5310 TOTAL ORGANIC CARBON (TOC)*

5310 A. Introduction

1. General Discussion

The organic carbon in water and wastewater is composed of a

variety of organic compounds in various oxidation states. Some

of these carbon compounds can be oxidized further by biological

or chemical processes, and the biochemical oxygen demand

(BOD), assimilable organic carbon (AOC), and chemical oxygen

demand (COD) methods may be used to characterize these

fractions. Total organic carbon (TOC) is a more convenient and

direct expression of total organic content than either BOD, AOC,

or COD, but does not provide the same kind of information. If a

repeatable empirical relationship is established between TOC

and BOD, AOC, or COD for a specific source water then TOC

can be used to estimate the accompanying BOD, AOC, or COD.

This relationship must be established independently for each set

of matrix conditions, such as various points in a treatment

process. Unlike BOD or COD, TOC is independent of the

oxidation state of the organic matter and does not measure other

organically bound elements, such as nitrogen and hydrogen, and

inorganics that can contribute to the oxygen demand measured

by BOD and COD. TOC measurement does not replace BOD,

AOC, and COD testing.

Measurement of TOC is of vital importance to the operation of

water treatment and waste treatment plants. Drinking water

TOCs range from less than 100 g/L to more than 25,000 g/L.

Wastewater may contain very high levels of organic compounds

(TOC 100 mg/L). Some of these applications may include

waters with substantial ionic impurities as well as organic matter.

In many applications, the presence of organic contaminants may

degrade ion-exchange capacity, serve as a nutrient source for undesired biological growth, or be otherwise detrimental to the process

for which the water is to be utilized. For drinking waters in particular, organic compounds may react with disinfectants to produce

potentially toxic and carcinogenic compounds.

To determine the quantity of organically bound carbon, the organic molecules must be broken down and converted to a single

molecular form that can be measured quantitatively. TOC methods

utilize high temperature, catalysts, and oxygen, or lower temperatures (100 °C) with ultraviolet irradiation, chemical oxidants, or

combinations of these oxidants to convert organic carbon to carbon

dioxide (CO2). The CO2 may be purged from the sample, dried, and

transferred with a carrier gas to a nondispersive infrared analyzer or

coulometric titrator. Alternatively, it may be separated from the

sample liquid phase by a membrane selective to CO2 into a highpurity water in which corresponding increase in conductivity is

related to the CO2 passing the membrane.

2. Fractions of Total Carbon

The methods and instruments used in measuring TOC analyze

fractions of total carbon (TC) and measure TOC by two or more

determinations. These fractions of total carbon are defined as:

inorganic carbon—the carbonate, bicarbonate, and dissolved CO2;

total organic carbon (TOC)—all carbon atoms covalently bonded in

organic molecules; dissolved organic carbon (DOC)—the fraction

of TOC that passes through a 0.45-m-pore-diam filter; suspended

organic carbon—also referred to as particulate organic carbon, the

fraction of TOC retained by a 0.45-m filter; purgeable organic

carbon—also referred to as volatile organic carbon, the fraction of

TOC removed from an aqueous solution by gas stripping under

specified conditions; and nonpurgeable organic carbon—the fraction of TOC not removed by gas stripping.

In most water samples, the inorganic carbon fraction is many

times greater than the TOC fraction. Eliminating or compensating for inorganic carbon interferences requires determinations of

both TC and inorganic carbon to measure TOC. Inorganic carbon

interference can be eliminated by acidifying samples to pH 2 or

less to convert inorganic carbon species to CO2. Subsequent

purging of the sample with a purified gas or vacuum degassing

removes the CO2 by volatilization. Sample purging also removes

purgeable organic carbon so that the organic carbon measurement made after eliminating inorganic carbon interferences is

actually a nonpurgeable organic carbon determination: determine purgeable organic carbon to measure TOC. In many surface and ground waters the purgeable organic carbon contribution to TOC is negligible. Therefore, in practice, the nonpurgeable organic carbon determination is substituted for TOC.

Alternatively, inorganic carbon interference may be compensated

for by separately measuring total carbon (TC) and inorganic carbon.

The difference between TC and inorganic carbon is TOC.

The purgeable fraction of TOC is a function of the specific

conditions and equipment employed. Sample temperature and

salinity, gas-flow rate, type of gas diffuser, purging-vessel dimensions, volume purged, and purging time affect the division

of TOC into purgeable and nonpurgeable fractions. When separately measuring purgeable organic carbon and nonpurgeable

organic carbon on the same sample, use identical conditions for

purging during the purgeable organic carbon measurement as in

purging to prepare the nonpurgeable organic carbon portion for

analysis. Consider the conditions of purging when comparing

purgeable organic carbon or nonpurgeable organic carbon data

from different laboratories or different instruments.

3. Selection of Method

The high-temperature combustion method (B) is suitable for

samples with higher levels of TOC that would require dilution

for the various persulfate methods (5310C or D). Generally, it

also will determine organic carbon from compounds that are

chemically refractory and not determined by 5310C or D. Hightemperature combustion may be desirable for samples containing

* Approved by Standard Methods Committee, 2000. Editorial revisions, 2011.

