ASTM D4839-03(2017)
(Test Method)Standard Test Method for Total Carbon and Organic Carbon in Water by Ultraviolet, or Persulfate Oxidation, or Both, and Infrared Detection
Standard Test Method for Total Carbon and Organic Carbon in Water by Ultraviolet, or Persulfate Oxidation, or Both, and Infrared Detection
SIGNIFICANCE AND USE
5.1 This test method is used for determination of the carbon content of water from a variety of natural, domestic, and industrial sources. In its most common form, this test method is used to measure organic carbon as a means of monitoring organic pollutants in industrial wastewater. These measurements are also used in monitoring waste treatment processes.
5.2 The relationship of TOC to other water quality parameters such as chemical oxygen demand (COD) and total oxygen demand (TOD) is described in the literature. 4
SCOPE
1.1 This test method covers the determination of total carbon (TC), inorganic carbon (IC), and total organic carbon (TOC) in water, wastewater, and seawater in the range from 0.1 mg/L to 4000 mg/L of carbon.
1.2 This test method was used successfully with reagent water spiked with sodium carbonate, acetic acid, and pyridine. It is the user's responsibility to ensure the validity of this test method for waters of untested matrices.
1.3 This test method is applicable only to carbonaceous matter in the sample that can be introduced into the reaction zone. The syringe needle or injector opening size generally limit the maximum size of particles that can be so introduced.
1.4 In addition to laboratory analyses, this test method may be applied to stream monitoring.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 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, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.7 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Buy Standard
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D4839 − 03 (Reapproved 2017)
Standard Test Method for
Total Carbon and Organic Carbon in Water by Ultraviolet, or
Persulfate Oxidation, or Both, and Infrared Detection
This standard is issued under the fixed designation D4839; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers the determination of total
carbon (TC), inorganic carbon (IC), and total organic carbon D1129 Terminology Relating to Water
D1192 Guide for Equipment for Sampling Water and Steam
(TOC)inwater,wastewater,andseawaterintherangefrom0.1
mg/L to 4000 mg/L of carbon. in Closed Conduits (Withdrawn 2003)
D1193 Specification for Reagent Water
1.2 This test method was used successfully with reagent
D2777 Practice for Determination of Precision and Bias of
water spiked with sodium carbonate, acetic acid, and pyridine.
Applicable Test Methods of Committee D19 on Water
It is the user’s responsibility to ensure the validity of this test
D3370 Practices for Sampling Water from Closed Conduits
method for waters of untested matrices.
D4129 Test Method for Total and Organic Carbon in Water
1.3 This test method is applicable only to carbonaceous
by High Temperature Oxidation and by Coulometric
matter in the sample that can be introduced into the reaction
Detection
zone. The syringe needle or injector opening size generally
D5847 Practice for Writing Quality Control Specifications
limit the maximum size of particles that can be so introduced.
for Standard Test Methods for Water Analysis
1.4 In addition to laboratory analyses, this test method may
3. Terminology
be applied to stream monitoring.
3.1 Definitions:
1.5 The values stated in SI units are to be regarded as
3.1.1 For definitions of terms used in this standard, refer to
standard. No other units of measurement are included in this
Terminology D1129.
standard.
3.2 Definitions of Terms Specific to This Standard:
1.6 This standard does not purport to address all of the
3.2.1 inorganic carbon (IC), n—carbon in the form of
safety concerns, if any, associated with its use. It is the
carbon dioxide, carbonate ion, or bicarbonate ion.
responsibility of the user of this standard to establish appro-
3.2.2 refractory material, n—that which cannot be oxidized
priate safety, health, and environmental practices and deter-
completely under the test method conditions.
mine the applicability of regulatory limitations prior to use.
3.2.3 total carbon (TC), n—the sum of IC and TOC.
1.7 This international standard was developed in accor-
dance with internationally recognized principles on standard-
3.2.4 total organic carbon (TOC), n—carbon in the form of
ization established in the Decision on Principles for the
organic compounds.
Development of International Standards, Guides and Recom-
4. Summary of Test Method
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
4.1 Fundamentals—Carbon can occur in water as an inor-
ganic and organic compound. This test method can be used to
1 2
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
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 Dec. 15, 2017. Published December 2017. Originally the ASTM website.
