5310
Total Organic Carbon
Methods A, B, D and E approved by Standard Methods Committee, 2022. Joint Task Group: Akin Babatola (chair), Amber Baylor, Dominic Brose, Richard Burrows, Brett
Clark, Sage Mosteller, Mary Johnson, William Lipps, Devon Morgan, Kawal Padda, Robin Parnell, Shannon Pratt.
Method C approved Standard Methods Committee, 2014. Joint Task Group: Edward W.D. Huffman (chair), George Aiken, Theresa M. Bousquet, Louis A. Kaplan, Lisa M.
Ramirez, Stephen J. Randtke.
5310
1. General Discussion
Organic carbon in environmental and other water matrices may
exist in a variety of oxidation states. Some of these compounds
can be oxidized further via biological or chemical processes. Bio-
chemical oxygen demand (BOD), carbonaceous BOD (CBOD),
biodegradable organic carbon (BOC), chemical oxygen demand
(COD), and total organic carbon (TOC) analytical methods may
be used to characterize these fractions. Total organic carbon pro-
vides a more convenient and direct expression of total organic con-
tent than BOD, CBOD, BOC, or COD. Analyses of TOC provide
a measurement of the organic content of a sample that is indepen-
dent of the organic matter’s oxidation state and does not measure
other organically bound elements (e.g., nitrogen and hydrogen)
or inorganics that can contribute to the oxygen demand measured
by BOD and COD. The amount of TOC in water sources may be
used to define the matrix and its quality and can range from ≤0.1
to 25 mg/L in drinking water to ≥300 mg/L in wastewater influ-
ent and industrial effluents. Although none of these techniques
(BOD, BOC, COD, TOC) are direct correlates of each other, sev-
eral studies have demonstrated that correlations can be developed
between any pair of them and TOC can be used as a surrogate for
some of these other parameters in certain cases. This has been
acceptable under some regulatory frameworks including National
Pollutant Discharge Elimination System (NPDES) permits. The
regulatory authority to develop a correlation is found in the Clean
Water Act 40 CFR § 133.104(b) (sampling and test procedures);
however, no methods are provided for establishing a long-term
correlation or other repeatable empirical relationship. A correla-
tion provides a measure of the strength of association between
two continuous variables. Regression quantifies the effect of one
continuous variable on another dependent continuous variable. A
long-term study consists of a minimum of one year of samples
collected no less than once weekly to capture seasonal variations
in operating conditions. For regions with little to no seasonal vari-
ation, studies shorter than one year may be sufficient. Although
a correlation establishes a relationship, regression establishes an
equation to quantify the relationship that can be used to report a
calculated value for the dependent variable. Correlation coeffi-
cients provide a metric of the strength of association between two
variables. Generally, those greater than 0.50 but less than 0.70
indicate a moderately weak to strong correlation and those greater
than 0.70 are sufficiently strong and indicative of an empirical
relationship. These relationships may need to be established inde-
pendently for each set of matrix conditions (e.g., various points in
a treatment process and water types).
https://doi.org/10.2105/SMWW.2882.104
A. Introduction
Organic contaminants in water may degrade ion-exchange
capacity, serve as a carbon or energy source for undesired bio-
logical growth, react with disinfectants to form byproducts that
could harm human health or aquatic organisms, or be otherwise
detrimental to the water’s purpose. Before organically bound car-
bon can be analyzed, the molecules must be converted into carbon
dioxide (CO2), a molecular form that can be measured quantita-
tively. Current TOC methods use one of the following means of
oxidation to convert organic carbon into carbon dioxide:
• high temperature combustion (typically 680 to 1200 °C) with
or without catalysts and oxygen or air,
• heated persulfate (typically 95 to 100 °C) with one or more
chemical oxidants and catalyst,
• UV irradiation with one or more chemical oxidants, or
• supercritical water oxidation (typically 375 °C and 22.1 MPa)
with chemical oxidant.
The CO2 may be purged from the sample, dried, and trans-
ferred via carrier gas to a nondispersive infrared analyzer or cou-
lometric titrator. Alternatively, CO2 may be separated from the
sample via a CO2-selective membrane into high-purity water,
where the increase in conductivity corresponds to the amount of
CO2 passing through the membrane.
2. Fractions of Total Carbon
The methods and instruments used to measure TOC analyze
fractions of total carbon (TC) and measure TOC via two or more
determinations. These fractions of total carbon are defined as:
• inorganic carbon (IC)—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-µm-pore-diameter filter;
• suspended organic carbon (also called particulate organic
carbon)—the fraction of TOC retained by a 0.45-µm filter;
• purgeable organic carbon (also called volatile organic car-
bon)—the fraction of TOC removed from an aqueous solu-
tion via gas stripping under specified conditions; and
• nonpurgeable organic carbon (NPOC)—the fraction of TOC
not removed by gas stripping. In most cases, inorganic car-
bon is purged and not determined, in which case only NPOC
is determined and purgeable organic carbon is assumed to be
negligible.
In many water samples, the IC fraction is many times larger than
the TOC fraction. The IC fraction can be eliminated by adjusting
1
 5310 Total Organic Carbon - A. Introduction
samples to pH 4 or less to convert the IC species to CO2. Samples
are normally adjusted to pH 2 or less; however, this may maximize
hydrophobic molecule loss to the sample vessel walls. Adjusting
to pH 4 minimizes such losses, but IC-removal efficiency must
be checked and carbonate minerals in unfiltered samples may not
completely dissolve. The CO2 is then removed by purging the
sample with a purified gas (free of both CO2 and organic con-
taminants) or by vacuum degassing. Sample purging also removes
purgeable organic carbon, so the organic carbon measurement
made after eliminating IC interferences is actually an NPOC
determination. In many surface and ground waters, the purgeable
organic carbon contribution to TOC is negligible, so in practice the
NPOC determination is commonly substituted for TOC.
Alternatively, TOC may be determined by separately mea-
suring TC and IC, and calculating the difference. If the sample
contains far more IC than TOC, subtracting IC from TC is not
the preferred approach to determining TOC because of the rel-
atively large error involved. The purgeable fraction of TOC is
a function of the specific conditions and equipment used. Sam-
ple 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 frac-
tions. When separately measuring purgeable organic carbon and
NPOC in the same sample, use identical purging conditions for
both fractions. Also, consider purging conditions when compar-
ing purgeable organic carbon or NPOC data from different labo-
ratories or instruments.
3. Method Selection
The high-temperature combustion (5310 B) and supercritical
water oxidation (5310 E) methods are suitable for samples with
higher TOC levels, which otherwise would have to be diluted for
some of the persulfate methods (5310 C). Generally, 5310 B and
5310 E determine organic carbon levels in compounds that are
chemically refractory. These compounds cannot be determined
by 5310 C. High-temperature combustion or supercritical water
oxidation may be desirable for samples containing high levels
of suspended organic carbon or more than 500 mg/L of chloride
or other halides, where carbon may not be oxidized efficiently
by persulfate or UV irradiation methods. When analyzing saline
waters, care must be taken when using the combustion method.
Manufacturers may offer different catalyst packing schemes that
increase the life of the column and minimize the formation of
salt cakes. Supercritical water oxidation reactors operate at lower
temperatures and cool rapidly to room temperature. This allows
the analyzer to be operated on very contaminated samples without
building up salts and particulates. Saline waters can additionally
be analyzed with dilution water flushes between samples to rinse.
For methods using chemical oxidizers (5310 C and 5310 E),
samples containing inorganic reducing compounds often con-
sume some of the oxidizer, causing incomplete oxidation of
organic compounds. The result is low NPOC, TC, and TOC
measurements and higher oxidizer consumption. Species that are
known to produce this effect are halides and nitrite. In 5310 E,
salts tend to precipitate in the reactor when supercritical condi-
tions are reached. This makes those species less reactive during
the oxidation, while the organic compounds are more soluble and
more reactive. This minimizes interference from inorganic com-
pound oxidizer scavenging.
https://doi.org/10.2105/SMWW.2882.104
Some water samples contain species that form toxic products
when they are acidified or oxidized. Species such as cyanide, sul-
fide, and fluoride produce toxic gases when acidified. Safety con-
siderations must be made before analyzing these samples.
Interlaboratory studies have shown biases on the order of
1 mg/L C using older high-temperature instruments. With newer
instruments, bias has been reduced and detection limits as low
as 0.010 mg/L C have been reported. Some high-temperature
combustion instruments are not designed for levels <1 mg/L C.
Method 5310 B accumulates nonvolatile residues in the analyzer,
while in 5310 C and 5310 E residuals are drained from the analy-
zer after each analysis. Method 5310 C generally provides better
sensitivity for lower-level samples (<1 mg/L C); it is useful for