Joint Task Group: 20th Edition—Edward W.D. Huffman (chair), Karl O. Brinkmann, Rick C. Dage, Patricia Snyder Fair, Louis A. Kaplan, P. Lawrence Meschi,

James W. O’Dell, Misha Plam.

1
high levels of suspended organic carbon, which may not be

efficiently oxidized by persulfate and/or UV methods. Interlaboratory studies have shown biases on the order of 1 mg/L using

older high-temperature instruments. With newer instruments,

detection limits as low as 10 g/L have been reported. Some

high-temperature combustion instruments are not designed for

levels below 1 mg/L. The high-temperature methods accumulate

nonvolatile residues in the analyzer, whereas, in 5310C, residuals are drained from the analyzer. Section 5310C generally

provides better sensitivity for lower-level (1 mg/L) samples.

Persulfate and/or UV oxidation are useful for TOC as low as

10 g/L. Because the range of sensitivity of the methods overlaps, other factors may dictate method choice in the range of

1 mg/L to 50 mg/L. A method may be chosen on the basis of

desired precision, ease of use, cost, etc. Section 5310D generally

is equivalent to 5310C, but the equipment for 5310D is no longer

manufactured.

To qualify a particular instrument for use, demonstrate that the

single-user precision and bias given in each method can be

reproduced. Also, preferably demonstrate the overall precision

by conducting in-house studies with more than one operator.

Evaluate the selected method to ensure that data quality objectives are attained. Evaluate method detection level in a matrix

as similar as possible to the unknowns as described in Section

1030C. Be aware that instrument blanks are handled in a variety

of ways in TOC analyzers and that the true magnitude of the

blank may not be readily apparent to the analyst. Some instruments “zero out” much of the blank by adjusting the zero on the

detector. Others enter blank values in units such as mv responses

rather than absolute concentrations, whereas other instruments

accumulate the total blank in the system during a blank run.

Carefully observe the variability of low-level measurements and

check it any time reagents or instrument operations are changed.

The following methods note that when a water blank is run there

is a contribution to the observed blank value from the level of

carbon in the blank water.

The methods show expected single-operator and multiplelaboratory precision. These equations are based on referenced

interlaboratory studies that in some cases were performed on

older equipment. The range of testing is important to observe

because the error and bias generally will be some significant

fraction of the low standard. Consult references to determine

type of equipment and conditions of the interlaboratory study.

Determine the performance of the instrument being used by

analyzing waters with matrices similar to those of unknowns,

using the procedures outlined in Section 1040B.

4. Bibliography

FORD, D.L. 1968. Total organic carbon as a wastewater parameter. Pub.

Works 99:89.

FREDERICKS, A.D. 1968. Concentration of organic carbon in the Gulf of

Mexico: Off. Naval Res. Rep. 68 –27T.

WILLIAMS, P.M. 1969. The determination of dissolved organic carbon in

seawater: A comparison of two methods. Limnol. Oceanogr.

14:297.

CROLL, B.T. 1972. Determination of organic carbon in water. Chem. Ind.

(London) 110:386.

SHARP, J. 1973. Total organic carbon in seawater— comparison of measurements using persulfate oxidation and high temperature combustion. Mar. Chem. 1:211.

BORTLIJZ, J. 1976. Instrumental TOC analysis. Vom Wasser 46:35.

VAN STEENDEREN, R.A. 1976. Parameters which influence the organic

carbon determination in water. Water SA 2:156.

TAKAHASHI, Y. 1979. Analysis Techniques for Organic Carbon and

Organic Halogen. Proc. EPA/NATO-CCMS Conf. on Adsorption

Techniques. Reston, Va.

STANDING COMMITTEE OF ANALYSIS, DEPARTMENT OF THE ENVIRONMENT,

NATIONAL WATER COUNCIL. 1980. The instrumental determination of

total organic carbon, total oxygen demand and related determinants.

1979. Her Majesty’s Stationery Off., London.

WERSHAW, R.L., M.J. FISHMAN, R.R. GRABBE & L.E. LOWE, eds. 1983.

Methods for the Determination of Organic Substances in Water and

Fluvial Sediments. U.S. Geological Survey Techniques of Water

Resources Investigations, Book 5. Laboratory Analysis. Chapter

A3.

KAPLAN, L.A. 1992. Comparison of high-temperature and persulfate

oxidation methods for determination of dissolved organic carbon in

freshwaters. Limnol. Oceanogr. 37:1119.

BENNER, R. & J.I. HEDGES. 1993. A test of the accuracy of freshwater

DOC measurements by high-temperature catalytic oxidation and

UV-promoted persulfate oxidation. Mar. Chem. 41:75.

WANGERSKY, P.J. 1993. Dissolved organic carbon methods: A critical

review. Mar. Chem. 41:61.