approved in 1988. Last previous edition approved in 2011 as D4839 – 03 (2011). The last approved version of this historical standard is referenced on
DOI: 10.1520/D4839-03R17. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4839 − 03 (2017)
make independent measurements of IC, TOC, and TC, and can 6.3 Homogenizing or sparging of a sample, or both, may
also determine IC by the difference of TC and TOC, and TOC cause loss of purgeable organic compounds, thus yielding a
as the difference of TC and IC. value lower than the true TOC level. (For this reason, such
measurements are sometimes known as nonpurgeable organic
4.2 The essentials of this test method are: (a) removal of IC,
carbon (NPOC)). The extent and significance of such losses
if desired, by acidification of the sample and sparging by
must be evaluated on an individual basis.This may be done by
carbon-free gas; (b) conversion of remaining carbon to CO by
comparing theTOC by difference (TC-IC) with the directTOC
action of persulfate, aided either by elevated temperature or
figure, that is, that obtained from a sparged sample. The
ultraviolet (UV) radiation; (c) detection of CO that is swept
difference, if any, between these TOC figures represents
out of the reactor by a gas stream; and (d) conversion of
purgeable organic carbon (POC) lost during sparging.
detector signal to a display of carbon concentration in mg/L.A
Alternatively, direct measurement of POC can be made during
diagram of suitable apparatus is given in Fig. 1.
sparging, using optional capabilities of the analyzer.
5. Significance and Use
6.4 Note that error will be introduced when the method of
difference is used to derive a relatively small level from two
5.1 This test method is used for determination of the carbon
large levels. For example, a ground water high in IC and low
content of water from a variety of natural, domestic, and
inTOCwillgiveapoorerTOCvalueas(TC-IC)thanbydirect
industrial sources. In its most common form, this test method
measurement.
is used to measure organic carbon as a means of monitoring
organic pollutants in industrial wastewater. These measure-
7. Apparatus
ments are also used in monitoring waste treatment processes.
7.1 Homogenizing Apparatus—Ahousehold blender is gen-
5.2 The relationship of TOC to other water quality param-
erally satisfactory for homogenizing immiscible phases in
eterssuchaschemicaloxygendemand(COD)andtotaloxygen
water.
demand (TOD) is described in the literature.
7.2 Sampling Devices—Microlitre-to-millilitre syringes are
6. Interferences and Limitations
typically required for this test method. Alternatives include
6.1 The oxidation of dissolved carbon to CO is brought
manually operated or automatically operated sampling valves.
about at relatively low temperatures by the chemical action of
Sampling devices with inside diameters as small as 0.15 mm
reactive species produced by hot or UV-irradiated persulfate
may be used with samples containing little or no particulate
ions. Even if oxygen is used as the sparging gas, it makes a
matter. Larger inside dimensions such as 0.4 mm will be
much lower contribution to oxidation than in high-temperature
required for samples with particulate matter.
(combustive) systems. Not all suspended or refractory material
NOTE 1—See 6.1 concerning oxidation of particulate matter.
may be oxidized under these conditions; analysts should take
7.3 Apparatus for Carbon Determination—This instrument
steps to determine what recovery is being obtained. This may
consists of reagent and sample introduction mechanism, a
be done by several methods: (a) by monitoring reaction
gas-spargedreactionvessel,agasdemisterordryer,orboth,an
progress to verify that oxidation has been completed; (b)by
optional CO trap, a CO -specific infrared detector, a control
rerunning the sample under more vigorous reaction conditions; 2 2
system, and a display. Fig. 1 shows a diagram of such an
(c) by analyzing the sample by an alternative method, such as
arrangement.
Test Method D4129, known to result in full recovery; or (d)by
7.3.1 Sparging requires an inert vessel with a capacity of at
spiking samples with known refractories and determining
least double the sample size with provision for sparging with
recovery.
50 to 100 mL/min of carbon free gas. This procedure will
6.2 Chloride ion tends to interfere with oxidative reaction
remove essentially all IC in 2 to 10 min, depending on design.
mechanisms in this test method, prolonging oxidation times
7.3.2 Oxidation—The reaction assembly contains reagent
and sometimes preventing full recovery. Follow manufactur-
and sample introduction devices, and a reactor vessel with
er’s instructions for dealing with this problem. See Appendix
sparging flow of carbon-free gas. The vessel may be heated by
X1 for supporting data.
an external source, and may contain a UV lamp. The reaction
vessel and sparging vessel (see 6.3) may be combined.
7.3.3 Gas Conditioning—The gas passing from the reactor
is dried, and the CO produced is either trapped and later
Handbook for Monitoring Industrial Wastewater, Section 5.3, U.S. Environ-
ment Protection Agency, August 1973, pp. 5–12.
FIG. 1 Diagram of Apparatus
D4839 − 03 (2017)
released to the detector, or routed directly to the detector 8.5 Persulfate Solution—Prepare by dissolving the appro-
through a chlorine-removing scrubber. priateweightofpotassiumorsodiumpersulfatein1Lofwater,
7.3.4 Detector—The CO in the gas stream is detected by a to produce the concentration specified by the instrument
CO -specific nondispersive infrared (NDIR) detector. manufacturer. If specified, add 1 mL of phosphoric acid (sp gr
7.3.5 Presentation of Results—The NDIR detector output is 1.69) and mix well. Store in a cool, dark place. Recipes for this
related to stored calibration data and then displayed as milli- reagentsolutionmaybemodifiedbymanufacturerstomeetthe
grams of carbon per litre. needs of specific applications, for example, high chloride
samples.
