Designation: D 6317 – 98 (Reapproved 2004)

Standard Test Method for

Low Level Determination of Total Carbon, Inorganic Carbon
and Organic Carbon in Water by Ultraviolet, Persulfate
Oxidation, and Membrane Conductivity Detection1
This standard is issued under the fixed designation D 6317; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

1. Scope 1.4 In addition to laboratory analyses, this test method may

1.1 This test method covers the determination of total be adapted to on line monitoring. See Test Method D 5997.
carbon (TC), inorganic carbon (IC), and total organic carbon 1.5 This standard does not purport to address all of the
(TOC) in water in the range from 10 to 1000 µg/L of carbon. safety concerns, if any, associated with its use. It is the
This method is for laboratory or grab sample applications and responsibility of the user of this standard to establish appro-
has been subjected to an interlaboratory study under the priate safety and health practices and determine the applica-
guidelines of D 2777. Test Method D 5997 can be used for bility of regulatory limitations prior to use.
on-line determinations. The test method utilizes persulfate or 2. Referenced Documents
ultraviolet oxidation of organic carbon, or both coupled with a
CO2 selective membrane to recover the CO2 into deionized 2.1 ASTM Standards: 2
water. The change in conductivity of the deionized water is D 1129 Terminology Relating to Water
measured and related to carbon concentration in the oxidized D 1192 Specification for Equipment for Sampling Water
sample. Inorganic carbon is determined in a similar manner and Steam3
without the oxidation step. In both cases, the sample is D 1193 Specification for Reagent Water
acidified to facilitate CO2 recovery through the membrane. The D 2777 Practice for Determination of Precision and Bias of
relationship between the conductivity measurement and carbon Applicable Methods of Committee D19 on Water
concentration is described by a set of chemometric equations D 3370 Practices for Sampling Water from Closed Conduits
for the chemical equilibrium of CO2, HCO3–, and H+, and the D 4210 Practice for Intralaboratory Quality Control Proce-
relationship between the ionic concentrations and the conduc- dures and a Discussion on Reporting Low-Level Data3
tivity. The chemometric model includes the temperature de- D 5997 Test Method for On-Line Monitoring of Total Car-
pendence of the equilibrium constants and the specific conduc- bon, Inorganic Carbon in Water by Ultraviolet, Persulfate
tances resulting in linear response of the method over the stated Oxidation, and Membrane Conductivity Detection

--````,,-`-`,,`,,`,`,,`---
range of TOC. See Test Method D 4519 for a discussion of the D 4519 Test Method for Determination of Anions and
measurement of CO2 by conductivity. Carbon Dioxide in High Purity Water by Cation Exchange
1.2 This test method has the advantage of a very high and Degassed Cation Conductivity
sensitivity detector that allows very low detection levels on 3. Terminology
relatively small volumes of sample. Also, use of two measure-
ment channels allows determination of CO2 in the sample 3.1 Definitions— For definitions of terms used in this test
independently of organic carbon. Isolation of the conductivity method, refer to Terminology D 1129.
detector from the sample by the CO2 selective membrane 3.2 Definitions of Terms Specific to This Standard:
results in a very stable calibration, with minimal interferences. 3.2.1 inorganic carbon (IC)—carbon in the form of carbon
1.3 This test method was used successfully with reagent dioxide, carbonate ion, or bicarbonate ion.
water spiked with various organic materials. It is the user’s 3.2.2 refractory material—that which cannot be oxidized
responsibility to ensure the validity of this test method for completely under the test method conditions.
waters of untested matrices. 3.2.3 total carbon (TC)—the sum of IC and TOC.

2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
1
This test method is under the jurisdiction of ASTM Committee D19 on Water contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
and is the direct responsibility of Subcommittee D19.03 on Sampling of Water and Standards volume information, refer to the standard’s Document Summary page on
Water-Formed Deposits, Surveillance of Water, and Flow Measurement of Water. the ASTM website.
3
Current edition approved Sept. 10, 1998. Published November 1998. Withdrawn.