HUTTE, R., R. GODEC & K. O’NEILL. 1994. Transferring NASA-sponsored advances in total organic carbon measurement to industrial

applications. Microcontamination 12(4):21.

KAPLAN, L.A. 1994. A field and laboratory procedure to collect, process,

and preserve freshwater samples for dissolved organic carbon analysis. Limnol. Oceanogr. 39:1470.

5310 B. High-Temperature Combustion Method

1. General Discussion

The high-temperature combustion method has been used for a

wide variety of samples, but its utility is dependent on particle

size reduction because it uses small-orifice syringes.

a. Principle: The sample is homogenized and diluted as necessary and a microportion is injected into a heated reaction

chamber packed with an oxidative catalyst such as cobalt oxide,

platinum group metals, or barium chromate. The water is vaporized and the organic carbon is oxidized to CO2 and H2O. The

CO2 from oxidation of organic and inorganic carbon is transported in the carrier-gas streams and is measured by means of a

nondispersive infrared analyzer, or titrated coulometrically.

Because total carbon is measured, inorganic carbon must be

removed by acidification and sparging or measured separately

and TOC obtained by difference.

Measure inorganic carbon by injecting the sample into a

reaction chamber where it is acidified. Under acidic conditions,

all inorganic carbon is converted to CO2, which is transferred to

the detector and measured. Under these conditions organic carbon is not oxidized and only inorganic carbon is measured.

Alternatively, convert inorganic carbonates to CO2 with acid

TOTAL ORGANIC CARBON (5310)/High-Temperature Combustion Method

2
and remove the CO2 by purging before sample injection. The

sample contains only the nonpurgeable organic carbon fraction

of total carbon: a purgeable organic carbon determination also is

necessary to measure TOC.

b. Interference: Removal of carbonate and bicarbonate by

acidification and purging with purified gas results in the loss of

volatile organic substances. The volatiles also can be lost during

sample blending, particularly if the temperature is allowed to

rise. Another important loss can occur if large carbon-containing

particles fail to enter the needle used for injection. Filtration,

although necessary to eliminate particulate organic matter when

only DOC is to be determined, can result in loss or gain of DOC,

depending on the physical properties of the carbon-containing

compounds and the adsorption or desorption of carbonaceous

material on the filter. Check filters for their contribution to DOC

by analyzing a filtered blank. Note that any contact with organic

material may contaminate a sample. Avoid contaminated glassware, plastic containers, and rubber tubing. Analyze sample

treatment, system, and reagent blanks.

Combustion temperatures above 950°C are required to decompose some carbonates. Systems that use lower temperatures must

destroy carbonates by acidification. Elemental carbon may not be

oxidized at lower temperatures but generally it is not present in

water samples nor is it formed during combustion of dilute

samples. The advantage of using lower temperatures (680°C) is

that fusion of dissolved salts is minimized, resulting in lower

blank values. Gases evolved from combustion, such as water,

halide compounds, and nitrogen oxides, may interfere with the

detection system. Consult manufacturers’ recommendations regarding proper selection of scrubber materials and check for any

matrix interferences.

The major limitation to high-temperature techniques is the

magnitude and variability of the blank. Instrument manufacturers

have developed new catalysts and procedures that yield lower

blanks, resulting in lower detection levels.

c. Minimum detectable concentration: 1 mg C/L or less,

depending on the instrument used. This can be achieved with

most high-temperature combustion analyzers although instrument performance varies. The minimum detectable concentration may be reduced by concentrating the sample, or by increasing the portion taken for analysis.

d. Sampling and storage: If possible, rinse bottles with sample

before filling and carry field blanks through sampling procedure

to check for any contamination that may occur. Collect and store

samples in glass bottles protected from sunlight and seal with

TFE-backed septa. Before use, wash bottles with acid, seal with

aluminum foil, and bake at 400°C for at least 1 h. Wash uncleaned TFE septa with detergent, rinse repeatedly with organicfree water, wrap in aluminum foil, and bake at 100°C for 1 h.

Check performance of new or cleaned septa by running appropriate blanks. Preferably use thick silicone rubber-backed TFE

septa with open ring caps to produce a positive seal. Less

rigorous cleaning may be acceptable if the concentration range is

relatively high. Check bottle blanks with each set of sample

bottles to determine effectiveness or necessity of cleaning. Preserve samples that cannot be examined immediately by holding

at 4°C with minimal exposure to light and atmosphere. Acidification with phosphoric or sulfuric acid to a pH 2 at the time of

collection is especially desirable for unstable samples, and may

be used on all samples: acid preservation, however, invalidates

any inorganic carbon determination on the samples.

2. Apparatus

a. Total organic carbon analyzer, using combustion techniques.

b. Sampling, injection, and sample preparation accessories, as

prescribed by instrument manufacturer.

c. Sample blender or homogenizer.

d. Magnetic stirrer and TFE-coated stirring bars.

e. Filtering apparatus and 0.45-m-pore-diam filters. Preferably use HPLC syringe filters with no detectable TOC blank.