TOC as low as 0.010 mg/L C.
Because the sensitivity range of the methods overlaps, other
factors may dictate method choice. A method may be chosen
based on desired precision, ease of use, cost, or other factors.
Samples high in particulate organic carbon are problematic
for any TOC technique. Even if the particulates can be homog-
enously suspended, they may selectively adhere to sample intro-
duction portions of the analyzer. The best approach is to filter
the samples using carbon-free filters and analyze the filtrate for
DOC, then analyze the filters for particulate organic carbon using
an appropriate carbon analyzer.
To qualify a particular instrument for use, demonstrate that the
single-user precision and bias given in each method can be repro-
duced. Preferably, demonstrate overall precision by conduct-
ing in-house studies with more than one operator. Evaluate the
selected method to ensure that data quality objectives are attained.
Evaluate the method detection level in a matrix as similar as
possible to the unknowns. Be aware that TOC analyzers handle
instrument blanks in a variety of ways 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 detec-
tor’s baseline reading. Some enter blank values in units (e.g., mv
responses) rather than absolute concentrations, and others accu-
mulate the total blank in the system during a blank run. Carefully
observe the variability of low-level measurements, and both the
method detection level and the blank whenever reagents or instru-
ment operations are changed.
Methods 5310 B, C, and E note that when a water blank is
analyzed, the carbon level in the blank water contributes to the
observed blank value. However, an instrument blank should only
represent the contribution of reagents or system upset (injection
blank). Organic carbon-free water exposed to the atmosphere can
rapidly gain TOC. Modern instrumentation provides schemes to
recycle previously combusted water or allows reagent blanks to
be run in the absence of injected water. Some instruments have
on-line capability or sample-introduction procedures so low-TOC
water can be injected without exposure to the atmosphere. Blank
values should be based on internally recycled water or reagent
blanks, and external blank water injections should not be sub-
tracted from determined sample values. Determine the back-
ground TOC level in the reagent water used to prepare standards.
Handle this water similarly to the standards and subtract the
background TOC level from the TOC level of the standards. Do
not subtract the background TOC level from the samples unless
they are diluted; in which case, subtract the dilution water’s con-
tribution to the TOC concentration. Evaluate each instrument or
external sparging system (or both) for IC removal. The efficiency
2
 5310 Total Organic Carbon - A. Introduction
of IC removal can be significantly altered by minor changes in the
sparging system or by changes in sample temperature. Whenever
the sparging system is altered, re-evaluate IC removal efficiency.
The methods show expected single-operator and multiple-laboratory
precision. These equations are based on referenced interlab-
oratory studies that, in some cases, were performed on older
equipment. Observe the testing range because the error and bias
generally is a significant fraction of the low standard. Consult
references to determine the type of equipment and conditions of
the interlaboratory study. Determine instrument performance by
analyzing waters with matrices similar to those of the unknowns.
4. Filtering Samples for DOC Determinations
Ideally, a 0.45-µm pore-size filter is required to determine
DOC; however, in practice, glass fiber filters with larger nominal
pore sizes are often used.
a. Filter apparatus: Glass, polytetrafluoroethylene (PTFE),
stainless steel, acetyl resin, or other material that neither adsorbs
nor leaches organic substances and is capable of holding the
selected filters may be used. Polypropylene syringes with syringe-
type filter holders or peristaltic pumps with in-line filter holders
may be used as an alternative to vacuum filtration.
b. Filters: Use a glass fiber filter without organic binder or else
filters made of PTFE, polycarbonate, silver, polyethersulfone,
or hydrophilic polypropylene. Other filters that neither adsorb
nor leach organic carbon into water may be used, especially if
colloidal matter must be removed. The specific filter used must
be documented along with the data. Filters commonly used are
2.2 to 4.7 cm in diameter, although this may vary. Syringe filters
are also common. Alternatively, centrifugation may be used to
remove colloidal material.
Prerinse the filter with organic-free water to remove soluble
impurities. Glass fiber filters may be combusted at high tem-
peratures (450 to 500 °C for at least 1 h) before rinsing. If alter-
nate separation techniques, filters, or filter preparations are used,
demonstrate that equivalent results are produced. Filter pore size
may influence test results, especially in raw waters. When filtering
samples, check applicable regulations to see if the filter must have
an absolute pore size of 0.45 µm because not all glass fiber filters
meet this requirement. For highly turbid samples, prefilters (includ-
ing glass fiber) may be used to remove interferences and minimize
clogging of 0.45-µm filters. Studies have shown that hydrophilic
polyethersulfone or polypropylene filters are the best options.1
c. Filter blanks: Filters can both release and adsorb DOC.
Before use, a filter must be rinsed to remove any potential DOC.
Also, for each filter type and manufacturer, determine and docu-
ment the volume required so the resulting filtrate analysis yields
a TOC result <1/2 the minimum reporting limit (MRL; see 1020
B). Begin with 3 successive rinses of 25 mL each, and analyze
the third rinse for TOC. If analysis of the third aliquot yields a
result <1/2 MRL, then the volume used is acceptable. If the value
exceeds 1/2 MRL, continue with another 25 mL rinse and ana-
lyze. Continue the process until a sufficient rinsing volume has
been determined.
d. Filter to waste: If possible, pass a portion of the sample
through the filter to waste before beginning to collect filtrate. For
the recommended filters, 25 mL was generally found to be
an adequate amount to discard before collecting sample. The
https://doi.org/10.2105/SMWW.2882.104
filter-to-waste volume can be determined on a low suspended
solids sample by collecting aliquots of filtrate and determining
DOC on the aliquots until the difference in DOC values between
sample and filtrate is insignificant.
e. Filter plugging: Filter plugging is a common problem. A
glass prefilter that has been heated to 500 °C for 1 hour in a muffle
furnace or an organic-free glass fiber filter that has been demon-
strated to be free of interferences and prerinsed immediately
before use has been shown to be effective in reducing plugging.
5. Quality Control Applicable to All Methods
a. Initial demonstration of performance: This should be done
whenever a new instrument is set up, a method or instrument is
modified, or a new operator is trained.
1) Initial demonstration of calibration and precision—Analyze
at least 4 replicates of a midrange calibration check sample pre-
pared from a different source than that used for the calibration.
The average obtained value should be within 15% of the theoret-
ical, and the relative standard deviation (RSD) should be <10%.
2) Method detection limit—Determine the method detection
limit (MDL) according to 5020 B.2.
3) Demonstration of IC-removal efficiency—Purged samples
may absorb organics or CO2 from the atmosphere, so analyze
samples immediately after purging or cap them tightly until an
aliquot is injected. Use the procedure in 5310 A.5b10 to demon-
strate IC removal efficiency. The necessary sparging time may be
determined by sparging for various times and selecting the time
required to obtain a value <1/2 MRL.
4) TOC carryover check—Immediately following the analysis
of the highest calibration standard, analyze a blank. The concen-
tration of the blank must be <1/2 MRL. If the blank has a value
>1/2 MRL, then the highest calibration point must be lowered until
the blank immediately following the point has a value <1/2 MRL.
Analyze the high calibration point/blank pair at the beginning of
every analytical day to verify that carryover is not occurring.
b. Ongoing quality control:
1) Holding time—For DOC, an unpreserved sample must be fil-
tered and then preserved within 48 hours of collection. For NPOC
analysis, adjust the original sample or filtrate to pH ≤2. Samples
must be stored at ≤6 °C. Preserve samples with HCl, H2SO4, or
H3PO4, depending on instrument recommendations. High chlo-
ride content in a sample may cause a bias to the reported results on
some instruments. Analyze all samples within 28 d of collection.
When determining IC and then TOC via difference and
high-temperature combustion, refrigerate sample, do NOT adjust
its pH, and analyze it as soon as possible because TOC may bio-
degrade significantly before the regulatory 28-d holding time
expires. Alternatively, determine IC on an unacidified sample and
then determine TOC by difference using a second, acidified sam-
ple. Keep in mind that the IC result for the acidified sample used
to determine TOC does not represent the IC concentration of the
unacidified sample.
2) Collect samples in glass bottles—Amber glass is preferred, but
clear glass may be used if the sample is protected from light. Alter-
native containers may be used if it is demonstrated that the container
does not remove or add TOC resulting in a level >1/2 MRL.
3) Calibration check sample—At least once per analytical
day, analyze a midrange calibration check sample prepared from
3