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 D 6317 – 98 (2004)
3.2.4 total organic carbon (TOC)—carbon in the form of (2) Conversion of remaining inorganic carbon to CO2 by
organic compounds. action of acid in both channels and oxidation of total carbon to
CO2 by action of ultraviolet (UV) radiation in the TC channel.
4. Summary of Test Method (Acid-persulfate can be added but is usually not required at
4.1 Carbon can occur in water as inorganic and organic TOC levels below 1 ppm).
compounds. This test method can be used to make independent (3) Detection of CO2 that is swept out of the U.V. reactor
measurements of IC and TC and can also determine TOC as the and delay coil by the liquid stream and passed through
difference of TC and IC. If IC is high relative to TOC it is membranes that allow the specific passage of CO2 to high
desirable to use a vacuum degassing unit to reduce the IC purity water where change in conductivity is measured and;
concentration as part of the measurement. Alternatively, the IC (4) Conversion of the conductivity detector signal to a
can be removed by acidifying and sparging the sample prior to display of carbon concentration in parts per million
injection into the instrument. The basic steps of the procedure (ppm=mg/L) or parts per billion (ppb=µg/L). The IC channel
are as follows: reading is subtracted from the TC channel to give a TOC
(1) Removal of IC, if desired, by vacuum degassing; reading. A diagram of suitable apparatus is given in Fig. 1.

