoride (HF) may be
soluble carbonates and insoluble organic materials.
removedbybubblingthegasstreamthroughwaterinthewater
vapor condenser.
5. Significance and Use
6.2 The capacity of the scrubbers for potentially interfering
5.1 This test method is necessary because of the need for
gases may vary with the type of samples being analyzed. If the
rapid reliable tests for carbonaceous material in waters and scrubber capacity is exceeded it can be recognized by the
sediments. titrationcontinuingbeyondthenormalanalysistimeatahigher
rate than the blank and high results for known carbon content
5.2 It is used for determining the concentration of organic
standards as well as by appearance changes in the scrubbers. If
carbon in water that comes from a variety of natural, domestic,
the scrubber capacity is exceeded during an analysis the
and industrial sources. Typically, these measurements are used
scrubbers should be replaced and the analysis repeated.
to monitor organic pollutants in domestic and industrial waste
Samples containing all concentrations of the potentially inter-
water.
fering species can be analyzed if the analyst uses great care to
5.3 When a sample is homogenized so that particulate,
ensure that the scrubbers are and remain effective for his
immiscible phases, and dissolved carbon from both organic
samples. The frequency of replacing the scrubbers will depend
and inorganic sources is determined, the measurement is called
on the nature of the samples.
total carbon (TC). When inorganic carbon response is elimi-
nated by removing the dissolved CO prior to the analysis or 7. Apparatus
the dissolved CO concentration subtracted from the total
7.1 Apparatus for total carbon, organic carbon, and inor-
carbon concentration, the measurement is called total organic
ganic carbon determinations—combustion furnace with gas
carbon (TOC). When particulates and immiscible phases are
supply, gas purification train, flow control, acid reaction train,
removed prior to analysis the measurement is called dissolved
and carbon dioxide coulometer. Fig. 1 and Fig. 2 show block
carbon (DC), or dissolved organic carbon (DOC) if inorganic
diagrams of the apparatus.
carbon response has been eliminated.
7.2 Sampling Devices— A spring-loaded .200-mL syringe
(carbon analyzer syringe) having an all metal tip and a 50 mm
5.4 Homogenizing or sparging of a sample, or both, may
cause loss of volatile organics, thus yielding a negative error.
Theextentandsignificanceofsuchlossesmustbeevaluatedon
Van Hall, C. E., Barth, D., and Stenger,V.A., “Elimination of Carbonates from
an individual basis. If significant quantities of volatile carbon-
Aqueous Solutions Prior to Organic Carbon Determinations,” Analytical Chemistry,
aceous materials are present or may be present in samples
Vol 37, 1965, pp. 769–771.
organiccarbonshouldbedeterminedbythedifferencebetween
Handbook for Monitoring Industrial Wastewater, U.S. Environment Protection
thetotalcarbonandtheinorganiccarbonconcentrations.When Agency, August 1973, pp. 5–10 to 5–12.
Instruments marketed by Coulometrics, Inc., a subsidiary of UIC Inc., P.O. Box
organic carbon determined both by difference and by sparging
563, Joliet, IL, 60434, or an equivalent, have been found satisfactory.
agree it is acceptable to determine organic carbon by sparging 7
Syringes manufactured by Hamilton Co., P.O. Box 10030, Reno, NV89510, or
for similar samples. an equivalent, have been found satisfactory for this purpose.
D 4129–98 (2003)
FIG. 2 CO Evolution Apparatus
long, 0.5-mm inside diameter needle with a square end is ment manufacturer. Fig. 1 illustrates the flow diagram and
recommended for water samples containing little or no particu- names the reagents used.
late matter. 8.5 Carbon Dioxide Coulometer Reagents—Cell solutions
7.3 Homogenizing Apparatus—A household blender with to absorb CO from the gas stream and convert it to a titratable
glass mixing chamber is generally satisfactory for homogeniz- acid and permit 100 % efficient coulometric titration.
ing immiscible phases in water. 8.6 Acid—Various acids may be used for acidification of
samples. Hydrochloric acid is recommended. Phosphoric and
8. Reagents
sulfuric acids are suitable if they do not cause materials to
precipitate from the sample. Nitric acid is not recommended
8.1 Purity of Reagents—Reagent grade chemicals shall be
because it may cause premature oxidation of organics in the
used in all tests. Unless otherwise indicated, it is intended that
sample.
all reagents shall conform to the specifications of the commit-
8.7 Organic Carbon Standard Solutions—Although the
tee onAnalytical Reagents of theAmerican Chemical Society.
method does not require sample standardization, proper opera-
Other grades may be used provided it is first ascertained that
tion of the instrument should be confirmed by injection of
the reagent is of sufficiently high purity to permit its use
standards of similar composition and concentration to the
without lessening the accuracy of the determination.
unknown.Standardsshouldbestablewatersolublecompounds
8.2 Purity of Water— Unless otherwise indicated, reference
such as KHP or benzoic acid of suitable purity.
towatershallbeunderstoodtomeanreagentwaterconforming
to the Specification D 1193, Type II. Where specified, carbon
9. Hazards
dioxide-free water is to be prepared by boiling distilled water
in a conical flask for 20 min. The boiled water is cooled in the
9.1 Injection of samples containing over 25 000 mg/LTOC
flask stoppered with a one-hole rubber stopper fitted to a soda or 0.5 mL water may cause explosion of the combustion tube.
lime-Ascarite drying tube. For large (10 to 20 L) volumes of
10. Sampling
carbon dioxide-free water, the absorbed carbon dioxide may be
removed by inserting a fritted-glass gas-dispersion tube to the
10.1 Collect the sample in accordance with Practices
bottom of the container and vigorously bubbling nitrogen
D 3370 or other applicable ASTM method(s).
through the water for at least 1 h. Carbon dioxide-free water
10.2 Preservation:
may be stored if properly protected from atmospheric contami-
10.2.1 To preserve samples for this analysis, store or ship
nation.
samplesinglassatorbelow4°C.Caution—Headspaceinthe
sample bottle or freezing the sample may contribute to the loss
NOTE 1—Glass containers are preferred for the storage of reagent water
of volatile organics from some samples.
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
10.3 For monitoring of waters containing solids or immis-
laboratory air. As volumes of fluid are withdrawn from the container, the
cible liquids of interest, use a mechanical homogenizer or
replacement air should be passed through a drying tube filled with equal
ultrasonic disintegrator to homogenize samples.
parts of 8 to 20-mesh soda lime, oxalic acid, and 4 to 8-mesh anhydrous
10.4 For waste water streams where carbon concentrations
calcium chloride, each product being separated from the other by a
are greater than the desired range of instrument operation,
glass-wool plug.
provide on-stream dilution of the sample if possible.
8.3 Gas Supply—Use oxygen of at least 99.6 % purity.
10.5 A1.1 gives additional guidelines for preparing heavily
8.4 Scrubber Tubes and Catalyst Packings as well as in-
contaminated water samples when using the sparge technique.
structions for their preparation are available from the equip-
10.6 A1.2 gives additional guidelines for samples contain-
ing solids and immiscible liquids.
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. Pharmaceutical Convention, Inc. (USPC), Rockville, hydroxethylcarbamic acid that is titrated coulometrically using a color indicator for
MD. end-point detection.
D 4129–98 (2003)
if the result is to be given in mg/L when samples are weighed into
11. Calibration and Standardization
combus
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