8. Reagents and Materials
8.6 Gas Supply—Agas free of CO and of organic matter is
8.1 Purity of Reagents—Reagent grade chemicals shall be
required. Use a purity as specified by the equipment manufac-
used in all tests. Unless otherwise indicated, it is intended that
turer. The use of oxygen is preferred for the UV-persulfate
all reagents conform to the specifications of the Committee on
method, and nitrogen or helium is preferred if a CO trap is
AnalyticalReagentsoftheAmericanChemicalSociety, where
used between reactor and detector.
such specifications are available. Other grades may be used,
9. Sampling and Sample Preservation
provided it is first ascertained that the reagent is of sufficient
purity to permit its use without lessening the accuracy of the
9.1 CollectthesampleinaccordancewithGuideD1192and
determination.
Practices D3370.
8.2 Purity of Water—Unless otherwise indicated, references
9.2 To preserve samples for this analysis, store samples in
towatershallbeunderstoodtomeanreagentwaterconforming
glass at 4°C. To aid preservation, acidify the samples to a pH
to Specification D1193, Type I or Type II. The indicated
of 2. It should be noted that acidification will enhance loss of
specification does not actually specify inorganic carbon or
inorganiccarbon.Ifthepurgeableorganicfractionisimportant,
organic carbon levels.These levels can affect the results of this
fill the sample bottles to overflowing with a minimum of
test method, especially at progressively lower levels of the
turbulence and cap them using a fluoropolymer-lined cap,
carboncontentinthesamplestobemeasured.Whereinorganic
without headspace.
carbon in reagent water is significant, CO -free water may be
9.3 For monitoring of waters containing solids or immis-
prepared from reagent water by acidifying to pH 2, then
cible liquids that are to be injected into the reaction zone, use
sparging with fritted-glass sparger using CO -free gas (time
a mechanical homogenizer or ultrasonic disintegrator. Filtering
will depend on volume and gas flow rate, and should be
or screening may be necessary after homogenization to reject
determined by test).Alternatively, if the carbon contribution of
particle sizes that are too large for injection. Volatile organics
the reagent water is known accurately, its effect may be
may be lost. See 6.3.
allowed for in preparation of standards and other solutions.
CO -freewatershouldbeprotectedfromatmosphericcontami- 9.4 Forwastewaterstreamswherecarbonconcentrationsare
nation. Glass containers are required for storage of water and greater than the desired range of instrument operation, dilute
standard solutions. the samples as necessary.
8.3 Acid—Various concentrated acids may be used for
10. Instrument Operation
acidification of samples and of the oxidizing reagent. Acids
10.1 Follow the manufacturer’s instructions for instrument
such as phosphoric (sp gr 1.69), nitric (sp gr 1.42), or sulfuric
warm-up, gas flows, and liquid flows.
(sp gr 1.84) are suitable for most applications. Sulfuric acid
should be used in the form of a 1 + 1 dilution, for safety
11. Calibration
reasons. Hydrochloric acid is not recommended.
11.1 Use the stock solution of 2000 mg/L of carbon, and
8.4 Organic Carbon, Standard Solution (2000 mg/L)—
various dilutions of it, for calibration.
Choose a water-soluble, stable reagent grade compound, such
NOTE 2—Dilutions should be made with CO -free water (see 8.2).
as benzoic acid or anhydrous potassium hydrogen phthalate
(KHC H O ). Calculate the weight of compound required to
8 4 4 11.2 Calibration protocols may vary with equipment manu-
make 1 L of organic carbon standard solution; for example,
facturers. However, in general, calibrate the instrument in
KHC H O = 0.471 g of carbon per gram, so one litre of 2 g/L
8 4 4 accordance with the manufacturer’s instructions, and use
of standard requires 2/0.471, or 4.25, grams of KHP. Dissolve
standards to verify such calibration in the specific range of
the required amount of standard in some CO -free water in a
2 interest for actual measurements. Plots of standard concentra-
1-L volumetric flask, add 1 mL of acid, and dilute to volume.
tionversusinstrumentreadingmaybeusedforcalibrationorto
This stock solution, or dilutions of it, may be used to calibrate
verify linearity of response.
and test performance of the carbon analyzer.
11.3 Establish instrument blank according to the manufac-
turer’s instructions.
Reagent Chemicals, American Chemical Society Specifications, American
12. Procedure
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
12.1 Mi
...