Glass fiber or silver membrane filters also can be used. Rinse

filters before use and monitor filter blanks.

3. Reagents

a. Reagent water: Prepare reagents, blanks, and standard solutions from reagent water with a TOC value less than 2  the

MDL (see Sections 1030 and 1080).

b. Acid: Phosphoric acid, H3PO4. Alternatively use sulfuric

acid, H2SO4.

c. Organic carbon stock solution: Dissolve 2.1254 g anhydrous primary-standard-grade potassium biphthalate, C8H5KO4,

in carbon-free water and dilute to 1000 mL; 1.00 mL  1.00 mg

carbon. Prepare laboratory control standards using any other

appropriate organic-carbon-containing compound of adequate

purity, stability, and water solubility. Preserve by acidifying with

H3PO4 or H2SO4 to pH 2, and store at 4°C.

d. Inorganic carbon stock solution: Dissolve 4.4122 g anhydrous sodium carbonate, Na2CO3, in water, add 3.497 g anhydrous sodium bicarbonate, NaHCO3, and dilute to 1000 mL;

1.00 mL  1.00 mg carbon. Alternatively, use any other inorganic carbonate compound of adequate purity, stability, and

water solubility. Keep tightly stoppered. Do not acidify.

e. Carrier gas: Purified oxygen or air, CO2-free and containing less than 1 ppm hydrocarbon (as methane).

f. Purging gas: Any gas free of CO2 and hydrocarbons.

4. Procedure

a. Instrument operation: Follow manufacturer’s instructions

for analyzer assembly, testing, calibration, and operation. Adjust

to optimum combustion temperature before using instrument;

monitor temperature to insure stability.

b. Sample treatment: If a sample contains gross solids or

insoluble matter, homogenize until satisfactory replication is

obtained. Analyze a homogenizing blank consisting of reagent

water carried through the homogenizing treatment.

If inorganic carbon must be removed before analysis, transfer a

representative portion (10 to 15 mL) to a 30-mL beaker, add acid to

reduce pH to 2 or less, and purge with gas for 10 min. Inorganic

carbon also may be removed by stirring the acidified sample in a

beaker while directing a stream of purified gas into the beaker.

Because volatile organic carbon will be lost during purging of the

acidified solution, report organic carbon as total nonpurgeable organic carbon. Check efficiency of inorganic carbon removal for

each sample matrix by splitting a sample into two portions and

adding to one portion an inorganic carbon level similar to that of the

TOTAL ORGANIC CARBON (5310)/High-Temperature Combustion Method

3
sample. The TOC values should agree; if they do not, adjust sample

container, sample volume, pH, purge gas flow rate, and purge time

to obtain complete removal of inorganic carbon.

If the available instrument provides for a separate determination of inorganic carbon (carbonate, bicarbonate, free CO2) and

total carbon, omit decarbonation and determine TOC by difference between TC and inorganic carbon.

If dissolved organic carbon is to be determined, filter sample

through 0.45-m-pore-diam filter; analyze a filtering blank.

c. Sample injection: Withdraw a portion of prepared sample using

a syringe fitted with a blunt-tipped needle. Select sample volume

according to manufacturer’s direction. Stir samples containing particulates with a magnetic stirrer. Select needle size consistent with

sample particulate size. Other sample injection techniques, such as

sample loops, may be used. Inject samples and standards into

analyzer according to manufacturer’s directions and record response. Repeat injection until consecutive measurements are obtained that are reproducible to within 10%.

d. Preparation of standard curve: Prepare standard organic

and inorganic carbon series by diluting stock solutions to cover

the expected range in samples within the linear range of the

instrument. Dilute samples higher than the linear range of the

instrument in reagent water. Inject and record peak height or area

of these standards and a dilution water blank. Plot carbon concentration in milligrams per liter against corrected peak height or

area on rectangular coordinate paper. This is unnecessary for

instruments provided with a digital readout of concentration.

With most TOC analyzers, it is not possible to determine separate

blanks for reagent water, reagents, and the entire system. In addition, some TOC analyzers produce a variable and erratic blank that

cannot be corrected reliably. In many laboratories, reagent water is

the major contributor to the blank value. Correcting only the instrument response of standards (which contain reagent water  reagents  system blank) creates a positive error, while also correcting samples (which contain only reagents and system blank contributions) for the reagent water blank creates a negative error.

Minimize errors by using reagent water and reagents low in carbon.

Inject samples and procedural blanks (consisting of reagent

water taken through any pre-analysis steps—values are typically

higher than those for reagent water) and determine sample organic carbon concentrations directly from the readout or measurements by comparing corrected instrument response to the

calibration curve. Instruments with coulometric detectors do not

require calibration curves. Regularly analyze laboratory control

samples to confirm performance of the instrument (see Quality

Control, below). These detectors accumulate the system blank;

therefore, monitor system blank regularly.

