Total and Organic Carbon in Water by High Temperature Oxidation and by Coulometric Detection
Total and Organic Carbon in Water by High Temperature Oxidation and by Coulometric Detection
Total and Organic Carbon in Water by High Temperature Oxidation and by Coulometric Detection
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This test method is under the jurisdiction of ASTM Committee D19 on Water For referenced ASTM standards, visit the ASTM website, www.astm.org, or
and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for 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.
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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
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4.2 Carbon dioxide is liberated from carbonates as well as the total carbon and the inorganic carbon concentrations. 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.5
bicarbonates, and dissolved carbon dioxide prior to total
carbon determination. To determine organic carbon by differ- 6. Interferences
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 (H2S), hydrogen chloride
and the paper by Van Hall.4 (HCl), hydrogen bromide (HBr), hydrogen iodide (HI), sulfur
4.3 Because of the various properties of carbon-containing dioxide (SO2), sulfur trioxide (SO3) free halogens, halogen
compounds in water, any preliminary treatment of a sample oxides, and nitrogen oxides. Hydrogen fluoride (HF) may be
prior to injection dictates a definition of the carbon measured. removed by bubbling the gas stream through water in the water
Filtration of the sample prior to injection will limit the carbon vapor condenser.
measured to dissolved carbonates and dissolved organic matter. 6.2 The capacity of the scrubbers for potentially interfering
Homogenizing permits determination of the carbon in in- gases may vary with the type of samples being analyzed. If the
soluble carbonates and insoluble organic materials. scrubber capacity is exceeded it can be recognized by the
5. Significance and Use titration continuing beyond the normal analysis time at a higher
rate than the blank and high results for known carbon content
5.1 This test method is necessary because of the need for standards as well as by appearance changes in the scrubbers. 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.
5.2 It is used for determining the concentration of organic Samples containing all concentrations of the potentially inter-
carbon in water that comes from a variety of natural, domestic, fering species can be analyzed if the analyst uses great care to
and industrial sources. Typically, these measurements are used ensure that the scrubbers are and remain effective for his
to monitor organic pollutants in domestic and industrial waste samples. The frequency of replacing the scrubbers will depend
water. on the nature of the samples.
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-
and inorganic sources is determined, the measurement is called
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 CO2 prior to the analysis or
and carbon dioxide coulometer.6Fig. 1 and Fig. 2 show block
the dissolved CO2 concentration subtracted from the total
diagrams of the apparatus.
carbon concentration, the measurement is called total organic
carbon (TOC). When particulates and immiscible phases are 7.2 Sampling Devices— A spring-loaded .200-mL syringe7
removed prior to analysis the measurement is called dissolved (carbon analyzer syringe) having an all metal tip and a 50 mm
carbon (DC), or dissolved organic carbon (DOC) if inorganic long, 0.5-mm inside diameter needle with a square end is
carbon response has been eliminated. recommended for water samples containing little or no particu-
late matter.
5.4 Homogenizing or sparging of a sample, or both, may
cause loss of volatile organics, thus yielding a negative error. 7.3 Homogenizing Apparatus—A household blender with
The extent and significance of such losses must be evaluated on glass mixing chamber is generally satisfactory for homogeniz-
an individual basis. If significant quantities of volatile carbo- ing immiscible phases in water.
naceous materials are present or may be present in samples
organic carbon should be determined by the difference between 5
Handbook for Monitoring Industrial Wastewater, U.S. Environment Protection
Agency, August 1973, pp. 5–10 to 5–12.
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Instruments marketed by Coulometrics, Inc., a subsidiary of UIC Inc., P.O. Box
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Van Hall, C. E., Barth, D., and Stenger, V. A., “Elimination of Carbonates from 563, Joliet, IL, 60434, or an equivalent, have been found satisfactory.
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Aqueous Solutions Prior to Organic Carbon Determinations,” Analytical Chemistry, Syringes manufactured by Hamilton Co., P.O. Box 10030, Reno, NV 89510, or
Vol 37, 1965, pp. 769–771. an equivalent, have been found satisfactory for this purpose.