--````,,-`-`,,`,,`,`,,`---

FIG. 1 Schematic Diagram of TOC Analyzer System

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 D 6317 – 98 (2004)
References 1-54 provide additional information on the method. 6.5 Contamination of the sample with both CO2 and organic
carbon is a severe problem as lower levels of analyte are
5. Significance and Use attempted. Throughout this method the analyst must be vigilant
5.1 This test method is used for determination of the carbon for all potential sources of contamination and must monitor
content of water from a variety of natural, domestic, and blanks and adjust operations to prevent contamination.
industrial sources. In its most common form, this test method
is used to measure organic carbon as a means of monitoring 7. Apparatus
organic impurities in high purity process water used in indus- 7.1 Apparatus for Carbon Determination—A typical instru-
tries such as nuclear power, pharmaceutical, and electronics. ment consists of reagent and sample introduction mechanism,
reaction vessel, detector, control system, and a display.5 Fig. 1
6. Interferences and Limitations shows a diagram of such an arrangement.
6.1 The oxidation of dissolved carbon to CO2 is brought 7.1.1 Sampling Needle— A double chambered needle ca-
about at relatively low temperatures by the chemical action of pable of piercing the sample bottle septum and pulling sample
reactive species produced by UV-irradiated persulfate ions and from the bottom of the bottle is used. The second chamber
water. Not all suspended or refractory material may be oxi- vents the top of the bottle to prevent vacuum build up as the
dized under these conditions; analysts should take steps to sample is withdrawn. Typically this needle is mounted on an
determine what recovery is being obtained. This may be done autosampler to provide unattended analysis of several samples.
by several methods: by rerunning the sample under more 7.1.2 I.C. Removal— Vacuum degassing requires the manu-
vigorous reaction conditions or by spiking samples with known facturer’s module5 which includes a vacuum pump and a
refractories and determining recovery. hollow fiber membrane assembly. Use of this vacuum degasser
6.2 Chloride ion above 250 mg/L tends to interfere with will remove essentially all IC as part of the analysis. The
oxidative reaction mechanisms in this test method. Follow membrane module consists of a tube and shell arrangement of
manufacturer’s instructions for dealing with this problem. microporous polypropylene hollow fibers. Sample flows along
Other interferences have been investigated and found to be the inside of the fibers, while air is passed on the shell
minimal under most conditions. Refer to the reference (2) for side-counterflow to the sample flow. The shell side pressure is
more information. reduced by means of a vacuum pump on the air outlet. The
6.3 Note that error will be introduced when the method of sample is acidified before introduction into the degasser to
difference is used to derive a relatively small level from two facilitate CO2 transport through the hollow fibers. Sparging
large levels. In this case the vacuum degassing unit on the requires an inert vessel with provision for sparging the acidi-
instrument should be used to reduce the concentration of IC fied sample with 50 to 100 mL/min of carbon free gas. This
prior to measurement. Alternatively, the sample can be acidi- procedure will remove essentially all IC in 2 to 10 min,
fied and sparged prior to introduction into the instrument. depending on design.
6.4 Use of the vacuum degassing unit or sparging the 7.1.3 Reactor—The sample flow is split after the addition of
sample may cause loss of volatile organic compounds, thus reagents. Half of the flow passes to the delay coil while the
yielding a value lower than the true TOC level. At low TOC other half passes into the oxidation reactor. The effluent from
levels, the degassing unit may introduce a measurable TOC and both streams passes over individual membranes that allow CO2
IC background. The user should characterize the background to pas through the membrane into prepurified water for
and performance of the degassing module for their application. detection.
Table 1 provides typical IC removal performance and back- 7.1.4 Membrane—The membrane is a CO2 selective fluo-
ground levels of the vacuum degassing unit. ropolymer which is hydrophobic and non-porous. Refer to the
bibliography for additional details.
7.1.5 Detector—The CO2 that has passed through the mem-
4
brane into the purified water is measured by conductivity
The boldface numbers in parentheses refer to the list of references found at the
end of this Test Method.
sensors. The temperature of the conductivity cell is also
automatically monitored so the readings can be corrected for
TABLE 1 Blank Contribution and IC. Removal Efficiency of
changes in temperature.
Vacuum Degassing Unit. 7.1.6 Data Display— The conductivity detector output is
Unit µg/LA TOC µg/LA IC IC level with 25 000
related to stored calibration data and then displayed as parts per
No. background background µg/L input million, (ppm = mg of carbon per litre) or parts per billion,
1 3.2 8.2 55 (ppb = µg of carbon per L). Values are given for TC, IC, and
2 3.2 22 61 TOC by difference.
3 2.4 8.0 105
4 4.2 13 89 8. Reagents and Materials
5 2.8 13 30
6 3.0 8.0 70 8.1 Purity of Reagents—Reagent grade chemicals shall be
7 4.8 8.9 67
8 4.7 8.3 63
used in all tests. Unless otherwise indicated, it is intended that
9 4.6 11 62
10 4.7 2.9 72
A 5
Values are the difference between before and after addition of the degasser to Instruments manufactured and marketed by Sievers Instruments, Inc., 6185
a high purity (<5 µg/L) water stream. Arapahoe Ave., Suite H1, Boulder, CO 80303 have been found satisfactory.
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 D 6317 – 98 (2004)
all reagents conform to the specifications of the Committee on volume. Dilutions of this stock solution are to be used to
Analytical Reagents of the American Chemical Society,6 where calibrate and test performance of the carbon analyzer.
such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficient 9. Sampling and Sample Preservation
purity to permit its use without lessening the accuracy of the 9.1 Collect the sample in accordance with Specification
determination. D 1192 and Practices D 3370.
8.2 Purity of Water— Unless otherwise indicated, refer- 9.2 Samples must be collected in contamination free bottles
ences to water shall be understood to mean reagent water sealed with a fluoropolymer lined septa. Specially cleaned (for
conforming to Type I or Type II in Specification D 1193. The TOC) 40 ml bottles are commercially available. The sample
indicated specification does not actually specify inorganic bottle should be rinsed several times with the sample, filled,
carbon or organic carbon levels. These levels can affect the and then tightly sealed.
results of this test method, especially at progressively lower 9.3 To preserve samples for this analysis, store samples in
levels of the carbon content in the samples to be measured. glass at 4 °C. To aid preservation, acidify the samples to a pH
Where inorganic carbon in reagent water is significant, CO2- of 2. It should be noted that acidification will enhance loss of
free water may be prepared from reagent water by acidifying to inorganic carbon. If the purgeable organic fraction is important,
pH 2, then sparging with fritted-glass sparger using CO 2-free fill the sample bottles to overflowing with a minimum of
gas (time will depend on volume and gas flow rate, and should turbulence and cap them using a fluoropolymer-lined cap,
--````,,-`-`,,`,,`,`,,`---