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: D4839 − 03 (Reapproved 2017)
Standard Test Method for
Total Carbon and Organic Carbon in Water by Ultraviolet, or
Persulfate Oxidation, or Both, and Infrared Detection
This standard is issued under the fixed designation D4839; 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 (´) 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 2.1 ASTM Standards:
carbon (TC), inorganic carbon (IC), and total organic carbon D1129 Terminology Relating to Water
(TOC) in water, wastewater, and seawater in the range from 0.1 D1192 Guide for Equipment for Sampling Water and Steam
mg/L to 4000 mg/L of carbon. in Closed Conduits (Withdrawn 2003)
D1193 Specification for Reagent Water
1.2 This test method was used successfully with reagent
D2777 Practice for Determination of Precision and Bias of
water spiked with sodium carbonate, acetic acid, and pyridine.
Applicable Test Methods of Committee D19 on Water
It is the user’s responsibility to ensure the validity of this test
D3370 Practices for Sampling Water from Closed Conduits
method for waters of untested matrices.
D4129 Test Method for Total and Organic Carbon in Water
1.3 This test method is applicable only to carbonaceous
by High Temperature Oxidation and by Coulometric
matter in the sample that can be introduced into the reaction
Detection
zone. The syringe needle or injector opening size generally
D5847 Practice for Writing Quality Control Specifications
limit the maximum size of particles that can be so introduced.
for Standard Test Methods for Water Analysis
1.4 In addition to laboratory analyses, this test method may
3. Terminology
be applied to stream monitoring.
3.1 Definitions:
1.5 The values stated in SI units are to be regarded as
3.1.1 For definitions of terms used in this standard, refer to
standard. No other units of measurement are included in this
Terminology D1129.
standard.
3.2 Definitions of Terms Specific to This Standard:
1.6 This standard does not purport to address all of the
3.2.1 inorganic carbon (IC), n—carbon in the form of
safety concerns, if any, associated with its use. It is the
carbon dioxide, carbonate ion, or bicarbonate ion.
responsibility of the user of this standard to establish appro-
3.2.2 refractory material, n—that which cannot be oxidized
priate safety, health, and environmental practices and deter-
completely under the test method conditions.
mine the applicability of regulatory limitations prior to use.
1.7 This international standard was developed in accor-
3.2.3 total carbon (TC), n—the sum of IC and TOC.
dance with internationally recognized principles on standard-
3.2.4 total organic carbon (TOC), n—carbon in the form of
ization established in the Decision on Principles for the
organic compounds.
Development of International Standards, Guides and Recom-
4. Summary of Test Method
mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
4.1 Fundamentals—Carbon can occur in water as an inor-
ganic and organic compound. This test method can be used to
1 2
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 Dec. 15, 2017. Published December 2017. Originally the ASTM website.
approved in 1988. Last previous edition approved in 2011 as D4839 – 03 (2011). The last approved version of this historical standard is referenced on
DOI: 10.1520/D4839-03R17. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4839 − 03 (2017)
make independent measurements of IC, TOC, and TC, and can 6.3 Homogenizing or sparging of a sample, or both, may
also determine IC by the difference of TC and TOC, and TOC cause loss of purgeable organic compounds, thus yielding a
as the difference of TC and IC. value lower than the true TOC level. (For this reason, such
measurements are sometimes known as nonpurgeable organic
4.2 The essentials of this test method are: (a) removal of IC,
carbon (NPOC)). The extent and significance of such losses
if desired, by acidification of the sample and sparging by
must be evaluated on an individual basis. This may be done by
carbon-free gas; (b) conversion of remaining carbon to CO by
comparing the TOC by difference (TC-IC) with the direct TOC
action of persulfate, aided either by elevated temperature or
figure, that is, that obtained from a sparged sample. The
ultraviolet (UV) radiation; (c) detection of CO that is swept
difference, if any, between these TOC figures represents
out of the reactor by a gas stream; and (d) conversion of
purgeable organic carbon (POC) lost during sparging.
detector signal to a display of carbon concentration in mg/L. A
Alternatively, direct measurement of POC can be made during
diagram of suitable apparatus is given in Fig. 1.
sparging, using optional capabilities of the analyzer.
5. Significance and Use
6.4 Note that error will be introduced when the method of
difference is used to derive a relatively small level from two
5.1 This test method is used for determination of the carbon
large levels. For example, a ground water high in IC and low
content of water from a variety of natural, domestic, and
in TOC will give a poorer TOC value as (TC-IC) than by direct
industrial sources. In its most common form, this test method
measurement.
is used to measure organic carbon as a means of monitoring
organic pollutants in industrial wastewater. These measure-
7. Apparatus
ments are also used in monitoring waste treatment processes.
