ASTM D4839-03(2011)
(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
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.
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.
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 and health practices and determine the applicability of regulatory limitations prior to use.
General Information
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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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D4839 − 03 (Reapproved 2011)
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 D1193 Specification for Reagent Water
D2777 Practice for Determination of Precision and Bias of
1.1 This test method covers the determination of total
Applicable Test Methods of Committee D19 on Water
carbon (TC), inorganic carbon (IC), and total organic carbon
D3370 Practices for Sampling Water from Closed Conduits
(TOC)inwater,wastewater,andseawaterintherangefrom0.1
D4129 Test Method for Total and Organic Carbon in Water
mg/L to 4000 mg/L of carbon.
by High Temperature Oxidation and by Coulometric
1.2 This test method was used successfully with reagent
Detection
water spiked with sodium carbonate, acetic acid, and pyridine.
D5847 Practice for Writing Quality Control Specifications
It is the user’s responsibility to ensure the validity of this test
for Standard Test Methods for Water Analysis
method for waters of untested matrices.
3. Terminology
1.3 This test method is applicable only to carbonaceous
matter in the sample that can be introduced into the reaction
3.1 Definitions—For definitions of terms used in this test
zone. The syringe needle or injector opening size generally
method, refer to Terminology D1129.
limit the maximum size of particles that can be so introduced.
3.2 Definitions of Terms Specific to This Standard:
1.4 In addition to laboratory analyses, this test method may
3.2.1 inorganic carbon (IC)—carbon in the form of carbon
be applied to stream monitoring.
dioxide, carbonate ion, or bicarbonate ion.
1.5 The values stated in SI units are to be regarded as 3.2.2 total organic carbon (TOC)—carbon in the form of
standard. No other units of measurement are included in this organic compounds.
standard.
3.2.3 total carbon (TC)—the sum of IC and TOC.
1.6 This standard does not purport to address all of the
3.2.4 refractory material—that which cannot be oxidized
safety concerns, if any, associated with its use. It is the
completely under the test method conditions.
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
4. Summary of Test Method
bility of regulatory limitations prior to use.
4.1 Fundamentals—Carbon can occur in water as an inor-
ganic and organic compound. This test method can be used to
2. Referenced Documents
make independent measurements of IC, TOC, and TC, and can
2.1 ASTM Standards:
also determine IC by the difference of TC and TOC, and TOC
D1129 Terminology Relating to Water
as the difference of TC and IC.
D1192 Guide for Equipment for Sampling Water and Steam
4.2 The essentials of this test method are: (a) removal of IC,
in Closed Conduits (Withdrawn 2003)
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
This test method is under the jurisdiction of ASTM Committee D19 on Water
ultraviolet (UV) radiation; (c) detection of CO that is swept
andisthedirectresponsibilityofSubcommitteeD19.06onMethodsforAnalysisfor
out of the reactor by a gas stream; and (d) conversion of
Organic Substances in Water.
Current edition approved May 1, 2011. Published June 2011. Originally
detector signal to a display of carbon concentration in mg/L.A
approved in 1988. Last previous edition approved in 2003 as D4839 – 03. DOI:
diagram of suitable apparatus is given in Fig. 1.
10.1520/D4839-03R11.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
5. Significance and Use
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
5.1 This test method is used for determination of the carbon
the ASTM website.
content of water from a variety of natural, domestic, and
The last approved version of this historical standard is referenced on
www.astm.org. industrial sources. In its most common form, this test method
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4839 − 03 (2011)
FIG. 1 Diagram of Apparatus
is used to measure organic carbon as a means of monitoring 7. Apparatus
organic pollutants in industrial wastewater. These measure-
7.1 Homogenizing Apparatus—Ahousehold blender is gen-
ments are also used in monitoring waste treatment processes.
erally satisfactory for homogenizing immiscible phases in
5.2 The relationship of TOC to other water quality param- water.
eterssuchaschemicaloxygendemand(COD)andtotaloxygen
7.2 Sampling Devices—Microlitre-to-millilitre syringes are
demand (TOD) is described in the literature.
typically required for this test method. Alternatives include
manually operated or automatically operated sampling valves.