5. Calculations

Calculate corrected instrument response of standards and samples by subtracting the reagent-water blank instrument response

from that of the standard and sample. Prepare a standard curve of

corrected instrument response vs. TOC concentration. Subtract

procedural blank from each sample instrument response and

compare to standard curve to determine carbon content. Apply

appropriate dilution factor when necessary. Subtract inorganic

carbon from total carbon when TOC is determined by difference.

NOTE: The reagent water blank may include an instrument contribution not dependent on reagent-water carbon, and a true response due to reagent-water carbon. When reagent-water carbon is

a significant fraction of reagent-water blank, a negative error no

larger than reagent-water blank is introduced in the sample values.

If TOC analyzer design permits isolation of each of the contributions to the total blank, apply appropriate blank corrections to

instrument response of standards (reagent blank, water blank, system blank) and sample (reagent blank and system blank).

6. Quality Control

The quality control practices considered to be an integral part

of each method are summarized in Table 5020:I.

Determine instrument detection limit according to Section 1030.

After every tenth analysis, analyze a blank and a laboratory

control sample prepared from a source of material other than the

calibration standards, at a level similar to the analytical samples.

Preferably prepare the laboratory control sample in a matrix similar

to that of the samples. Alternatively, periodically make known

additions to samples to ensure recovery from unknown matrices.

7. Precision

The difficulty of sampling particulate matter on unfiltered samples limits the precision of the method to approximately 5 to 10%.

Interlaboratory studies of high-temperature combustion methods

have been conducted in the range above 2 mg/L.1 The resulting

equation for single-operator precision on matrix water is:

So  0.027x  0.29

Overall precision is:

St  0.044x  1.49

where:

So  single-operator precision,

St  overall precision, and

x  TOC concentration, mg/L.

8. Reference

1. AMERICAN SOCIETY FOR TESTING AND MATERIALS. 1994. Standard Test

Method for Total and Organic Carbon in Water by High Temperature

Oxidation and by Coulometric Detection. D4129 – 88. Annual Book

of ASTM Standards. American Soc. Testing & Materials, Philadelphia, Pa.

9. Bibliography

KATZ, J., S. ABRAHAM & N. BAKER. 1954. Analytical procedure using a

combined combustion-diffusion vessel: Improved method for combustion of organic compounds in aqueous solution. Anal. Chem.

26:1503.

VAN HALL, C.E., J. SAFRANKO & V. A. STENGER. 1963. Rapid combustion

method for the determination of organic substances in aqueous

solutions. Anal. Chem. 35:315.

SCHAFFER, R.B. et al. 1965. Application of a carbon analyzer in waste

treatment. J. Water Pollut. Control Fed. 37:1545.

VAN HALL, C.E., D. BARTH & V. A. STENGER. 1965. Elimination of

carbonates from aqueous solutions prior to organic carbon determinations. Anal. Chem. 37:769.

BUSCH, A.W. 1966. Energy, total carbon and oxygen demand. Water

Resour. Res. 2:59.

TOTAL ORGANIC CARBON (5310)/High-Temperature Combustion Method

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BLACKMORE, R.H. & D. VOSHEL. 1967. Rapid determination of total

organic carbon (TOC) in sewage. Water Sewage Works 114:398.

WILLIAMS, R.T. 1967. Water-pollution instrumentation—Analyzer looks

for organic carbon. Instrum. Technol. 14:63.

AMERICAN SOCIETY FOR TESTING AND MATERIALS. 1994. Standard Test

Method for Total Organic Carbon in Water. D2579-93. Annual

Book of ASTM Standards. American Soc. Testing & Materials,

Philadelphia, Pa.

5310 C. Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method

1. General Discussion

Many instruments utilizing persulfate oxidation of organic carbon

are available. They depend either on heat or ultraviolet irradiation

activation of the reagents. These oxidation methods provide rapid

and precise measurement of trace levels of organic carbon in water.

a. Principle: Organic carbon is oxidized to carbon dioxide,

CO2, by persulfate in the presence of heat or ultraviolet light.

The CO2 produced may be purged from the sample, dried, and

transferred with a carrier gas to a nondispersive infrared (NDIR)

analyzer, or be coulometrically titrated, or be separated from the

liquid stream by a membrane that allows the specific passage of

CO2 to high-purity water where a change in conductivity is

measured and related to the CO2 passing the membrane.

Some instruments utilize an ultraviolet lamp submerged in a

continuously gas-purged reactor that is filled with a constantfeed persulfate solution. The samples are introduced serially into

the reactor by an autosampler or they are injected manually. The

CO2 produced is sparged continuously from the solution and is

carried in the gas stream to an infrared analyzer that is specifically tuned to the absorptive wavelength of CO2. The instrument’s microprocessor calculates the area of the peaks produced

by the analyzer, compares them to the peak area of the calibration standard stored in its memory, and prints out a calculated

organic carbon value in milligrams per liter.