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8. Reagents replacement air should be passed through a drying tube filled with equal
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.
tee on Analytical Reagents of the American Chemical Society.8
Other grades may be used provided it is first ascertained that 8.4 Scrubber Tubes and Catalyst Packings as well as
the reagent is of sufficiently high purity to permit its use instructions for their preparation are available from the equip-
without lessening the accuracy of the determination. ment manufacturer.9Fig. 1 illustrates the flow diagram and
names the reagents used.
8.2 Purity of Water— Unless otherwise indicated, reference
to water shall be understood to mean reagent water conforming 8.5 Carbon Dioxide Coulometer Reagents—Cell solutions
to the Specification D1193, Type I. Other reagent water types to absorb CO2 from the gas stream and convert it to a titratable
may be used, provided it is first ascertained that the water is of acid and permit 100 % efficient coulometric titration.9
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
prepared by boiling distilled water in a conical flask for 20 min.
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
tube. For large (10 to 20 L) volumes of carbon dioxide-free 8.7 Organic Carbon Standard Solutions—Although the
water, the absorbed carbon dioxide may be removed by method does not require sample standardization, proper opera-
inserting a fritted-glass gas-dispersion tube to the bottom of the tion of the instrument should be confirmed by injection of
container and vigorously bubbling nitrogen through the water standards of similar composition and concentration to the
for at least 1 h. Carbon dioxide-free water may be stored if unknown. Standards should be stable water soluble compounds
properly protected from atmospheric contamination. such as KHP or benzoic acid of suitable purity.
NOTE 1—Glass containers are preferred for the storage of reagent water
and most standard solutions. It is necessary to provide protection against 9. Hazards
changes in quality due to the absorption of gases or water vapor from the
9.1 Injection of samples containing over 25 000 mg/L TOC
laboratory air. As volumes of fluid are withdrawn from the container, the
or 0.5 mL water may cause explosion of the combustion tube.
8
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
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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 CO2 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.
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10. Sampling 12.4.1 When a micropipet can be used with the sample,
10.1 Collect the sample in accordance with Practices D3370 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 WO3.
Position the boat (capillary) in the ladle and place the ladle in
10.2 Preservation: the cool portion of the combustion tube through the introduc-
10.2.1 To preserve samples for this analysis, store or ship tion port. After closing the introduction port, allow 60 s for the
samples in glass at or below 4°C. Caution— Head space in the oxygen gas stream to sweep out air that entered then move the
sample bottle or freezing the sample may contribute to the loss ladle into the furnace.
of volatile organics from some samples.
NOTE 2—The WO3 is used to minimize potential difficulties caused by
10.3 For monitoring of waters containing solids or immis- salts in samples. Use of the WO3 will minimize the splattering of the
cible liquids of interest, use a mechanical homogenizer or sample which allows salts in the sample to degrade the combustion tube.
ultrasonic disintegrator to homogenize samples. The WO3 also helps prevent salts from reacting with CO2 forming
carbonates which then decompose slowly lengthening the analysis time
10.4 For waste water streams where carbon concentrations and increasing the instrument blank.
are greater than the desired range of instrument operation,
provide on-stream dilution of the sample if possible. 12.4.2 When a precise volume (0.200 mL) of the sample
cannot be obtained, weigh the sample into the combustion boat
10.5 A1.1 gives additional guidelines for preparing heavily or capillary tube and introduce it into the combustion zone as
contaminated water samples when using the sparge technique. described in 12.4.1.
10.6 A1.2 gives additional guidelines for samples contain-
NOTE 3—When weighing samples the size of the sample may be
ing solids and immiscible liquids.
increased. The carbon content must not exceed 4 mg or the water content
exceed 0.4 mL.