7.1 Homogenizing Apparatus—A household blender is gen-
5.2 The relationship of TOC to other water quality param-
erally satisfactory for homogenizing immiscible phases in
eters such as chemical oxygen demand (COD) and total oxygen
water.
demand (TOD) is described in the literature.
7.2 Sampling Devices—Microlitre-to-millilitre syringes are
6. Interferences and Limitations
typically required for this test method. Alternatives include
6.1 The oxidation of dissolved carbon to CO is brought
manually operated or automatically operated sampling valves.
about at relatively low temperatures by the chemical action of
Sampling devices with inside diameters as small as 0.15 mm
reactive species produced by hot or UV-irradiated persulfate
may be used with samples containing little or no particulate
ions. Even if oxygen is used as the sparging gas, it makes a
matter. Larger inside dimensions such as 0.4 mm will be
much lower contribution to oxidation than in high-temperature
required for samples with particulate matter.
(combustive) systems. Not all suspended or refractory material
NOTE 1—See 6.1 concerning oxidation of particulate matter.
may be oxidized under these conditions; analysts should take
7.3 Apparatus for Carbon Determination—This instrument
steps to determine what recovery is being obtained. This may
consists of reagent and sample introduction mechanism, a
be done by several methods: (a) by monitoring reaction
gas-sparged reaction vessel, a gas demister or dryer, or both, an
progress to verify that oxidation has been completed; (b) by
optional CO trap, a CO -specific infrared detector, a control
rerunning the sample under more vigorous reaction conditions; 2 2
system, and a display. Fig. 1 shows a diagram of such an
(c) by analyzing the sample by an alternative method, such as
arrangement.
Test Method D4129, known to result in full recovery; or (d) by
7.3.1 Sparging requires an inert vessel with a capacity of at
spiking samples with known refractories and determining
least double the sample size with provision for sparging with
recovery.
50 to 100 mL/min of carbon free gas. This procedure will
6.2 Chloride ion tends to interfere with oxidative reaction
remove essentially all IC in 2 to 10 min, depending on design.
mechanisms in this test method, prolonging oxidation times
7.3.2 Oxidation—The reaction assembly contains reagent
and sometimes preventing full recovery. Follow manufactur-
and sample introduction devices, and a reactor vessel with
er’s instructions for dealing with this problem. See Appendix
sparging flow of carbon-free gas. The vessel may be heated by
X1 for supporting data.
an external source, and may contain a UV lamp. The reaction
vessel and sparging vessel (see 6.3) may be combined.
7.3.3 Gas Conditioning—The gas passing from the reactor
is dried, and the CO produced is either trapped and later
Handbook for Monitoring Industrial Wastewater, Section 5.3, U.S. Environ-
ment Protection Agency, August 1973, pp. 5–12.
FIG. 1 Diagram of Apparatus
D4839 − 03 (2017)
released to the detector, or routed directly to the detector 8.5 Persulfate Solution—Prepare by dissolving the appro-
through a chlorine-removing scrubber. priate weight of potassium or sodium persulfate in 1 L of water,
7.3.4 Detector—The CO in the gas stream is detected by a to produce the concentration specified by the instrument
CO -specific nondispersive infrared (NDIR) detector. manufacturer. If specified, add 1 mL of phosphoric acid (sp gr
7.3.5 Presentation of Results—The NDIR detector output is 1.69) and mix well. Store in a cool, dark place. Recipes for this
related to stored calibration data and then displayed as milli- reagent solution may be modified by manufacturers to meet the
grams of carbon per litre. needs of specific applications, for example, high chloride
samples.
8. Reagents and Materials
8.6 Gas Supply—A gas free of CO and of organic matter is
8.1 Purity of Reagents—Reagent grade chemicals shall be
required. Use a purity as specified by the equipment manufac-
used in all tests. Unless otherwise indicated, it is intended that
turer. The use of oxygen is preferred for the UV-persulfate
all reagents conform to the specifications of the Committee on
method, and nitrogen or helium is preferred if a CO trap is
Analytical Reagents of the American Chemical Society, where
used between reactor and detector.
such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficient 9. Sampling and Sample Preservation
purity to permit its use without lessening the accuracy of the
9.1 Collect the sample in accordance with Guide D1192 and
determination.
Practices D3370.