Other UV-persulfate instruments use continuous-flow injection of the sample into the instrument. Removal of inorganic

carbon by vacuum degassing is provided optionally. The sample

is acidified and persulfate added. Sample flow is split; one

channel passes to a delay coil while the other passes through the

UV reactor. The CO2 from each stream is separated from the

sample stream by membranes selectively permeable to CO2 that

allow the CO2 to pass into high-purity water where change in

conductivity is measured. CO2 from the non-UV-irradiated

stream represents inorganic carbon. CO2 from the irradiated

stream represents TC. The instrument automatically converts the

detector signals to unit of concentration (mg/L or g/L). The

TOC is calculated as the difference between the TC and inorganic carbon channels.

Heated-persulfate instruments utilize a digestion vessel heated

to 95 to 100°C. Samples are added by direct injection, loop

injection, line injection, or autosampler. After inorganic carbon

is removed by acidification and sparging, a measured amount of

persulfate solution is added to the sample. After an oxidation

period, the resulting CO2 is sparged from the solution and carried

to an infrared analyzer specifically tuned to the absorptive wavelength of CO2. The instrument’s microprocessor converts the

detector signal to organic carbon concentrations in mg/L based

on stored calibration data.

b. Interferences: See 5310B.1b. Insufficient acidification will

result in incomplete release of CO2.

The intensity of the ultraviolet light reaching the sample

matrix may be reduced by highly turbid samples or with aging of

the ultraviolet source, resulting in sluggish or incomplete oxidation. Large organic particles or very large or complex organic

molecules such as tannins, lignins, and humic acid may be

oxidized slowly because persulfate oxidation is rate-limited.

However, oxidation of many large biological molecules such as

proteins and monoclonal antibodies proceeds rapidly. Because

the efficiency of conversion of organic carbon to CO2 may be

affected by many factors, check efficiency of oxidation with

selected model compounds representative of the compounds of

interest in a matrix representative of the sample.

Some instruments give low results for certain difficult-to-oxidize

compounds under certain conditions. The following compounds are

difficult to oxidize, are sufficiently soluble in water, and can be

mixed and measured accurately at trace levels: urea, nicotinic acid,

pyridine, n-butanol, acetic acid, leucine, acetonitrile, octoxynol-9,

tartaric acid, 1,10-phenanthroline, 1-glutonic acid, 2-propanol, and

sodium dodecylbenzenesulfonate. Use these compounds as matrix

additions to evaluate oxidation efficiency.

Persulfate oxidation of organic molecules is slowed in samples

containing significant concentrations of chloride by the preferential

oxidation of chloride; at concentrations above 0.05% chloride, oxidation of organic matter may be inhibited. To remove this interference add mercuric nitrate* to the persulfate solution in UV-persulfate instruments, or extend reaction time and/or increase amount of

persulfate solution in heated-persulfate instruments.

With any organic carbon measurement, contamination during

sample handling and treatment is a likely source of interference.

This is especially true of trace analysis. Take extreme care in

sampling, handling, and analysis of samples below 1 mg TOC/L.

c. Minimum detectable concentration: Concentration of 0.01 mg

TOC/L can be measured by some instruments if scrupulous attention is given to minimizing sample contamination and method

background. See Section 1030 for procedures to evaluate the MDL

for a specific instrument. Use the high-temperature combustion

method (B) for high concentrations of TOC or dilute the sample,

ensuring that the dilution process does not contaminate the sample.

d. Sampling and storage: See 5310B.ld.

2. Apparatus

a. Total organic carbon analyzer utilizing persulfate oxidation

principle.

*NOTE: If mercuric nitrate is used to complex the chloride, use an appropriate

disposal method for the treated waste to prevent mercury contamination.

TOTAL ORGANIC CARBON (TOC) (5310)/Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method

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b. Sampling and injection accessories, as specified by the

instrument manufacturer.

3. Reagents

a. Reagents listed in 5310B.3.

b. Persulfate solution: Different instrument manufacturers recommend different forms and concentrations of peroxydisulfate.

Typical preparations are as follows:

1) Sodium peroxydisulfate, 10%: Dissolve 100 g reagent in

water; bring volume to 1 L.

2) Ammonium peroxydisulfate, 15%: Dissolve 150 g reagent in

water; bring volume to 1 L.

3) Potassium peroxydisulfate, 2%: Dissolve 20 g reagent in

water; bring volume to 1 L.

Check blank values from reagents and, if values are high,

purify reagent or use a higher-purity source.

4. Procedure

a. Instrument operation: Follow manufacturer’s instructions

for assembly, testing, calibration, and operation.

b. Sample preparation: If a sample contains gross particulates

or insoluble matter, homogenize until a representative portion

can be withdrawn through the syringe needle, autosampler tubing, or sample inlet system of continuous on-line monitor.

If dissolved organic carbon is to be determined, filter sample

and a reagent water blank through 0.45-m filter. HPLC syringe

filters have been found to pass water without contamination.

Glass fiber or silver membrane filters also can be used. Check

filter blanks regularly.

To determine nonpurgeable organic carbon, transfer 15 to

30 mL sample to a flask or test tube and acidify to a pH of 2.