 5310 Total Organic Carbon - B. High-Temperature Combustion Method
a different source than that used for the initial calibration. The
results must be within 10% of the theoretical.
4) Initial instrument blank—Analyze a blank consisting of
recycled water or low TOC water. The purpose is to determine if
there is any TOC present in the instrument that may contaminate
the system. Instrument blank results must be <1/2 MRL and not
affect the linearity of the calibration curve. If the result is higher,
analyze several blanks to clear the system.
5) Method blank—After the initial calibration or after an exist-
ing calibration has been verified, and before sample analysis, a
method blank must be analyzed. The method blank consists of
low TOC water as well as any reagents that have been added to
samples. The value of the blank must be <1/2 MRL.
6) Continuing blank check—After every 10 samples, analyze a
blank preferably consisting of recycled combusted water or low-
TOC water. The blank must contain any reagents that have been
added to the samples. With some instruments, this is difficult to
do regularly. If so, monitor a given lot of reagent water through-
out the day’s run. The results for subsequent reagent-water blanks
must be <1/2 MRL.
7) Continuing calibration check—After every 10 samples, ana-
lyze 1 of 3 calibration check samples—low range, midrange, and
high range standard concentrations—on a rotating basis. The low
range standard must be at or below the minimum reporting level.
The low range sample must agree within 50% of the true value,
and the midrange and high range samples must agree within 15%.
8) Duplicates—Perform a duplicate analysis for every 10 sam-
ples (or part thereof) analyzed. The RPD (relative percent dif-
ference) must be less than 15%. The duplicate analysis can be a
duplicated fortified sample.
9) Fortified sample—Spike one sample per every 10 samples
analyzed or part thereof. Spike at 50% to 200% of the expected
concentration. The spike level must be greater than 5 times the
MRL and generally within 50% to 200% of the expected concen-
tration. The recovery must be between 85% and 115%.
10) Inorganic carbon check—Confirm that inorganic carbon is
sufficiently removed from the samples on a frequency that corre-
sponds to the laboratories’ routine periodic maintenance schedule
or when maintenance has been conducted on an instrument that
may affect the tool or technique for inorganic carbon removal.
Prepare a 102.5 mg/L IC test solution (based on bicarbonate cal-
culations and impurities) and analyze the solution to confirm that
the result is <1/2 MRL. The IC removal check may be performed
on a different matrix, but the IC level in the check sample must be
higher than those in the unknown samples.
c. Corrective actions:
1) High blank values—Consult instrument manual. Check for
contamination of reagents, sample containers, and equipment.
Both high inorganic-matrix samples and high-TOC samples may
5310 B. High-Temperature Combustion Method
1. General Discussion
The high-temperature combustion method has been used for
a wide variety of samples, but when applied to particle-laden
https://doi.org/10.2105/SMWW.2882.104
cause an ongoing elevated blank. Diluting samples may help.
Higher MRLs may be required.
2) Bad calibration check samples—Consult instrument man-
ual. The instrument may need to be recalibrated.
3) Poor spike recovery or poor duplicate precision—This sug-
gests a matrix problem, or it may be caused by nonhomogenous
suspended particulates in the sample. Consult instruction manual.
Diluting samples may help resolve sample matrix issues.
Reference
1. Karanfil T, Erdogan I, Schlautman MA. Selecting filter mem-
branes for measuring DOC and UV254. J. Am Water Works Assoc.
2003;95(3):86–100.
Bibliography
Fredericks AD. Concentration of organic carbon in the Gulf of Mexico.
Rep. 68–27T, Office of Naval Research; 1968.
Williams PM. The determination of dissolved organic carbon in seawater:
A comparison of two methods. Limnol Oceanogr. 1969;14:297.
Croll BT. Determination of organic carbon in water. Chem Ind (London).
1972;110:386.
Sharp J. Total organic carbon in seawater—comparison of measurements
using persulfate oxidation and high temperature combustion. Mar
Chem. 1973;1(3):211–229.
Takahashi Y. Analysis techniques for organic carbon and organic halogen.
In: Proceedings of the EPA/NATO-CCMS Conference on Adsorption
Techniques. Reston (VA); 1979.
Standing Committee of Analysts, National Water Council. The instru-
mental determination of total organic carbon, total oxygen demand
and related determinands. London, UK: Her Majesty’s Stationery
Office; 1979.
Kaplan LA. Comparison of high-temperature and persulfate oxidation
methods for determination of dissolved organic carbon in freshwaters.
Limnol Oceanogr. 1992;37(5):1119–1125.
Benner R, Hedges JI. A test of the accuracy of freshwater DOC mea-
surements by high-temperature catalytic oxidation and UV-promoted
persulfate oxidation. Marine Chem. 1993;41(1-3):161–165.
Wangersky PJ. Dissolved organic carbon methods: A critical review.
Marine Chem. 1993;41(1–3):61–74.
Hutte R, Godec R, O’Neill K. Transferring NASA-sponsored advances
in total organic carbon measurement to industrial applications. Micro-
contamination. 1994;12(4):21.
Kaplan LA. A field and laboratory procedure to collect, process, and pre-
serve freshwater samples for dissolved organic carbon analysis. Lim-
nol Oceanogr. 1994;39(6):1470–1476.
Aiken G, Kaplan LA, Weishaar J. Assessment of relative accuracy in the
determination of organic matter concentrations in aquatic systems. J
Environ Monit. 2002:4:70–74.
Potter BB, Wimsatt JC. Method 415.3, Rev. 1.2. Determination of total
organic carbon and specific UV absorbance at 254 nm in source water
and drinking water. Washington DC: U.S. Environmental Protection
Agency; 2009.
samples, particle-size reduction may be necessary because the
method uses small-orifice syringes and sampling tubing.
a. Principle: The sample is homogenized and diluted as nec-
essary, and a portion is injected into a heated reaction chamber
4
 5310 Total Organic Carbon - B. High-Temperature Combustion Method
packed with an oxidative catalyst (e.g., cobalt oxide, platinum
group metals, or barium chromate). The water is vaporized, and
organic carbon oxidizes to CO2 and H2O. The CO2 from IC
release and organic carbon oxidation is transported in the carrier-
gas stream and measured via a nondispersive infrared analyzer, or
titrated coulometrically.
Because total carbon is measured, remove IC via acidification
and sparging, or measure it separately and calculate the difference
to obtain TOC.
Measure IC by injecting the sample into a reaction chamber,
where it is acidified. Under acidic conditions, all IC converts to
CO2, which is transferred to the detector and measured. Under
these conditions, organic carbon is not oxidized so only IC is
measured.
Alternatively, convert IC to CO2 with acid and remove the
CO2 by purging before sample injection. The sample then con-
tains only the NPOC fraction of total carbon. To determine TOC,
purgeable organic carbon also must be measured. (Note: NPOC
is reported as TOC when analyzing samples for drinking water
regulatory purposes.)
b. Interference: Removing carbonate and bicarbonate via acid-
ification and purging with purified gas results in the loss of vol-
atile organics. Volatiles also can be lost during storage or 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 or sampling tube used for injection. Although
filtration eliminates particulate carbon when determining DOC
only, it can result in DOC loss or gain, depending on the physi-
cal properties of carbonaceous compounds and the adsorption or
desorption of carbonaceous material on the filter (see 5310 A.4
for sample filtering requirements). Check the filters contribution
to DOC by analyzing a filtered blank. (Note: Any contact with
organic material may contaminate a sample. Avoid contaminated
glassware, plastic containers, and rubber tubing.) Analyze sample
treatment, system, and reagent blanks. Some carbonates require
combustion temperatures above 650 °C to decompose, so lower-
temperature systems must destroy carbonates via acidification.
Elemental carbon may not be oxidized at lower temperatures, but
it generally is not present in water samples or formed during the
combustion of dilute samples. However, at lower temperatures
(680 °C), dissolved salt fusion is minimized, resulting in lower
blank values.
Combustion gases (e.g., water, halide compounds, and nitro-
gen oxides) may interfere with the detection system. Consult
manufacturers’ recommendations regarding proper selection
and maintenance of scrubber materials and check for any matrix
interferences.
The major limitation to high-temperature techniques is the
blank’s magnitude and variability. Instrument manufacturers have
developed new catalysts and procedures that yield lower blanks,
resulting in lower detection levels.
c. Minimum detectable concentration: Although instrument
performance varies, most high-temperature combustion analyz-
ers can detect 1 mg/L of carbon or less. To reduce the minimum
detectable concentration, it may be possible to increase the por-
tion injected for analysis.
d. Sampling and storage: If possible, rinse bottles with sample
before filling. Field blanks can be used to check for atmospheric con-
tamination during sampling by exposing the field blank to the same
atmospheric conditions as samples during the sampling procedure.
https://doi.org/10.2105/SMWW.2882.104
Collect and store samples in glass bottles protected from sunlight
and seal with PTFE-backed septa (preferably thick silicone rubber-
backed PTFE septa with open ring caps to produce a positive seal).
Alternative containers may be used if it is demonstrated that the con-
tainer does not remove or add TOC >1/2 MRL. Check bottle blanks