8.2 Purity of Water—Unless otherwise indicated, references
9.2 To preserve samples for this analysis, store samples in
to water shall be understood to mean reagent water conforming
glass at 4°C. To aid preservation, acidify the samples to a pH
to Specification D1193, Type I or Type II. The indicated
of 2. It should be noted that acidification will enhance loss of
specification does not actually specify inorganic carbon or
inorganic carbon. If the purgeable organic fraction is important,
organic carbon levels. These levels can affect the results of this
fill the sample bottles to overflowing with a minimum of
test method, especially at progressively lower levels of the
turbulence and cap them using a fluoropolymer-lined cap,
carbon content in the samples to be measured. Where inorganic
without headspace.
carbon in reagent water is significant, CO -free water may be
9.3 For monitoring of waters containing solids or immis-
prepared from reagent water by acidifying to pH 2, then
cible liquids that are to be injected into the reaction zone, use
sparging with fritted-glass sparger using CO -free gas (time
a mechanical homogenizer or ultrasonic disintegrator. Filtering
will depend on volume and gas flow rate, and should be
or screening may be necessary after homogenization to reject
determined by test). Alternatively, if the carbon contribution of
particle sizes that are too large for injection. Volatile organics
the reagent water is known accurately, its effect may be
may be lost. See 6.3.
allowed for in preparation of standards and other solutions.
CO -free water should be protected from atmospheric contami- 9.4 For wastewater streams where carbon concentrations are
nation. Glass containers are required for storage of water and greater than the desired range of instrument operation, dilute
standard solutions. the samples as necessary.
8.3 Acid—Various concentrated acids may be used for
10. Instrument Operation
acidification of samples and of the oxidizing reagent. Acids
10.1 Follow the manufacturer’s instructions for instrument
such as phosphoric (sp gr 1.69), nitric (sp gr 1.42), or sulfuric
warm-up, gas flows, and liquid flows.
(sp gr 1.84) are suitable for most applications. Sulfuric acid
should be used in the form of a 1 + 1 dilution, for safety
11. Calibration
reasons. Hydrochloric acid is not recommended.
11.1 Use the stock solution of 2000 mg/L of carbon, and
8.4 Organic Carbon, Standard Solution (2000 mg/L)—
various dilutions of it, for calibration.
Choose a water-soluble, stable reagent grade compound, such
NOTE 2—Dilutions should be made with CO -free water (see 8.2).
as benzoic acid or anhydrous potassium hydrogen phthalate
(KHC H O ). Calculate the weight of compound required to
8 4 4 11.2 Calibration protocols may vary with equipment manu-
make 1 L of organic carbon standard solution; for example,
facturers. However, in general, calibrate the instrument in
KHC H O = 0.471 g of carbon per gram, so one litre of 2 g/L
8 4 4 accordance with the manufacturer’s instructions, and use
of standard requires 2/0.471, or 4.25, grams of KHP. Dissolve
standards to verify such calibration in the specific range of
the required amount of standard in some CO -free water in a
2 interest for actual measurements. Plots of standard concentra-
1-L volumetric flask, add 1 mL of acid, and dilute to volume.
tion versus instrument reading may be used for calibration or to
This stock solution, or dilutions of it, may be used to calibrate
verify linearity of response.
and test performance of the carbon analyzer.
11.3 Establish instrument blank according to the manufac-
turer’s instructions.
Reagent Chemicals, American Chemical Society Specifications, American
12. Procedure
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standa
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D4839 − 03 (Reapproved 2011) D4839 − 03 (Reapproved 2017)
Standard Test Method for
Total Carbon and Organic Carbon in Water by Ultraviolet, or
Persulfate Oxidation, or Both, and Infrared Detection
This standard is issued under the fixed designation D4839; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope
1.1 This test method covers the determination of total carbon (TC), inorganic carbon (IC), and total organic carbon (TOC) in
water, wastewater, and seawater in the range from 0.1 mg/L to 4000 mg/L of carbon.
1.2 This test method was used successfully with reagent water spiked with sodium carbonate, acetic acid, and pyridine. It is the
user’s responsibility to ensure the validity of this test method for waters of untested matrices.
1.3 This test method is applicable only to carbonaceous matter in the sample that can be introduced into the reaction zone. The
syringe needle or injector opening size generally limit the maximum size of particles that can be so introduced.
1.4 In addition to laboratory analyses, this test method may be applied to stream monitoring.
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 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 safety, health, and healthenvironmental practices and determine the
applicability of regulatory limitations prior to use.
1.7 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2.1 ASTM Standards:
D1129 Terminology Relating to Water
D1192 Guide for Equipment for Sampling Water and Steam in Closed Conduits (Withdrawn 2003)
D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Closed Conduits
D4129 Test Method for Total and Organic Carbon in Water by High Temperature Oxidation and by Coulometric Detection
D5847 Practice for Writing Quality Control Specifications for Standard Test Methods for Water Analysis
3. Terminology
3.1 Definitions—Definitions: For definitions of terms used in this test method, refer to Terminology D1129.
3.1.1 For definitions of terms used in this standard, refer to Terminology D1129.
3.2 Definitions of Terms Specific to This Standard:
3.2.1 inorganic carbon (IC)—(IC), n—carbon in the form of carbon dioxide, carbonate ion, or bicarbonate ion.