be determined by test). The carbon contribution of the reagent without headspace.

water should be determined and its effect allowed for in 9.4 For water samples where carbon concentrations are
preparation of standards and other solutions. CO2-free water greater than the desired range of instrument operation, dilute
should be protected from atmospheric contamination. Glass the samples as necessary.
containers are required for storage of water and standard 9.5 For accurate measurements of samples containing < 0.5
solutions. Continuous U.V. treatment of water with recycling mg/L stringent measures must be taken to minimize contami-
through appropriate mixed bed ion exchange resins may be nation. Low level samples exposed to ambient air will gener-
necessary to maintain an adequately low TOC reagent water. ally increase in both inorganic and organic carbon. Sample
8.3 Persulfate Reagent (15 % w/v)—Prepare ammonium container and all sampling devices must be clean and exposure
persulfate solution to a concentration of 15 % w/v by dissolv- of the sample to the atmosphere must be minimized. Blanks
ing 15 g of ammonium peroxydisulfate in water and diluting to should be carried through all steps of the sampling and analysis
100 mL. Verify that it contains less than 2000 µg/L organic procedure to check for contamination.
carbon contamination. Certification of reagent assay should be
10. Instrument Operation
available. Reagents in prepackaged containers from the instru-
ment manufacturer have been found to be acceptable. 10.1 Follow the manufacturer’s instructions for setting up
8.4 Acid Reagent (6M)—Prepare acid solution to a concen- the instrument and adjusting reagent flows. Ensure that the pH
tration of 6M and verify that it contains less than 600 µg/L of the waste stream is below four (4) in all cases. Additional
organic carbon contamination. Since halogens are potential acid is required if a vacuum degassing unit is used for IC
interferences, use only sulfuric or phosphoric acid for reagents. removal. Follow manufacturer’s instructions for reagent flows
Sulfuric acid is prepared by diluting 336 mL of 95 % reagent when using a degassing unit.
(sp gr 1.84) to 1 L with reagent water. Phosphoric acid is
11. Calibration
prepared by diluting 410 mL of 85 % reagent (sp gr 1.69) to 1
L with water. Certification of reagent assay should be available. 11.1 Use appropriate dilutions of the standard solution of
Reagents in prepackaged containers from the instrument manu- 1000 mg/L of carbon to check the instrument calibration.
facturer have been found to be acceptable. 11.2 Calibration protocols may vary with equipment manu-
8.5 Organic Carbon, Standard Solution (1000 mg/L)— facturers. However, in general, calibrate the instrument in
Choose a water-soluble, stable reagent grade compound, such accordance with the manufacturer’s instructions, and use
as benzoic acid or anhydrous potassium hydrogen phthalate standards to verify such calibration in the specific range of
(KHC8H4O4). Calculate the weight of compound required to interest for actual measurements. Plots of standard concentra-
make 1 L of organic carbon standard solution; for example, tion versus instrument reading may be used for calibration or to
KHC8H 4O4 = 0.471 g of carbon per g, so one L of 1 g/L of verify linearity of response.
standard requires 1/0.471, or 2.12, grams of KHP. Dissolve the 11.3 Below 500 µg/L, contamination of reagents is a severe
required amount of standard in some CO2-free water in a 1-L problem. Because of this it is recommended that the general
volumetric flask, add 1 mL of sulfuric acid, and dilute to calibration check of the instrument be carried out with stan-
dards above 500 µg/L. The response of the instrument is
extremely linear, allowing calibration at higher levels without
loss of accuracy at low levels. See 14.1 for data regarding
6
Reagent Chemicals, American Chemical Society Specifications. American linearity of the response.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory 12. Procedure
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, 12.1 The sample is introduced into the instrument by
MD. piercing the septum with a double chambered needle. The