6. Interferences and Limitations
Sampling devices with inside diameters as small as 0.15 mm
6.1 The oxidation of dissolved carbon to CO is brought
may be used with samples containing little or no particulate
about at relatively low temperatures by the chemical action of
matter. Larger inside dimensions such as 0.4 mm will be
reactive species produced by hot or UV-irradiated persulfate
required for samples with particulate matter.
ions. Even if oxygen is used as the sparging gas, it makes a
NOTE 1—See 6.1 concerning oxidation of particulate matter.
much lower contribution to oxidation than in high-temperature
(combustive) systems. Not all suspended or refractory material 7.3 Apparatus for Carbon Determination—This instrument
may be oxidized under these conditions; analysts should take consists of reagent and sample introduction mechanism, a
gas-spargedreactionvessel,agasdemisterordryer,orboth,an
steps to determine what recovery is being obtained. This may
be done by several methods: (a) by monitoring reaction optional CO trap, a CO -specific infrared detector, a control
2 2
system, and a display. Fig. 1 shows a diagram of such an
progress to verify that oxidation has been completed; (b)by
rerunning the sample under more vigorous reaction conditions; arrangement.
7.3.1 Sparging requires an inert vessel with a capacity of at
(c) by analyzing the sample by an alternative method, such as
Test Method D4129, known to result in full recovery; or (d)by least double the sample size with provision for sparging with
50 to 100 mL/min of carbon free gas. This procedure will
spiking samples with known refractories and determining
recovery. remove essentially all IC in 2 to 10 min, depending on design.
7.3.2 Oxidation—The reaction assembly contains reagent
6.2 Chloride ion tends to interfere with oxidative reaction
and sample introduction devices, and a reactor vessel with
mechanisms in this test method, prolonging oxidation times
sparging flow of carbon-free gas. The vessel may be heated by
and sometimes preventing full recovery. Follow manufactur-
an external source, and may contain a UV lamp. The reaction
er’s instructions for dealing with this problem. See Appendix
vessel and sparging vessel (see 6.3) may be combined.
X1 for supporting data.
7.3.3 Gas Conditioning—The gas passing from the reactor
6.3 Homogenizing or sparging of a sample, or both, may
is dried, and the CO produced is either trapped and later
cause loss of purgeable organic compounds, thus yielding a
released to the detector, or routed directly to the detector
value lower than the true TOC level. (For this reason, such
through a chlorine-removing scrubber.
measurements are sometimes known as nonpurgeable organic
7.3.4 Detector—The CO in the gas stream is detected by a
carbon (NPOC)). The extent and significance of such losses
CO -specific nondispersive infrared (NDIR) detector.
must be evaluated on an individual basis. This may be done by
7.3.5 Presentation of Results—The NDIR detector output is
comparing theTOC by difference (TC-IC) with the directTOC
related to stored calibration data and then displayed as milli-
figure, that is, that obtained from a sparged sample. The
grams of carbon per litre.
difference, if any, between these TOC figures represents
purgeable organic carbon (POC) lost during sparging.
8. Reagents and Materials
Alternatively, direct measurement of POC can be made during
8.1 Purity of Reagents—Reagent grade chemicals shall be
sparging, using optional capabilities of the analyzer.
used in all tests. Unless otherwise indicated, it is intended that
6.4 Note that error will be introduced when the method of
all reagents conform to the specifications of the Committee on
difference is used to derive a relatively small level from two
large levels. For example, a ground water high in IC and low
inTOCwillgiveapoorerTOCvalueas(TC-IC)thanbydirect
measurement.
Handbook for Monitoring Industrial Wastewater, Section 5.3, U.S. Environ-
ment Protection Agency, August 1973, pp. 5–12.
D4839 − 03 (2011)
Analytical Reagents of the American Chemical Society, method, and nitrogen or helium is preferred if a CO trap is
where such specifications are available. Other grades may be used between reactor and detector.
used, provided it is first ascertained that the reagent is of
9. Sampling and Sample Preservation
sufficient purity to permit its use without lessening the accu-
racy of the determination.
9.1 Collect the sample in accordance with Specification
D1192 and Practice D3370.