3.2.2 total organicrefractory material, carbon n—(TOC)—carbon in the form of organic compounds.that which cannot be
oxidized completely under the test method conditions.
This test method is under the jurisdiction of ASTM Committee D19 on Water and is the direct responsibility of Subcommittee D19.06 on Methods for Analysis for
Organic Substances in Water.
Current edition approved May 1, 2011Dec. 15, 2017. Published June 2011December 2017. Originally approved in 1988. Last previous edition approved in 20032011 as
D4839 – 03.D4839 – 03 (2011). DOI: 10.1520/D4839-03R11.10.1520/D4839-03R17.
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.
The last approved version of this historical standard is referenced on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4839 − 03 (2017)
3.2.3 total carbon (TC)—(TC), n—the sum of IC and TOC.
3.2.4 refractory material—total organic carbon (TOC), n—that which cannot be oxidized completely under the test method
conditions.carbon in the form of organic compounds.
4. Summary of Test Method
4.1 Fundamentals—Carbon can occur in water as an inorganic and organic compound. This test method can be used to make
independent measurements of IC, TOC, and TC, and can also determine IC by the difference of TC and TOC, and TOC as the
difference of TC and IC.
4.2 The essentials of this test method are: (a) removal of IC, if desired, by acidification of the sample and sparging by
carbon-free gas; (b) conversion of remaining carbon to CO by action of persulfate, aided either by elevated temperature or
ultraviolet (UV) radiation; (c) detection of CO that is swept out of the reactor by a gas stream; and (d) conversion of detector
signal to a display of carbon concentration in mg/L. A diagram of suitable apparatus is given in Fig. 1.
5. Significance and Use
5.1 This test method is used for determination of the carbon content of water from a variety of natural, domestic, and industrial
sources. In its most common form, this test method is used to measure organic carbon as a means of monitoring organic pollutants
in industrial wastewater. These measurements are also used in monitoring waste treatment processes.
5.2 The relationship of TOC to other water quality parameters such as chemical oxygen demand (COD) and total oxygen
demand (TOD) is described in the literature.
6. Interferences and Limitations
6.1 The oxidation of dissolved carbon to CO is brought about at relatively low temperatures by the chemical action of reactive
species produced by hot or UV-irradiated persulfate ions. Even if oxygen is used as the sparging gas, it makes a much lower
contribution to oxidation than in high-temperature (combustive) systems. Not all suspended or refractory material may be oxidized
under these conditions; analysts should take steps to determine what recovery is being obtained. This may be done by several
methods: (a) by monitoring reaction progress to verify that oxidation has been completed; (b) by rerunning the sample under more
vigorous reaction conditions; (c) by analyzing the sample by an alternative method, such as Test Method D4129, known to result
in full recovery; or (d) by spiking samples with known refractories and determining recovery.
6.2 Chloride ion tends to interfere with oxidative reaction mechanisms in this test method, prolonging oxidation times and
sometimes preventing full recovery. Follow manufacturer’s instructions for dealing with this problem. See Appendix X1 for
supporting data.
6.3 Homogenizing or sparging of a sample, or both, may cause loss of purgeable organic compounds, thus yielding a value
lower than the true TOC level. (For this reason, such measurements are sometimes known as nonpurgeable organic carbon
(NPOC)). The extent and significance of such losses must be evaluated on an individual basis. This may be done by comparing
the TOC by difference (TC-IC) with the direct TOC figure, that is, that obtained from a sparged sample. The difference, if any,
between these TOC figures represents purgeable organic carbon (POC) lost during sparging. Alternatively, direct measurement of
POC can be made during sparging, using optional capabilities of the analyzer.
6.4 Note that error will be introduced when the method of difference is used to derive a relatively small level from two large
levels. For example, a ground water high in IC and low in TOC will give a poorer TOC value as (TC-IC) than by direct
measurement.
7. Apparatus
7.1 Homogenizing Apparatus—A household blender is generally satisfactory for homogenizing immiscible phases in water.
FIG. 1 Diagram of Apparatus
Handbook for Monitoring Industrial Wastewater, Section 5.3, U.S. Environment Protection Agency, August 1973, pp. 5–12.
D4839 − 03 (2017)
7.2 Sampling Devices—Microlitre-to-millilitre syringes are typically required for this test method. Alternatives include
manually operated or automatically operated sampling valves. Sampling devices with inside diameters as small as 0.15 mm may
be used with samples containing little or no particulate matter. Larger inside dimensions such as 0.4 mm will be required for
samples with particulate matter.