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 D 6317 – 98 (2004)
analyzer in either the grab sample or autosampler mode will
pull sample out of the sample bottle, into the analyzer.
12.2 If inorganic carbon is to be removed by vacuum
degassing, or if I. C. removal is unnecessary, no additional
sample preparation is required. If inorganic carbon is to be
removed by sparging prior to sample introduction, acidify to
approximately pH 2 with concentrated acid (if not already
done) inject through the needle and sparge through the needle
with an appropriate flow of gas. Use of the double chambered
needle prevents contamination of the sample during sparging.
Other configurations that prevent sample contamination are
acceptable. Samples with high alkali content or buffer capacity
may require larger amounts of acid. In such cases, incorporate
this dilution into the calculation of results. If incomplete
sparging of CO2 from IC is suspected, sparge and analyze the
sample and then repeat the procedure until appropriate condi-

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tions are established.
12.3 Follow manufacturers’ instructions for introducing the
sample into the analyzer. The sample may be directly aspirated,
sampled from an auto sampler, or connected directly into a
source for continuous on-line monitoring.
13. Calculation FIG. 2 Instrument Response Versus Carbon Concentration

13.1 Read carbon values directly from the digital display,

printer, or computer connected to a suitable data interface on
required recoveries (6 10 %) on the QC sample. The data from
the instrument.
the other ten laboratories was used for this evaluation.
13.2 Blank correction should be applied to samples that
14.2.1 Results of this collaborative study may not be typical
have been prepared or diluted with reagent water. In the case of
of results for matrices other than those studied.
materials prepared in reagent water, the entire blank value
14.2.2 Ten samples (five pairs) were analyzed at each
obtained in the reagent water should be subtracted. In the case
laboratory for Organic Carbon. The study samples included
of dilution, the blank should be corrected for the dilution factor
eight samples made from sucrose (NIST 170) and two samples
and subtracted from the obtained value.
made from benzoic acid (Baker 0076-001). The samples
14. Precision and Bias contained an IC background level of approximately 100 µg/L.
In addition, blank and QC samples were sent with concentra-
14.1 Linearity of the response over the entire measurement
tions noted on the labels to ensure proper performance of the
range allows calibration at a single higher level concentration.
method. All participants used autosamplers that took ten
This facilitates preparation of accurate standards minimizing
consecutive aliquots of each sample vial. The first three were
the effect of contamination. Fig. 2 shows instrument response
ignored to insure that the instrument was completely purged of
for carbon versus carbon concentration over five orders of
the previous sample. The mean of the remaining seven values
magnitude from 0.25 µg/L C to 25 000 µg/L C for two
was used for all subsequent calculations. Each laboratories
instruments calibrated at 25 000 µg/L C. As stated in Section
blank data was subjected to the outlier test and the average
11, the user should confirm proper operation of the instrument
blank value for each laboratory was subtracted from each
by running check samples in the range of test samples.
result. Table 2 summarizes blank values and deviations for
14.2 An interlaboratory study was conducted to determine
each participant’s study.
the precision and bias for the determination of Organic Carbon
14.2.3 Data was evaluated as defined in D 2777–96 and
in water.7 Standards prepared in reagent water were sent to
summarized in Table 3. Labs 1 and 11 were eliminated as
twelve (12) laboratories for evaluation. One laboratory did not
outliers by the ranking test. No individual outliers were found,
complete analysis of all samples. A second lab failed to get
so all data from the remaining eight laboratories was used for
the evaluation. The last two rows of Table 3 show the standard
7
Supporting data for the precision and bias statements have been filed at ASTM deviations and relative standard deviations for seven replicates
headquarters. from a single sample container.