11. Calibration and Standardization
NOTE 4—The density of the sample must be known to report the results
11.1 Set up the analyzer and fill coulometer cell in accor- if the result is to be given in mg/L when samples are weighed into
dance with the manufacturer’s specifications. Adjust the gas combustion boats.
flow to 80 to 100 mL/min. Set the readout to milligrams per 12.5 Consistent analysis times must be used for all samples
litre except when other than 0.200-mL samples are used in and blanks. The time must be sufficient for all CO2 to be swept
which case set the readout to micrograms. from the combustion tube to the coulometer and titrated as
11.2 Analyze samples of carbon dioxide-free water as evidenced by stable coulometer readings. The time required
instructed in Section 12 for samples to determine the instru- will depend upon the nature of the samples and is normally 3
ment blank, B. to 7 min. High-level samples require longer analysis times than
11.3 Calibration is not required, however, inject appropriate low level samples and may result in higher blank levels,
standard(s) prior to and following analysis of samples to especially if the samples are high in salts. If samples of a large
confirm proper operation. The standard concentration(s) should concentration range are being analyzed care must be used when
be approximately that of the samples to be analyzed. If the analyzing lower level samples following much higher level
recovery of standards is unacceptable the cause of poor results samples. Additional blanks must be run to confirm that the
should be determined and corrected. Low results suggest a leak blank is reasonable and consistent.
or exhausted combustion tube packing. High results suggest 12.6 Carbonate carbon may be determined using the meth-
contamination of the samples or exhausted scrubber or com- ods given in Test Methods D513 or as instructed by equipment
bustion tube fillings. manufacturer.
12. Procedure
13. Calculation
12.1 Condition each sample to bring the homogenous car-
bon content within range. Although analyses of samples 13.1 Read total carbon values of 0.200-mL samples directly
containing up to 20 000 mg/L TOC is possible, dilution to from the digital display. Correct these values by subtracting the
TOC levels below 1000 is preferable if the sample contains blank value, B, obtained with carbon dioxide-free water and
salts or forms a precipitate upon acidification. correct for any dilutions made to obtain original sample values.
12.2 See 12.3, 12.4, and 12.5 for total carbon and TOC by 13.2 For organic carbon values of acidified and sparged
sparging; 12.6 applies to carbonate carbon determinations 0.200-mL samples, read the values directly from the digital
when organic carbon is to be determined by difference. display. Correct these values by subtracting the blank value B,
and correct for any dilutions in acidifying or other steps to
12.3 Syringe Injection of Samples—Rinse the syringe sev- obtain original sample values.
eral times with the solution to be analyzed, then fill to precise
volume (0.200 mL). Wipe off the excess from the needle tip 13.3 For organic carbon values determined by difference the
with soft paper tissue, taking care that no lint adheres to the result is obtained as follows:
needle. Insert the sample syringe into the injection port, inject O5T2C
the sample, and reset the coulometer to zero. Leave the syringe
in the holder until the analysis is completed. where:
O = organic carbon for original sample, mg/L
12.4 Ladle Introduction of Samples:
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T = total carbon corrected for any blank and dilutions 15. Precision and Bias10
mg/L, and 15.1 The overall and single-operator precision of this test
C = carbonate carbon corrected for any blank and dilutions method varies with the concentration. The precision for stan-
calculated in accordance with the instructions for the dards and for laboratory samples of interest are shown in Fig.
method used, mg/L. 3.
NOTE 5—The digital display of the coulometer is set for readout in
milligrams of carbon per litre for 0.200-mL samples. When other sample 15.2 The observed precision and bias for a series of potas-
volumes are used the readout may be changed to compensate for the sium hydrogen phthalate in water standards were as shown in
volume change or the correct value calculated using the new sample Table 1.
volume without changing the display units. The readout may also be set to
be in micrograms of carbon. 15.3 The recoveries from standard solutions and samples of
13.4 When total carbon or organic carbon is determined by interest were as shown in Table 2.
introduction in a boat, capsule or capillary tube, the concen- 15.4 Nine laboratories participated in the collaborative test-
tration of carbon is determined as follows if the volume used is ing using syringe injection of sparged samples. Samples of
not 0.200 mL: interest included: distilled, deionized, municipal tap, natural,
c 5 m/V or md/W brine, waste, oil shale retort, and industrial process waters. For
other matrices or other techniques (ladle introduction, TOC
where: calculated by difference between total carbon and dissolved
c = concentration of carbon, mg/L, CO2) the precision and accuracy may vary. It is the user’s
m = micrograms of carbon in sample, corrected for instru- responsibility to determine the validity of the method and the
ment blank, resulting precision and accuracy.