NOTE 1—See 6.1 concerning oxidation of particulate matter.
7.3 Apparatus for Carbon Determination—This instrument consists of reagent and sample introduction mechanism, a
gas-sparged reaction vessel, a gas demister or dryer, or both, an optional CO trap, a CO -specific infrared detector, a control
2 2
system, and a display. Fig. 1 shows a diagram of such an arrangement.
7.3.1 Sparging requires an inert vessel with a capacity of at least double the sample size with provision for sparging with 50
to 100 mL/min of carbon free gas. This procedure will remove essentially all IC in 2 to 10 min, depending on design.
7.3.2 Oxidation—The reaction assembly contains reagent and sample introduction devices, and a reactor vessel with sparging
flow of carbon-free gas. The vessel may be heated by an external source, and may contain a UV lamp. The reaction vessel and
sparging vessel (see 6.3) may be combined.
7.3.3 Gas Conditioning—The gas passing from the reactor is dried, and the CO produced is either trapped and later released
to the detector, or routed directly to the detector through a chlorine-removing scrubber.
7.3.4 Detector—The CO in the gas stream is detected by a CO -specific nondispersive infrared (NDIR) detector.
2 2
7.3.5 Presentation of Results—The NDIR detector output is related to stored calibration data and then displayed as milligrams
of carbon per litre.
8. Reagents and Materials
8.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, Society, where
such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficient purity
to permit its use without lessening the accuracy of the determination.
8.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water conforming to
Specification D1193, Type I or Type II. The indicated specification does not actually specify inorganic carbon or organic carbon
levels. These levels can affect the results of this test method, especially at progressively lower levels of the carbon content in the
samples to be measured. Where inorganic carbon in reagent water is significant, CO -free water may be prepared from reagent
water by acidifying to pH 2, then sparging with fritted-glass sparger using CO -free gas (time will depend on volume and gas flow
rate, and should be determined by test). Alternatively, if the carbon contribution of the reagent water is known accurately, its effect
may be allowed for in preparation of standards and other solutions. CO -free water should be protected from atmospheric
contamination. Glass containers are required for storage of water and standard solutions.
8.3 Acid—Various concentrated acids may be used for acidification of samples and of the oxidizing reagent. Acids such as
phosphoric (sp gr 1.69), nitric (sp gr 1.42), or sulfuric (sp gr 1.84) are suitable for most applications. Sulfuric acid should be used
in the form of a 1 + 1 dilution, for safety reasons. Hydrochloric acid is not recommended.
8.4 Organic Carbon, Standard Solution (2000 mg/L)—Choose a water-soluble, stable reagent grade compound, such as benzoic
acid or anhydrous potassium hydrogen phthalate (KHC H O ). Calculate the weight of compound required to make 1 L of organic
8 4 4
carbon standard solution; for example, KHC H O = 0.471 g of carbon per gram, so one litre of 2 g/L of standard requires 2/0.471,
8 4 4
or 4.25, grams of KHP. Dissolve the required amount of standard in some CO -free water in a 1-L volumetric flask, add 1 mL of
acid, and dilute to volume. This stock solution, or dilutions of it, may be used to calibrate and test performance of the carbon
analyzer.
8.5 Persulfate Solution—Prepare by dissolving the appropriate weight of potassium or sodium persulfate in 1 L of water, to
produce the concentration specified by the instrument manufacturer. If specified, add 1 mL of phosphoric acid (sp gr 1.69) and mix
well. Store in a cool, dark place. Recipes for this reagent solution may be modified by manufacturers to meet the needs of specific
applications, for example, high chloride samples.
8.6 Gas Supply—A gas free of CO and of organic matter is required. Use a purity as specified by the equipment manufacturer.
The use of oxygen is preferred for the UV-persulfate method, and nitrogen or helium is preferred if a CO trap is used between
reactor and detector.
9. Sampling and Sample Preservation
9.1 Collect the sample in accordance with SpecificationGuide D1192 and PracticePractices D3370.
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 Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National
Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.
D4839 − 03 (2017)
9.2 To preserve samples for this analysis, store samples in glass at 4°C. To aid preservation, acidify the samples to a pH of 2.
It should be noted that acidification will enhance loss of inorganic carbon. If the purgeable organic fraction is important, fill the
sample bottles to overflowing with a minimum of turbulence and cap them using a fluoropolymer-lined cap, without headspace.
9.3 For monitoring of waters containing solids or immiscible liquids that are to be injected into the reaction zone, use a
mechanical homogenizer or ultrasonic disintegrator. Filtering or screening may be necessary after homogenization to reject particle
sizes that are too large for injection. Volatile organics may be lost. See 6.3.
9.4 For wastewater streams where carbon concentrations are greater than the desire
...
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