TABLE 2 Summary of Blank Values from Participating Laboratories

Lab No. 1 2 3 4 5 6 7 8 9 10 11 12
No. Retained values 5 5 3 5 5 5 4 5 5 5 5 5
Ave Blank µg/L 14.6 26.8 29.8 48.1 14.3 14.9 22.9 22.4 36.3 12.5 19.4 26.5
Overall Std Dev 0.8 7.0 8.8 4.0 2.5 5.4 2.3 3.1 10.2 2.5 2.5 4.7
% RSD 5.25 26.26 29.58 8.32 17.46 36.40 10.00 13.76 28.15 20.33 12.77 17.79

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TABLE 3 Final Statistical Summary for Total Organic Carbon
Conc: (µg/L) 10 11 25 28 50 55 100 110 495 550
Number of Retained Values 8 8 8 8 8 8 8 8 8 8
True Concentration 10.0 11.0 25.0 28.0 50.0 55.0 100.0 110.0 495.0 550.0
Mean Recovery 8.53 6.04 20.58 23.14 49.19 51.13 96.70 103.08 482.45 541.33
% Recovery 85.25 54.89 82.30 82.63 98.38 92.95 96.70 93.70 97.46 98.42
Overall Std Dev (St) 4.45 3.62 3.92 2.17 4.77 2.57 6.51 4.39 17.40 21.75
Overall Std Dev, % 52.19 59.92 19.07 9.40 9.69 5.03 6.73 4.26 3.61 4.02
Number of Retained Pairs 8 8 8 8 8
Single Std Dev (So) 5.28 1.87 2.00 3.46 3.59
Analyst Relative deviation, % 72.47 8.54 4.00 3.47 0.70
7 Replicate Runs Std. Dev 0.46 0.40 0.96 0.39 0.55 0.52 0.60 0.48 1.17 1.36
7 Replicate Runs Std Dev, % 1.41 1.39 1.62 0.82 0.58 0.68 0.50 0.37 0.25 0.26

14.2.4 The following equations are developed using an 15. Quality Control
unweighted least squares regression of the data obtained in this 15.1 In order to be certain that analytical values obtained
study: from using this test method are valid and accurate within the
slope intercept (1) confidence limits of the test, the following quality control
XBAR 5 0.9859~C! – 3.1485, ~R 5 0.999! 2 procedures should be followed when running the test.
15.1.1 Analyst Performance Check—If the analyst has not
St 5 0.0325~C! 1 2.4914, ~R 2 5 0.9628! performed the test before or if he/she has never generated
So 5 0.0007~C! 1 3.1582,~R 2 5 0.0105! single operator precision, a precision and accuracy study must
be performed to demonstrate analyst capability. Analyze seven
where: replicates of a standard solution prepared from a certified
St = overall precision reference material containing a concentration of analyte similar
So = single operator precision to that expected in test samples and with the range of 10 to 550
C = concentration µg/L. Each replicate must be taken through the complete
14.2.5 Fig. 3 shows the regression fitted to relate overall analytical test method including any sample preservation steps.
standard deviations to concentration. Calculate the mean and standard deviation of these values and
14.2.6 Discussion—The relatively high and variable blank compare to the acceptable ranges of precision and bias that
values shown in Table 2 suggest that there is variable contami- may be calculated by the user using the precision and bias
nation between sample containers. This is further supported by relationships listed in Section 14. This study should be re-
the good single container precision for seven replicate runs peated until the single operator precision and the mean values
from the same sample container as shown in the last two rows are within acceptable limits.
of Table 3. These data, showing much higher deviations 15.1.2 Calibration Verification—See 11.1
between vials than within one vial, suggests that the variability 15.1.3 Analyze a test method blank each time the test is run.
and detection limits suggested by the study are limited by the Use low TOC reagent water in place of a sample and analyze
cleanliness of the sample vials and sample preparation opera- as described in Section 12. The variability of blank values
tions. The users of this method must carefully evaluate the obtained must be less than the that specified by the user after
cleanliness of their sample handling and preparation tech- consideration of the precision and bias relationships near zero
niques. concentration.
15.1.4 In order to verify the quantitative value of the
laboratory’s calibration standard, analyze an independent ref-
erence material submitted as a regular sample (if practical) to
the analyst periodically. The concentration of the reference
material should be in the range of 10 to 550 µg/L. The value
obtained must fall within the control limits specified by the
outside source or the control limits used to evaluate the
laboratory’s routine calibration checks.
15.1.5 To ensure that the test method is in control, analyze
a quality control sample at the beginning and end of the run. If
large numbers of samples are analyzed in a single day, analyze
the QC sample after every 20 samples. The QC sample must be
taken through all the steps of the procedure including sample
preservation and preparation. The value obtained for the QC
sample should be within x̄ 6 3ST control limits that may be
calculated from the ST and x̄ relationships in 14.
--````,,-`-`,,`,,`,`,,`---