with each set of sample bottles to determine the effectiveness of,
or need for, cleaning. Wash bottles with detergent, rinse copiously
with reagent water, seal with aluminum foil, and bake at 400 °C
for at least 1 h. Wash uncleaned PTFE septa with detergent, rinse
repeatedly with organic-free water, wrap in aluminum foil, and bake
at 100 °C for 1 h. Alternatively, soak septa in 10% sodium persulfate
for 1 hour at 60 °C and rinse thoroughly with organic-free water.
Check performance of new or cleaned septa by running appropriate
blanks. Less rigorous cleaning may be acceptable if a carbon con-
centration range more than 10 times the blank will be determined.
If samples cannot be examined immediately, refrigerate and hold
them with minimal exposure to light and atmosphere. If NPOC will
be determined, use appropriate acid during collection to adjust pH
to ≤2. Keep in mind, however, that acid preservation invalidates any
IC determination. The choice of acid depends on the instrument
manufacturer; consult the instruction manual. Also, acidification
may cause both inorganic and organic materials to precipitate. If
this happens, try another acid. In general, changing acid will not
affect precipitation of organics but may prevent precipitation of
inorganics that may adsorb organics and the particles may cause
clogging of the sample-introduction system. Any precipitate should
be well suspended before the sample is injected into the analyzer.
Precipitated organic material often can be redissolved by adding
NaOH free of CO2 and organic matter. Be sure to treat blanks and
samples identically. Maintain acidified samples just above freezing
up to 6 °C during shipment and store them at ≤6 °C until analy-
sis (maximum holding time is 28 d). Sample stability depends on
the type of organics and sample matrix involved; analyze samples
as soon as possible. When determining IC and then TOC, refrig-
erate the sample but do NOT adjust pH. Then analyze it as soon
as possible because TOC may biodegrade significantly before the
regulatory 28-d holding time expires. Alternatively, determine IC
independently on an unacidified sample, and then determine TOC
via difference using a second, acidified sample (recognizing that
the IC result for the second sample, used to determine TOC, will
not represent the IC concentration in the first sample).
e. Quality control (QC): The QC practices considered to be
an integral part of this method are summarized in Table 5020:1.
Additionally, follow all QC described in the method itself.
2. Apparatus
a. Total organic carbon analyzer, using high-temperature com-
bustion techniques.
b. Sampling, injection, and sample preparation accessories, as
prescribed by instrument manufacturer.
c. Sample blender or homogenizer.
d. Magnetic stirrer and PTFE-coated stirring bars.
e. Filtering apparatus and filters: See 5310 A.4.
3. Reagents
a. Reagent water: Prepare reagents, blanks, and standard solu-
tions from ASTM Type I water whose TOC content is <1/2 MRL.
5
 5310 Total Organic Carbon - B. High-Temperature Combustion Method
b. Acid: Refer to instrument manufacturer’s specifications.
Check the acid for TOC content.
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 organ-
ic-carbon-containing compound of adequate purity, stability, and
water solubility. Commercially prepared standards may be used.
To preserve, use appropriate acid to adjust pH to ≤2, and store
sample just above freezing up to 6 °C. Use the same acid in stan-
dards, samples, and blanks.
d. IC stock solution: Dissolve 4.4122 g anhydrous sodium car-
bonate, Na2CO3, in water; add 3.497 g anhydrous sodium bicar-
bonate, NaHCO3; and dilute to 1000 mL (1.00 mL = 1.00 mg
carbon). Alternatively, use another IC compound of adequate
purity, stability, and water solubility. Keep tightly stoppered. Do
not acidify. (Note: This solution is used to prepare standards for
the analyzer’s IC channel.)
e. IC-removal check solution: Because inorganic salts are not
soluble in a single concentrated solution, prepare 4 separate stock
solutions (A-D).
• Prepare Solution A by dissolving 2.565 g magnesium sulfate
heptahydrate (MgSO4 ⋅ 7H2O in low-TOC water and diluting
to 1 L with low-TOC water.
• Prepare Solution B by dissolving 0.594 g ammonium chloride
(NH4Cl), 2.050 g calcium chloride dehydrate (CaCl2 ⋅ 2H2O),
0.248 g calcium nitrate tetrahydrate [Ca(NO3)2 ⋅ 4H2O],
0.283 g potassium chloride (KCl), and 0.281 g sodium chlo-
ride (NaCl) to 1 L of low-TOC water.
• Prepare Solution C by adding 2.806 g sodium bicarbonate
(NaHCO3) and 0.705 g sodium phosphate dibasic heptahy-
drate (Na2HPO4 ⋅ 7H2O) to low-TOC water and diluting to 1
L with low-TOC water.
• Prepare Solution D by dissolving 1.862 g sodium-meta sili-
cate nonahydrate (Na2SiO3 ⋅ 9H2O) in low-TOC water and
diluting to 1 L with low-TOC water.
Take a 10-mL aliquot from each solution (A-D) and add it to
a 40-mL vial. Acidify with 40 µL of an appropriate acid; use the
same acid used for sample preservation.
f. Carrier gas: Purified oxygen or air (as specified by instru-
ment manufacturer), CO2-free and containing less than 1 ppm
hydrocarbon (as methane). Contaminated gases or gas lines will
result in elevated background levels. Commercial gas purifiers
are available.
g. Purging gas: Any appropriate gas that meets the carrier-gas
specifications.
4. Procedure
a. Instrument operation: Follow manufacturer’s instructions for
assembling, testing, calibrating, and operating analyzer. Adjust to
optimum combustion temperature before using instrument; mon-
itor temperature to ensure stability.
b. Sample treatment: If a sample contains gross solids or insol-
uble matter, homogenize until satisfactory replication is obtained.
Sometimes dilution helps to dissolve or suspend solids. If the
sample solids cannot be dispersed so they can be representa-
tively inserted into the analyzer, then consider filtering the sam-
ple through a quartz filter and analyzing the retentate for carbon.
https://doi.org/10.2105/SMWW.2882.104
When determining DOC, filter samples (see 5310 A.4). Analyze
a homogenizing blank (reagent water carried through the homog-
enizing treatment).
When measuring NPOC, first remove IC in accordance with
instrument manufacturer’s instructions. Check IC-removal effi-
ciency (5310 A.5b10). Alternatively, transfer a representative por-
tion (10 to 15 mL) to an appropriate tube or container, add acid
to reduce pH to ≤2, and purge with gas for the time determined
in 5310 A.5. When samples are purged externally before being
injected into the oxidation zone, acidifying them to pH ≤2 may
cause most hydrophobic molecules to be lost to the sample vessel
walls. Acidifying to pH 4 minimizes such losses, but check IC-
removal efficiency. Some instruments automatically purge samples
as part of the TOC analysis cycle. Volatile organic carbon will be
lost when the acidified solution is purged, so report organic car-
bon as total NPOC. If the instrument separately determines IC
(carbonate, bicarbonate, free CO2) and total carbon, verify sparg-
ing efficiency for the TOC determination. If the instrument deter-
mines TOC by calculating the difference between TC and IC, IC
still may need to be sparged from the sample to avoid excessive
error. To verify that the instrument is operating appropriately,
analyze standards with IC levels higher than those in samples and
TOC levels near the MRL to show proper recoveries.
c. Sample injection: Withdraw a portion of prepared sample
using a syringe fitted with a blunt-tipped needle. Select the sample
volume according to manufacturer’s directions. Stir particle-laden
samples with a magnetic stirrer. Select needle size consistent
with sample particle size. Other sample-injection techniques
(e.g., sample loops) may be used. Inject samples and standards
into analyzer according to manufacturer’s directions and record
response. Repeat injection until at least 3 replicate measurements
are reproducible to within ±10% RSD.
d. Preparation of standard curve: Prepare standard organic and
IC series by diluting stock solutions to create a range of samples
that spans the instrument’s linear range. Include a minimum of a
reagent water blank and 4 calibration levels within the curve. Use
reagent water to dilute samples above the instrument’s linear range.
Inject each standard and dilution water blank and record its peak
height or area. Plot carbon concentration in milligrams per liter
against corrected peak height or area (unnecessary for instruments
that digitally compute concentration). Instruments with coulomet-
ric detectors and computerized IR detectors do not require cali-
bration curves. For instruments with these detectors, demonstrate
linearity and verify that the instrument is operating correctly by
evaluating blanks and standards covering the analytical range.
In many laboratories, reagent water is the major contributor
to the blank’s results. However, correcting only the instrument
response to standards (which contain reagent water, reagents, and
system blank) creates a positive error; correcting the instrument
response to reagent-water blanks (which contain only reagents
and system blank contributions) creates a negative error. Many
analyzers allow combustion water to be recycled through the ana-
lyzer and analyzed as a blank. Others allow the trapped water to
be sampled and re-injected. This should be done with and without
purging to determine the TOC contribution of the purging step.
Inject samples and determine organic carbon concentrations
directly from the readout or from measurements by comparing
corrected instrument response to the calibration curve. Regularly
analyze laboratory-control samples to confirm instrument perfor-
mance (see 5310 A.5). Monitor the system blank regularly.
6
 5310 Total Organic Carbon - B. High-Temperature Combustion Method