8.2 Purity of Water—Unless otherwise indicated, references
towatershallbeunderstoodtomeanreagentwaterconforming
9.2 To preserve samples for this analysis, store samples in
to Specification D1193, Type I or Type II. The indicated
glass at 4°C. To aid preservation, acidify the samples to a pH
specification does not actually specify inorganic carbon or
of 2. It should be noted that acidification will enhance loss of
organic carbon levels.These levels can affect the results of this
inorganiccarbon.Ifthepurgeableorganicfractionisimportant,
test method, especially at progressively lower levels of the
fill the sample bottles to overflowing with a minimum of
carboncontentinthesamplestobemeasured.Whereinorganic
turbulence and cap them using a fluoropolymer-lined cap,
carbon in reagent water is significant, CO -free water may be
without headspace.
prepared from reagent water by acidifying to pH 2, then
9.3 For monitoring of waters containing solids or immis-
sparging with fritted-glass sparger using CO -free gas (time
cible liquids that are to be injected into the reaction zone, use
will depend on volume and gas flow rate, and should be
a mechanical homogenizer or ultrasonic disintegrator. Filtering
determined by test).Alternatively, if the carbon contribution of
or screening may be necessary after homogenization to reject
the reagent water is known accurately, its effect may be
particle sizes that are too large for injection. Volatile organics
allowed for in preparation of standards and other solutions.
may be lost. See 6.3.
CO -freewatershouldbeprotectedfromatmosphericcontami-
9.4 Forwastewaterstreamswherecarbonconcentrationsare
nation. Glass containers are required for storage of water and
standard solutions. greater than the desired range of instrument operation, dilute
the samples as necessary.
8.3 Acid—Various concentrated acids may be used for
acidification of samples and of the oxidizing reagent. Acids
10. Instrument Operation
such as phosphoric (sp gr 1.69), nitric (sp gr 1.42), or sulfuric
10.1 Follow the manufacturer’s instructions for instrument
(sp gr 1.84) are suitable for most applications. Sulfuric acid
warm-up, gas flows, and liquid flows.
should be used in the form of a 1 + 1 dilution, for safety
reasons. Hydrochloric acid is not recommended.
11. Calibration
8.4 Organic Carbon, Standard Solution (2000 mg/L)—
11.1 Use the stock solution of 2000 mg/L of carbon, and
Choose a water-soluble, stable reagent grade compound, such
various dilutions of it, for calibration.
as benzoic acid or anhydrous potassium hydrogen phthalate
(KHC H O ). Calculate the weight of compound required to
8 4 4
NOTE 2—Dilutions should be made with CO -free water (see 8.2).
make 1 L of organic carbon standard solution; for example,
11.2 Calibration protocols may vary with equipment manu-
KHC H O = 0.471 g of carbon per gram, so one litre of 2 g/L
8 4 4
facturers. However, in general, calibrate the instrument in
of standard requires 2/0.471, or 4.25, grams of KHP. Dissolve
accordance with the manufacturer’s instructions, and use
the required amount of standard in some CO -free water in a
standards to verify such calibration in the specific range of
1-L volumetric flask, add 1 mL of acid, and dilute to volume.
interest for actual measurements. Plots of standard concentra-
This stock solution, or dilutions of it, may be used to calibrate
tionversusinstrumentreadingmaybeusedforcalibrationorto
and test performance of the carbon analyzer.
verify linearity of response.
8.5 Persulfate Solution—Prepare by dissolving the appro-
11.3 Establish instrument blank according to the manufac-
priateweightofpotassiumorsodiumpersulfatein1Lofwater,
turer’s instructions.
to produce the concentration specified by the instrument
manufacturer. If specified, add 1 mL of phosphoric acid (sp gr
12. Procedure
1.69) and mix well. Store in a cool, dark place. Recipes for this
12.1 Mixorblendeachsamplethoroughlyandcarryoutany
reagentsolutionmaybemodifiedbymanufacturerstomeetthe
necessary dilution to bring the carbon content within range of
needs of specific applications, for example, high chloride
the instrument.
samples.
12.2 If inorganic carbon is to be measured directly, inject
8.6 Gas Supply—Agas free of CO and of organic matter is
the sample into the analyzer under appropriate conditions.
required. Use a purity as specified by the equipment manufac-
turer. The use of oxygen is preferred for the UV-persulfate
12.3 If inorganic carbon is to be removed by sparging prior
to sample introduction, acidify to approximately pH 2 with
concentrated acid (if not already done) and sparge with an
appropriate flow of gas. Samples with high alkali content or
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
buffer capacity may require larger amounts of acid. In such
listed by the American Chemical Society, see A
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