V = volume of sample, mL,
15.5 The testing program required laboratories to test
d = density of sample, g/mL, and
W = weight of sample used, g. samples covering the full concentration range of the method, 2
NOTE 6—In some cases, such as for sediments, it may be desirable to to 20 000 mg TOC/L (five samples of potassium hydrogen
know the concentration per gram of sample instead of per litre, in which phthalate in distilled water and three samples of interest
case the following may be used: c = m / W × 1000 where c is now the analyzed before and after spike additions).
concentration of carbon in milligrams per litre.
NOTE 7—The full concentration range is seldom encountered in normal
practice and presented some difficulties for the participants. The problems
14. Report
14.1 The results may be reported in milligrams per litre or
other units as desired. The units used must be clearly noted in 10
Supporting data have been filed at ASTM International Headquarters and may
the report. be obtained by requesting Research Report RR:D19-1094.
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TABLE 1 Precision and Bias
Added
Sample Amount, X̄, mg/L SO, mg/L % SO ST, mg/L % ST Bias, mg/L % Bias Significant?
mg/L
102 22 21.2 A 1.8 8.3 2.4 11.2 −0.8 −3.6 no
103 180 178. A 7.3 4.1 13.5 7.6 −2. −1.1 no
104 2200 2160. A 19. 0.9 61. 2.8 −40. −1.8 yes B
104 18 000 17800. A 130. 0.7 420. 2.3 −200. −1.1 no
A
Value after subtracting result for blank, sample 101 which had an X̄ of 2.7 mg/L and an So of 0.9 mg/L.
B
This bias is statistically significant at the 95 % confidence level. The user of the method may not find the bias significant in his application.
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ANNEXES
(Mandatory Information)
A1.1 Improper preparation of heavily contaminated water BON CONCENTRATION BELOW THE RANGE OF THE
samples may yield erroneously low results. Acidification of METHOD. Determine the approximate level initially if uncer-
such water can cause separation of organics that may be lost tain.
during subsequent sampling and injection. For example, an A1.2.3 While stirring, acidify the diluted sample to pH 2 to
organic acid may be soluble in a high-pH water but, because of 3 slowly so as to keep any particles formed small in size and
its high concentration, not soluble upon acidification. This well dispersed. A dilute acid may be required to accomplish
problem can be solved by first diluting the sample and then this. Note the quality of acid added for later volumetric
acidifying slowly while stirring. Dilution tends to keep the correction of results if a known sample volume is not being
organics in solution and minimizes problems if salts are diluted to a known final volume.
present, while slow acidification of the diluted sample tends to
keep the insolubles formed small in particle size and well A1.2.4 Sparge the sample to complete removal of dissolved
dispersed. If the TOC concentration is not much smaller than CO2.
the TC concentration, determination of TOC by difference may A1.2.5 Blend the acidified sample, if necessary, and while
be preferred over determination of TOC by use of the sparge stirring, take an aliquot for analysis using an appropriate
technique. syringe or micropipet.
A1.2 The procedure for acidifying and sparging samples is NOTE A1.1—For some samples it has been found convenient to add
as follows: sufficient alkali to cause the organic acids to redissolve. If this is done the
sample should be analyzed immediately afterwards to minimize the
A1.2.1 Blend the water sample, if necessary, to produce a absorption of CO2 from the air.
homogeneous sample suitable for dilution. A1.2.6 The blank correction for the instrument should be
A1.2.2 Dilute the blended sample sufficiently with water to performed on CO2 free water treated identically to the samples
improve solubility and suspension of potentially insoluble to compensate for organic contaminants in the reagents added
organics. CAUTION—DO NOT REDUCE ORGANIC CAR- to the samples.
A2.1 If the sample is relatively homogeneous, no condition- A2.3 For laboratory analysis of samples containing immis-
ing will be required except for possible dilution and mixing. cible liquid or solid phases of interest, homogenize the sample
in a glass household-type blender or an ultrasonic disintegrator.
A2.2 Samples containing solids of no interest should be Reproducibility of results will indicate when homogenization
filtered prior to analysis. Sedimentation or centrifugation may
of the sample is complete.
also be employed for solids removal if desired.
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