Table 5310:1. Statistical Summary of Results of TOC Determination by High Temperature Combustion for 3 Matrices Evaluated Using Youden Pairs

Matrix 1 2 3 4 10 11
Number of usable values 6 6 6 6 7 7
True concentration, C (mg/L) – – – – 50.1 40.1
Mean recovery, XBAR – – – – 49.8 40.2
Percent recovery – – – – 99.4 100
Overall standard deviation, St 0.34 0.56 1.19 1.36 4.28 3.18
Overall relative standard deviation (%) 8.78 16.2 14.2 14.0 8.60 7.90
Number of usable pairs 6 ... 6 ... 7 ...
Single operator standard deviation, So 0.372 ... 0.59 ... 1.32 ...
Single operator relative standard deviation (%) 10.2 ... 6.58 ... 2.94 ...
– Cannot calculate recovery because natural matrices contain an unknown concentration of TOC.
Reprinted, with permission, from ASTM D7573-18ae1 Standard Test Method for Total Carbon and Organic Carbon in Water by High Temperature Catalytic Combustion
and Infrared Detection, copyright ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428. A copy of the complete standard may be obtained from
ASTM, www.astm.org.

5. Calculations 7. Precision

Calculate the corrected instrument response to standards and
samples by subtracting the instrument-blank results from those
of the standard and sample. Prepare a standard curve of cor-
rected instrument response vs. TOC concentration. Only subtract
reagent water blank from standards prepared in reagent water or
from the portion of diluted samples containing reagent water. The
instrument response is compared to the standard curve to deter-
mine carbon content. Apply the appropriate dilution factor when
necessary. Subtract IC from total carbon when TOC is determined
by calculating the 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 the reagent-water blank is introduced in sample values.
Using recycled water permits isolation of each contribution to the
total blank. Apply appropriate blank corrections to the instrument
response to standards (reagent blank, reagent water blank, system
blank) and sample (reagent blank and system blank).
6. Quality Control
See 5310 A.5.
The difficulty of sampling particulates can limit the method’s
precision.
A collaborative study of the high-temperature combustion
method has been conducted on 9 water matrices in the range of
0.5 to 50 mg/L of carbon.1 These data are shown in Tables 5310:1
and 5310:2.
Reference
1. ASTM D7573-18ae1. Standard test method for total carbon and organic
carbon in water by high temperature catalytic combustion and infrared
detection. West Conshohocken (PA): ASTM International; 2019.
Bibliography
Van Hall CE, Barth D, Stenger VA. Elimination of carbonates from
aqueous solutions prior to organic carbon determination. Anal Chem.
1965;37(6):769–771.
Busch AW. Energy, total carbon, and oxygen demand. Water Resource
Res. 1966;2(1):59–69.
Blackmore RH, Voshel D. Rapid determination of total organic carbon
(TOC) in sewage. Water Sewage Works. 1967;114:398–401.
American Society for Testing & Materials. Standard test method for total
organic carbon in water; D2579-93. In: Annual Book of ASTM Stan-
dards. West Conshohocken (PA): ASTM International; 1994.

Table 5310:2. Statistical Summary of Determination of TOC by High Temperature Combustion in Additional Matrices
Matrix 5 6 7 8 9 12
Number of useable values 14 12 12 14 12 12
True concentration (mg/L) 5.39 N/A N/A 21.0 N/A 0.501
Mean recovery (mg/L) 5.67 1.61 1.68 21.9 3.63 0.808
% Recovery 105 N/A N/A 104 N/A 161
Overall standard deviation, St 0.777 0.265 0.350 2.53 0.374 0.162
Overall relative standard 13.71 16.48 20.99 11.54 10.28 20.02
deviation (%)
Single operator standard deviation So 0.549 0.243 0.329 1.156 0.317 0.150
Single operator relative standard
9.68 15.47 19.75 5.27 8.71 18.59
deviation (%)
Reprinted, with permission, from ASTM D7573-18ae1 Standard Test Method for Total Carbon and Organic Carbon in Water by High Temperature Catalytic Combustion
and Infrared Detection, copyright ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428. A copy of the complete standard may be obtained from
ASTM, www.astm.org.