15.1.6 To check for interferences in the specific matrix

FIG. 3 being tested, perform a recovery spike on at least one sample

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 D 6317 – 98 (2004)
from each set of samples being analyzed by spiking a portion must be qualified with a warning that the data are suspect or an
of the sample with a known concentration of TOC and taking alternate test method should be used.
it through the complete procedure. The spike concentration 15.1.7 To check the precision of sample analyses, analyze a
plus the background concentration of TOC must not exceed the sample in duplicate each day or shift the test is run. When large
upper limit of the method. However, the total concentration of numbers of samples are being analyzed, analyze one out of
(analyte) in the spiked sample must be greater than the lower every twenty samples in duplicate. Calculate the standard
level of quantitation. Calculate percent recovery of the spike deviation of these replicate values and compare to the single
(P) using the following formula:
operator precision found in the collaborative study using an F
@A~V s 1 V! – BVs# test. Alternatively, accumulate data from duplicate analyses
P 5 100 CV (2)
and develop a relationship between single operator precision
where: and concentration within the laboratory.

--````,,-`-`,,`,,`,`,,`---
A = concentration found in spiked sample,
B = concentration found in unspiked sample, 16. Keywords
C = concentration of analyte in spiking solution,
16.1 carbon; carbon dioxide; high-purity water; inorganic
Vs = volume of sample used, and
V = volume added with spike carbon; low temperature oxidation; membrane conductivity
The percent recovery of the spike should fall within limits to detection; organic carbon; total carbon
be specified in advance by the user. If it does not, an
interference may be present and the data for the set of samples

REFERENCES

(1) Godec, R. D., Kosenka, P.K., Hutte, R.S., “Method and Apparatus for (4) Barley, R., Hutte, R., O’Neill, K., “Application of TOC Monitoring in
the Determination of Dissolved Carbon in Water”, U.S. Patent No. Semiconductor Manufacturing”, Ultrapure Water, July/August 1994,
5,132,094 (July 21, 1992). 20-25.
(2) Godec, R., O’Neill, K., Hutte, R., “New Technology for TOC Analysis (5) Bollinger, M. J., Craig, C. A., Godec, R., Kosenka, P., O’Niell, K, “A
in Water”, Ultrapure Water, Dec. 1992, 17-22. Novel Approach to Verifying TOC Instrument Accuracy,” Proceedings
(3) Deak-Phillips, A., Rathgraber, K., Hutte, R., “On-Line Application of
of the 16 th Annual Semiconductor Pure Water and Chemicals Confer-
a new TOC Analyzer in the Power Industry”, Proceedings of the 1993
ence, March, 1997
Chemistry On-line Process Instrumentation Seminar, Clearwater, FL.

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