Purge according to manufacturer’s recommendations. In some

instruments this is performed internally. Check efficiency of

inorganic carbon removal for each sample matrix by splitting a

sample into two portions; to one of the portions, add inorganic

carbon to a level similar to that of the sample. The TOC values

should agree. If the values do not agree, adjust conditions such

as sample container, sample volume, pH, purge-gas flow rate,

and purge time to obtain complete removal of inorganic carbon.

c. Sample injection: See 5310B.4c.

d. Standard curve preparation: Prepare an organic carbon

standard series over the range of organic carbon concentrations

in the samples. Run standards and blanks and record analyzer’s

response. Determine instrument response for each standard and

blank. Unless carbon dioxide is trapped and desorbed, producing

consistent peak heights, determinations based on peak height

may be inadequate because of differences in the rate of oxidation

of standards and samples. Correct instrument response of standards by subtracting reagent water blank and plot organic carbon

concentration in milligrams per liter against corrected instrument

response. For instruments providing a digital computation of

concentration, this is not necessary. Be sure that the instrument’s

algorithm includes blank correction and linearity of response.

Analyze standards having concentrations above and below those

determined in the samples, preferably prepared in a similar

matrix, to confirm proper instrument operation.

5. Calculation

See 5310B.5, or use instrument manufacturer’s procedure.

6. Quality Control

See 5310B.6.

7. Precision and Bias

Interlaboratory studies of persulfate and/or UV with NDIR

detection methods have been conducted in the range of 0.1 mg/L

to 4000 mg/L of carbon.1 The resulting equation for organic

carbon, single-operator precision is:

So  0.04x  0.1

Overall precision is expressed as:

St  0.08x  0.1

where:

So  single-operator precision,

St  overall precision, and

x  TOC concentration, mg/L.

An interlaboratory study was conducted for the membrane

conductivity method,† covering samples with 1 to 25 mg/L

organic carbon concentrations. The resulting equation for singleoperator precision is:

So  0.012x  0.022

Overall precision is expressed as:

St  0.027x  0.09

where terms are defined as above.

8. Reference

1. AMERICAN SOCIETY FOR TESTING AND MATERIALS. 1994. Standard Test

Method for Total Carbon in Water by Ultraviolet, or Persulfate

Oxidation, or Both, and Infrared Detection. D4839-88. Annual Book

of ASTM Standards. American Soc. Testing & Materials, Philadelphia, Pa.

9. Bibliography

BEATTIE, J., C. BRICKER & D. GARVIN. 1961. Photolytic determination of

trace amounts of organic material in water. Anal. Chem. 33:1890.

ARMSTRONG, F.A.J., P.M. WILLIAMS & J.D.H. STRICKLAND. 1966. Photooxidation of organic matter in sea water by ultraviolet radiation,

analytical and other applications. Nature 211:481.

BRAMER, H.C., M.J. WALSH & S.C. CARUSO. 1966. Instrument for monitoring trace organic compounds in water. Water Sewage Works

113:275.

DOBBS, R.A., R.H. WISE & R.B. DEAN. 1967. Measurement of organic

carbon in water using the hydrogen flame ionization detector. Anal.

Chem. 39P:1255.

† Data may be obtained from Standard Methods technical information manager at

www.standardmethods.org/contact/.

TOTAL ORGANIC CARBON (TOC) (5310)/Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method

6
MONTGOMERY, H.A.C. & N.S. THOM. 1967. The determination of low

concentrations of organic carbon in water. Analyst 87:689.

ARMSTRONG, F.A.J. & S. TIBBITS. 1968. Photochemical combustion of

organic matter in seawater for nitrogen, phosphorus and carbon

determination. J. Mar. Biol. Assoc. U.K. 48:143.

JONES, R.H. & A.F. DAGEFORD. 1968. Application of a high sensitivity

total organic carbon analyzer. Proc. Instr. Soc. Amer. 6:43.

TAKAHASHI, Y., R.T. MOORE & R.J. JOYCE. 1972. Direct determination of

organic carbon in water by reductive pyrolysis. Amer. Lab. 4:31.

COLLINS, K.J. & P.J. LEB. WILLIAMS. 1977. An automated photochemical

method for the determination of dissolved organic carbon in sea and

estuarine waters. Mar. Chem. 5:123.

GRAVELET-BLONDIN, L.R., H.R. VAN VLIET & P.A. MYNHARDT. 1980. An

automated method for the determination of dissolved organic carbon in fresh water. Water SA 6:138.

OAKE, R.J. 1981. A Review of Photo-Oxidation for the Determination of

Total Organic Carbon in Water. Water Research Center, Technical

Rep. (TR 160). Medmenham, England.

VAN STEENDEREN, R.A. & J.S. LIN. 1981. Determination of dissolved

organic carbon in water. Anal. Chem. 53:2157.

AIKEN, G.R. 1992. Chloride interference in the analysis of dissolved organic

carbon by the wet oxidation method. Environ. Sci. Technol. 26:2435.