https://doi.org/10.2105/SMWW.2882.104 7
 5310 Total Organic Carbon - C. Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method
5310 C. Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method
1. General Discussion
Many instruments that use persulfate to oxidize organic carbon
are available. They depend either on catalyzed heat or UV irradi-
ation to activate the reagents. These oxidation methods measure
trace levels of organic carbon in water rapidly and precisely.
a. Principle: Persulfate oxidizes organic carbon to CO2 in the
presence of heat and a catalyst or UV light (or both). The CO2
produced may be purged from the sample, dried, and transferred
with a carrier gas to a nondispersive infrared (NDIR) analyzer, be
coulometrically titrated, or be separated from the liquid stream by
a membrane that specifically allows CO2 to pass into high-purity
water. The change in the high-purity water’s conductivity corre-
sponds to the amount of CO2 passing the membrane.
Some instruments use a UV lamp submerged in a continuously
gas-purged reactor filled with a constant-feed persulfate solution.
The samples are either introduced serially into the reactor by an
autosampler or injected manually. The CO2 produced is sparged
continuously from the solution and is carried in the gas stream
to an infrared analyzer specifically tuned to the absorptive wave-
length 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 sample
injection and have an option for IC removal via vacuum degassing.
The sample is acidified, persulfate is added, and then the sample
flow is split. One channel passes to a delay coil, while the other
passes through the UV reactor. CO2 is separated from each sample
stream by CO2-selective membranes into high-purity water, whose
change in conductivity is measured. CO2 from the non-UV-irradiated
stream represents IC. CO2 from the irradiated stream represents TC.
The instrument automatically converts the detector signals to units
of concentration (mg/L or µg/L of carbon). The TOC is calculated
as the difference between the TC and IC channels.
Heated-persulfate instruments use a catalyst in a digestion ves-
sel heated to 95 to 100 °C. Samples are added by direct injection,
loop injection, line injection, or autosampler. After IC is removed
via 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 infra-
red analyzer specifically tuned to the absorptive wavelength of
CO2. The instrument’s microprocessor converts the detector sig-
nal into organic carbon concentrations in milligrams per liter of
carbon, based on stored calibration data.
b. Interferences: Chloride interferes with persulfate oxidation,
so HCl must not be used to acidify samples for this method
(see 5310 B.1). Insufficient acidification or sparging results in
incomplete removal of IC (see 5310 A.5b10).
The intensity of the UV light reaching the sample matrix may
be reduced by highly turbid samples or aging lamps, resulting in
sluggish or incomplete oxidation. Large organic particles or large
or complex organic molecules (e.g., tannins, lignins, and humic
acid) may oxidize slowly or incompletely because persulfate
oxidation is rate-limited. However, many large biological mole-
cules (e.g., proteins and monoclonal antibodies) oxidize rapidly.
Because the organic carbon-to-CO2 conversion efficiency may
https://doi.org/10.2105/SMWW.2882.104
be affected by many factors, check the oxidation efficiency with
selected model compounds representative of the compounds of
interest in a matrix representative of the sample.
Some instruments give low results for difficult-to-oxidize com-
pounds under certain conditions. The following compounds are
difficult to oxidize, are sufficiently water-soluble, 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,
• caffeine, and
• sodium dodecylbenzenesulfonate.
Use these compounds as matrix additions to evaluate oxidation
efficiency.
In samples containing significant concentrations of chloride,
persulfate oxidation of organic molecules is slowed by the prefer-
ential oxidation of chloride. When chloride concentrations exceed
0.05%, organic matter oxidation may be inhibited. To remove this
interference, extend reaction time or increase the amount of per-
sulfate solution in heated-persulfate instruments.
With any organic carbon measurement, contamination during
sample handling and treatment is a likely source of interference.
Take extreme care when sampling, handling, and analyzing sam-
ples <1 mg/L TOC.
c. Minimum detectable concentration: Concentrations <0.1 mg/L
TOC can be measured by some instruments if scrupulous atten-
tion is given to minimizing sample contamination and method
background.
d. Sampling and storage: See 5310 B.ld.
e. Quality control (QC): See 5310 A.5. The QC practices con-
sidered to be an integral part of this method are summarized in
Table 5020:1. Also, follow all QC described in the method itself.
2. Apparatus
a. Total organic carbon analyzer using persulfate oxidation
principle.
b. Sampling and injection accessories, as specified by the
instrument manufacturer.
c. Filtering apparatus: See 5310 A.4.
3. Reagents
a. Reagents listed in 5310 B.3.
b. Persulfate solution: Different instrument manufacturers rec-
ommend different forms and concentrations of peroxydisulfate.
Typical preparations are as follows:
8
 5310 Total Organic Carbon - C. Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method
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
the reagent or use a higher-purity source.
4. Procedure
a. Instrument operation: Follow manufacturer’s instructions
for assembling, testing, calibrating, and operating the analyzer.
b. Sample preparation: If a sample contains particulates,
homogenize until a representative portion can be withdrawn
through the syringe needle, autosampler tubing, or sample inlet
system of continuous on-line monitor.
When determining DOC, filter the sample and a reagent water
blank through a filter consistent with the specification contained
in 5310 A.4.
When determining NPOC, transfer an appropriate volume of
sample to an appropriate container and acidify to pH 2. Purge
according to the IC-removal procedure in 5310 A.5. Some instru-
ments include the IC-removal steps, but they must be evaluated as
specified in 5310 A.5.
c. Sample injection: See 5310 B.4c.
d. Standard curve preparation: Prepare an organic carbon stan-
dard series that spans the range of organic carbon concentrations
in samples. Run standards and blanks, and record the analyzer’s
response. Determine instrument response for each standard and
blank. Unless CO2 is trapped and desorbed, producing consis-
tent peak heights, determinations based on peak height may be
inadequate because of differences in the oxidation rates of stan-
dards and samples. Correct the instrument response to standards
by subtracting reagent water blank and plotting organic carbon
concentration in milligrams per liter against corrected instru-
ment response. (This is unnecessary for instruments that digitally
compute concentration.) Be sure that the instrument’s algorithm
includes blank correction and linearity of response. To confirm
proper instrument operation, analyze standards with concentra-
tions above and below those determined in the samples (prefera-
bly prepared in a similar matrix).
5. Calculation
See 5310 B.5 or use instrument manufacturer’s procedure.
6. Quality Control
See 5310 A.5.
7. Precision and Bias
Collaborative studies of heated persulfate and UV persulfate
with NDIR detection methods have been conducted in the range
of 0.1 to 4000 mg/L of carbon.1 The resulting equation for organic
carbon (single-operator precision) is:
So = 0.04x + 0.1
https://doi.org/10.2105/SMWW.2882.104
Overall precision is expressed as:
St = 0.08x + 0.1
where:
So = single-operator precision,
x = TOC concentration (mg/L of carbon), and
St = overall precision.
A collaborative study was conducted for the membrane con-
ductivity method, (data may be obtained from Standard Methods
manager, American Water Works Association) covering samples
with organic carbon concentrations between 1 and 25 mg/L of
carbon. The resulting equation for single-operator precision is:
So = 0.012x – 0.022
Overall precision is expressed as:
St = 0.027x + 0.09
where terms are defined as above.
Reference
1. American Society for Testing & Materials. Standard test method for
total carbon in water by ultraviolet, or persulfate oxidation, or both,
and infrared detection; D4839-88. In: Annual Book of ASTM Stan-
dards. West Conshohocken (PA): ASTM International; 1994.
Bibliography
Beattie J, Bricker C, Garvin D. Photolytic determination of trace amounts
of organic material in water. Anal Chem. 1961;33:1890.
Armstrong FAJ, Williams PM, Strickland JDH. Photooxidation of organic
matter in sea water by ultraviolet radiation, analytical and other appli-
cations. Nature 1966;211:481–483.
Bramer HC, Walsh MJ, Caruso SC. Instrument for monitoring trace
organic compounds in water. Water Sewage Works. 1966;113:275–
278.
Dobbs RA, Wise RH, Dean RB. Measurement of organic carbon in
water using the hydrogen flame ionization detector. Anal Chem.
1967;39(11):1255–1258.
Montgomery HAC, Thom NS. The determination of low concentrations
of organic carbon in water. Analyst. 1962;87(1038):689–697.
Armstrong FAJ, Tibbitts S. Photochemical combustion of organic matter
in sea water for nitrogen, phosphorus and carbon determination. J Mar
Biol Assoc UK. 1968;48(1):143–152.
Jones RH, Dageford AF. Application of a high sensitivity total organic
carbon analyzer. Proc Instr Soc Amer. 1968;6:43.
Takahashi Y, Moore RT, Joyce RJ. Direct determination of organic carbon
in water by reductive pyrolysis. Internatl Lab USA. 1972;4:21–28.
Collins KJ, Leb PJ. Williams. An automated photochemical method for
the determination of dissolved organic carbon in sea and estuarine
waters. Marine Chem. 1977;5(2):123–141.
Gravelet-Blondin LR, Van Vliet HR, Mynhardt PA. An automated method
for the determination of dissolved organic carbon in fresh water. Water
SA. 1980;6(3):138–143.
Oake RJ. A Review of photo-oxidation for the determination of total
organic carbon in water; technical report. (TR 160). Medmenham
(England): Water Research Center; 1981.
9
 5310 Total Organic Carbon - E. Supercritical Water Oxidation Method
Van Steenderen RA, Lin JS. Determination of dissolved organic carbon
in water. Anal Chem. 1981;53(13):2157–2158.
Aiken GR. Chloride interference in the analysis of dissolved organic
carbon by the wet oxidation method. Environ Sci Technol.
1992;26(12):2435–2439.
5310 D. (Reserved)
5310 E. Supercritical Water Oxidation Method
1. General Discussion
Supercritical water oxidation (SCWO) has been used by the
hazardous waste industry in the treatment of aqueous waste
streams and contaminated soils since approximately 1992.1
Supercritical water oxidation for TOC analysis uses heat, pres-
sure, and chemical reagents to oxidize organic carbon.
a. Principle: A sample is homogenized with reagents, diluted,
and sent to the reactor, which is sealed, heated, and pressurized
to achieve SCWO conditions (>374 °C, 21.7 MPa).2 Supercriti-
cal water acts as an organic solvent, increasing the solubility of
organic carbon in water and decreasing the solubility of inorganic
species such as salts.3 The oxidation of organics from the addi-
tion of the persulfate progresses rapidly at elevated temperatures.
After oxidation, the cooled sample passes through a gas-liquid
separator where the CO2 produced from oxidation is separated
from the matrix solution and subsequently measured via nondis-
persive infrared detection (NDIR) optimized to the absorptive
wavelength of CO2.
Supercritical water oxidation can determine TC or NPOC
directly. TOC cannot be obtained directly and requires separate
measurements to determine IC and TC. Remove IC via acidifica-
tion and sparging or measure it separately and calculate the differ-
ence between TC and IC to obtain TOC. At pH 2 or less, all IC is
converted to CO2, and the CO2 can be transferred to the NDIR via
carrier gas and measured. Under these conditions, organic carbon
is not oxidized so only IC is measured.
The determination of NPOC is by acidic conversion of IC to
CO2. The IC related CO2 is removed by purging before sample
injection into the reactor. Measurements of NPOC only determine
the nonpurgeable fraction of the organic carbon. To determine
TOC, purgeable organic carbon also must be measured.
b. Interference: Acidification and purging with purified gas to
remove carbonate and bicarbonate before analysis results in the
loss of volatile organics. The resulting measurement only con-
tains the nonpurgeable organic fraction of TOC. Additional TOC
loss is possible if large carbon-containing particles do not enter
the needle or sampling tube used for injections. Although filtra-
tion eliminates particulate carbon when determining DOC only, it
can result in DOC loss or gain, depending on the physical proper-
ties of carbonaceous compounds and the adsorption or desorption
of carbonaceous material on the filter (see 5310 A.4). Check the
filter’s contribution to DOC by analyzing a filtered blank.
Acid preservation invalidates any IC determination because of
the loss of IC when converting carbonates and bicarbonates to
CO2, which is liberated as a gas before analysis.
https://doi.org/10.2105/SMWW.2882.104
Godec R, O’Neil K, Hutte R. New Technology for TOC Analysis in
Water. Ultrapure Water 1992;9(9):17.
Babatola A, Xu T. Faster and smarter: a BOD-to-TOC conversion enables
quick response to process control needs. Water Env Lab Solutions.
2010;17(5):7.
Any contact with organic material may contaminate a sample.
Avoid contaminated glassware, plastic containers, and rubber
tubing. Analyze sample treatment, system, and reagent blanks.
Unlike high-temperature techniques, the moderate temperature
(≥374 °C) of the SCWO reactor does not affect the magnitude and
variability of the blank.
c. Minimum detectable concentration: SCWO analyzers can
detect concentrations as low as 0.050 mg/L of carbon. See Sec-
tion 1020 B.4 for procedures to evaluate the MDL for a specific
instrument.
d. Sampling and storage: See 5310 B.1d.
e. Quality control (QC): The QC practices considered to be
an integral part of this method are summarized in Table 5020:1.
Additionally, follow all QC described in this method.
2. Apparatus
a. Total organic carbon analyzer, using supercritical water oxi-
dation techniques.
b. Sampling and injection accessories, as specified by the
instrument manufacturer.
3. Reagents
a. Reagents listed in 5310 B.3.
b. Persulfate solution: Typical oxidizer preparation includes
sodium peroxydisulfate (Na2S2O8), 30%. Dissolve 300 g in
reagent water; and dilute to 1 L.
4. Procedure
a. Instrument operation: Follow the manufacturer’s instruc-
tions for analyzer assembly, testing, calibration, and operation.
b. Sample treatment: If the sample contains particulates or
insoluble matter, homogenize it until the particulate diameter is
smaller than the inner diameter of the syringe needle, autosam-
pler tubing, or sample inlet. Continuous stirring of a sample con-
taining small diameter settleable solids may increase the sample’s
uniformity. Dilution may help dissolve and suspend solids. If the
sample solids cannot be dispersed so they can be representatively
inserted into the analyzer, consider filtering the sample through a
quartz filter and analyzing the retentate for carbon. When deter-
mining DOC, filter the samples (5310 A.4). Analyze a reagent
water blank carried through the homogenizing treatment.
If the instrument separately determines IC and TC, verify the
sparging efficiency for the TOC determination. If the instrument
10
 5310 Total Organic Carbon - E. Supercritical Water Oxidation Method

Table 5310:3. Collaborative Results of Supercritical Water Oxidation TOC in Reagent Watera

Concentration of Average TOC (mg/L) TOC Grand

Compound SD
Compound (mg/L) Lab 1 Lab 2 Lab 3 Lab 4 Average (mg/L)

0.5 KHP 0.61 0.50 0.47 0.5 0.52 0.06

Sucrose 0.43 0.49 0.49 0.51 0.48 0.03
Nicotinic acid 0.52 0.48 0.48 0.51 0.50 0.02
Urea 0.48 0.5 0.49 0.48 0.49 0.01
2 KHP 2.31 1.95 1.91 1.99 2.04 0.18
Sucrose 2.31 1.98 1.92 2.00 2.05 0.18
Nicotinic acid 1.99 1.96 1.93 2.03 1.98 0.04
Urea 2.08 2.05 1.96 1.98 2.02 0.06
4 KHP 4.31 3.92 3.93 4.03 4.05 0.18
Sucrose 4.25 3.96 3.86 3.96 4.01 0.17
Nicotinic Acid 3.99 3.95 3.98 4.07 4.00 0.05
Urea 4.40 4.06 3.98 3.99 4.11 0.20
8 KHP 8.18 7.89 7.95 7.99 8.00 0.13
Sucrose 8.06 7.97 7.82 8.03 7.97 0.11
Nicotinic acid 7.97 8.08 8.05 8.08 8.05 0.05
Urea 8.07 8.24 8.00 8.03 8.09 0.11
10 KHP 10.10 10.50 10.10 10.30 10.25 0.19
Sucrose 10.30 10.30 9.97 9.84 10.10 0.23
Nicotinic acid 10.50 10.30 10.20 10.20 10.30 0.14
Urea 10.30 10.70 10.20 10.10 10.33 0.26
25 KHP 25.00 26.00 25.20 25.20 25.35 0.44
Sucrose 25.30 25.60 25.20 24.90 25.25 0.29
Nicotinic acid 25.70 26.20 25.50 25.40 25.70 0.36
Urea 25.10 26.30 25.50 25.00 25.48 0.59
50 KHP 50.10 50.30 49.90 50.10 50.10 0.16
Sucrose 50.70 50.20 49.60 49.90 50.10 0.47
Nicotinic acid 49.90 50.50 50.40 49.80 50.15 0.35
Urea 50.10 50.80 50.40 49.80 50.28 0.42
75 KHP 75.50 74.60 75.40 73.20 74.68 1.06
Sucrose 75.20 72.90 73.50 72.60 73.55 1.16
Nicotinic Acid 75.30 73.10 75.50 73.60 74.38 1.20
Urea 75.40 75.60 75.30 73.90 75.05 0.78
a
The samples were prepared in the Applications Lab at SUEZ WTS. Two separate aliquots of each sample were run with 3 replicates on the instruments. In each lab, 2 ana-
lysts carried out the analyses.
Note: Lab 1 results were obtained at Pace Analytical in Minneapolis, MN; Lab 2 results were obtained at Eurofins Test America in Arvada CO; Lab 3 results were obtained
at Suez WTS Laboratory in Boulder, CO; Lab 4 results were obtained at Eurofins Test America in Pittsburgh, PA.
Reference
1. Standard Methods validation report for the Sievers InnoVox laboratory TOC analyzer. Boulder (CO): Suez Water Technologies & Solutions; 2020.