GODEC, R., K. O’NEIL & R. HUTTE. 1992. New Technology for TOC

Analysis in Water. Ultrapure Water 9(9):17.

5310 D. Wet-Oxidation Method

1. General Discussion

The wet-oxidation method is suitable for the analyses of water,

water-suspended sediment mixtures, seawaters, brines, and

wastewaters containing at least 0.1 mg nonpurgeable organic

carbon/L. The method is not suitable for the determination of

volatile organic constituents.

a. Principle: The sample is acidified, purged to remove inorganic carbon, and oxidized with persulfate in an autoclave at

temperatures from 116 to 130°C. The resultant carbon dioxide

(CO2) is measured by nondispersive infrared spectrometry.

b. Interferences: See 5310B.1b and C.1.b

c. Minimum detectable concentrations: High concentrations of

reducing agents may interfere. Concentration of 0.10 mg TOC/L

can be measured if scrupulous attention is given to minimizing

sample contamination and method background. Use the hightemperature combustion method (B) for high concentrations of

TOC.

d. Sampling and storage: See 5310B.1d.

2. Apparatus

a. Ampules, precombusted, 10-mL, glass.

b. Ampule purging and sealing unit.

c. Autoclave.

d. Carbon analyzer.

e. Homogenizer.

3. Reagents

In addition to the reagents specified in 5310B.3a, c, e, and f,

the following reagents are required:

a. Phosphoric acid solution, H3PO4, 1.2N: Add 83 mL H3PO4

(85%) to water and dilute to 1 L with water. Store in a tightly

stoppered glass bottle.

b. Potassium persulfate, reagent-grade, granular. Avoid using

finely divided forms.

4. Procedure

Follow manufacturer’s instructions for instrument assembly,

testing calibration, and operation. Add 0.5 mL 1.2N H3PO4,

solution to precombusted ampules.

To analyze for dissolved organic carbon, follow the filtration procedure in 5310B. Homogenize sample to produce a

uniform suspension. Rinse homogenizer with reagent water

after each use. Pipet water sample (10.0 mL maximum) into

an ampule. Adjust smaller volumes to 10 mL with reagent

water. Prepare one reagent blank (10 mL reagent water plus

acid and oxidant) for every 15 to 20 water samples. Prepare

standards covering the range of 0.1 to 40 mg C/L by diluting

the carbon standard solution. Immediately place filled ampules on purging and seating unit and purge them at rate of

60 mL/min for 6 min with purified oxygen. Add 0.2 g potassium persulfate using a dipper calibrated to deliver 0.2 g to

the ampule. Seal samples according to the manufacturer’s

instructions. Place sealed samples, blanks, and a set of standards in ampule racks in an autoclave and digest 4 h at

temperature between 116 and 130°C.

Set sensitivity range of carbon analyzer by adjusting the zero

and span controls in accordance with the manufacturer’s instructions. Break combusted ampules in the cutter assembly of the

carbon analyzer, sweep CO2 into the infrared cell with nitrogen

gas, and record area of each CO2 peak. CAUTION: Because

combusted ampules are under positive pressure, handle with

care to prevent explosion.

5. Calculations

Prepare an analytical standard curve by plotting peak area of

each standard versus concentration (mg/L) of organic carbon

standards. The relationship between peak area and carbon concentration is curvilinear. Define operating curves each day samples are analyzed.

Report nonpurgeable organic carbon concentration as follows:

0.1 mg/L to 0.9 mg/L, one significant figure; 1.0 mg/L and

above, two significant figures.

6. Quality Control

See 5310B.6.

7. Precision and Bias

Multiple determinations of four different concentrations of

aqueous potassium acid phthalate samples at 2.00, 5.00, 10.0,

TOTAL ORGANIC CARBON (TOC) (5310)/Wet-Oxidation Method

7
and 40.0 mg C/L resulted in mean values of 2.2, 5.3, 9.9, and

38 mg/L and standard deviations of 0.13, 0.15, 0.11, and 1.4,

respectively.

Precision also may be expressed in terms of percent relative

standard deviation as follows:

Number of

Replicates

Mean

mg/L

Relative Standard

Deviation

%

9 2.2 5.9

10 5.3 2.8

10 9.9 1.1

10 38.0 3.7

8. Bibliography

WILLIAMS, P.M. 1969. The determination of dissolved organic carbon in

seawater: A comparison of two methods. Limnol. Oceanogr. 14:297.

OCEANOGRAPHY INTERNATIONAL CORP. 1970. The total carbon system

operating manual. College Station, Tex.

MACKINNON, M.D. 1981. The measurement of organic carbon in seawater. In E.K. Duursma & R. Dawson, eds., Marine Organic Chemistry: Evolution, Composition, Interactions and Chemistry of Organic Matter in Seawater. Elsevier Scientific Publishing Co., New

York, N.Y.

TOTAL ORGANIC CARBON (TOC) (5310)/Wet-Oxidation Method

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