determines TOC by calculating the difference between TC and 7. Precision and Bias
IC, the IC still may need to be sparged from the sample to avoid
excessive error when IC is significantly larger than TOC. To ver- Collaborative studies of the SCWO method have been con-
ify the instrument’s performance for proper recoveries, analyze ducted in the range 0.5 to 75 mg/L C4 (Table 5310:3 through
standards with IC levels higher than those in samples and TOC Table 5310:6). The equation for organic carbon in reagent water,
levels near the MRL. single-operator precision is:
c. Sample injection: See Section 5310 B.4.c.
d. Standard curve: See Section 5310 B.4d. So = 0.009x + 0.040

5. Calculations Overall precision is:

See 5310 B.5, or use the manufacturer’s instructions. St = 0.014x + 0.089

6. Quality Control where:

So = single-operator precision,
See 5310 A.5. St = overall precision, and
x = TOC concentration (mg/L).

https://doi.org/10.2105/SMWW.2882.104 11
 5310 Total Organic Carbon - E. Supercritical Water Oxidation Method

Table 5310:4. Collaborative Results of Supercritical Water Oxidation TOC in Municipal Watera

Concentration of Average TOC (mg/L) TOC Average

Compound SD
Compound (mg/L) Lab 1 Lab 1 Lab 3 Lab 4 (mg/L)

0.5 KHP 0.46 0.45 0.48 0.55 0.49 0.05

Sucrose 0.51 0.47 0.51 0.51 0.50 0.02
Nicotinic acid 0.56 0.52 0.50 0.51 0.52 0.03
Urea 0.50 0.43 0.51 0.52 0.49 0.04
2 KHP 1.97 1.95 2.03 2.00 1.99 0.04
Sucrose 2.09 1.98 1.99 2.00 2.02 0.05
Nicotinic acid 2.09 2.03 2.04 2.05 2.05 0.03
Urea 2.11 1.94 2.00 1.92 1.99 0.09
4 KHP 4.19 3.98 4.02 4.02 4.05 0.09
Sucrose 4.23 3.95 4.09 4.02 4.07 0.12
Nicotinic acid 4.17 4.11 4.07 3.96 4.08 0.09
Urea 3.99 3.95 4.06 4.02 4.01 0.05
8 KHP 8.19 8.07 8.17 7.98 8.10 0.10
Sucrose 8.35 8.06 8.07 8.15 8.16 0.13
Nicotinic acid 8.17 8.1 8.19 8.12 8.15 0.04
Urea 8.09 8.12 8.24 8.06 8.13 0.08
a
The samples were prepared in the Applications Lab at SUEZ WTS. Two separate aliquots of each sample were run with 3 replicates on the instruments. In each lab, 2 ana-
lysts carried out the analyses.
Note: Lab 1 results were obtained at Pace Analytical in Minneapolis, MN; Lab 2 results were obtained at Eurofins Test America in Arvada CO; Lab 3 results were obtained
at Suez WTS Laboratory in Boulder, CO; Lab 4 results were obtained at Eurofins Test America in Pittsburgh, PA.
Reference
1. Standard Methods validation report for the Sievers InnoVox laboratory TOC analyzer. Boulder (CO): Suez Water Technologies & Solutions; 2020.

Table 5310:5. Collaborative Results of Supercritical Water Oxidation TOC in Seawatera

Concentration of Average TOC (mg/L) Average TOC
Compound SD
Compound (mg/L) Lab 1 Lab 2 Lab 3 Lab 4 (mg/L)
10 KHP 10.1 10.1 10 9.99 10.05 0.06
Sucrose 10.3 10.1 9.94 10 10.09 0.16
Nicotinic acid 10 9.98 10.2 10.1 10.07 0.10
Urea 10.9 10.7 10.8 10.4 10.70 0.22
25 KHP 24.9 25.2 25 24.6 24.93 0.25
Sucrose 24.9 24.5 24.5 24.3 24.55 0.25
Nicotinic acid 25.1 24.9 24.9 23.8 24.68 0.59
Urea 25.2 26.6 26.3 25.4 25.88 0.68
50 KHP 48.4 48.4 48.4 47.4 48.15 0.50
Sucrose 48.5 48.1 47.1 47.9 47.90 0.59
Nicotinic acid 48.8 48.2 48.9 47.4 48.33 0.69
Urea 50.7 51.3 51.3 49.4 50.68 0.90
75 KHP 73 72 71.8 69.4 71.55 1.53
Sucrose 72.5 71 70.9 69.7 71.03 1.15
Nicotinic acid 71.9 71 73.1 71.4 71.85 0.91
Urea 75.5 74.9 76.7 73.3 75.10 1.41
a
The samples were prepared in the Applications Lab at SUEZ WTS. Two separate aliquots of each sample were run with 3 replicates on the instruments. In each lab, 2 ana-
lysts carried out the analyses.
Note: Lab 1 results were obtained at Pace Analytical in Minneapolis, MN; Lab 2 results were obtained at Eurofins Test America in Arvada CO; Lab 3 results were obtained
at Suez WTS Laboratory in Boulder, CO; Lab 4 results were obtained at Eurofins Test America in Pittsburgh, PA.
Reference
1. Standard Methods validation report for the Sievers InnoVox laboratory TOC analyzer. Boulder (CO): Suez Water Technologies & Solutions; 2020.

https://doi.org/10.2105/SMWW.2882.104 12
 5310 Total Organic Carbon - E. Supercritical Water Oxidation Method

Table 5310:6. Overall Precision and Bias for Supercritical Water References
Oxidation TOC Method
Average 1. Barner H, Huang C, Johnson T, Jacobs G, Martch M, Killilea W.
TOC TOC Standard % Supercritical water oxidation: An emerging technology. J Hazardous
Matrix (mg/L) (mg/L) Deviation RSD Bias Materials. 1992;31(1):1–17.
2. Crooker P, Ahluwalia K, Fan Z, Prince J. Operating results from super-
Reagent water 0.5 0.50 0.04 7.41 –0.01 critical water oxidation plants. Ind Eng Chem Res. 2000;39(12):4865–
2.0 2.03 0.12 5.97 0.03 4870.
4.0 4.05 0.15 3.72 0.05 3. Kritzer P, Dinjus E. An assessment of supercritical water oxidation
8.0 8.02 0.10 1.26 0.02 (SCWO): Existing problems, possible solutions and new reactor con-
10.0 10.29 0.21 2.04 0.29 cepts. Chem Eng J. 2001;83(3):207–214.
25.0 25.55 0.43 1.67 0.55 4. Standard Methods validation report for the Sievers InnoVox labora-
50.0 50.24 0.34 0.68 0.24 tory TOC analyzer. Boulder (CO): Suez Water Technologies & Solu-
75.0 74.78 1.11 1.48 –0.23 tions; [DATE].
Municipal water 0.5 0.50 0.03 6.88 0.00
2.0 2.01 0.06 2.75 0.01
4.0 4.05 0.09 2.13 0.05
8.0 8.13 0.09 1.07 0.13
Seawater 10.0 10.23 0.31 3.05 0.23
25.0 25.01 0.69 2.76 0.01
50.0 48.76 1.30 2.67 –1.24
75.0 72.38 2.00 2.77 –2.62

Published Online: August 27, 2018

Revised: May 23, 2022
https://doi.org/10.2105/SMWW.2882.104 13