Designation: D888 – 12

Standard Test Methods for

Dissolved Oxygen in Water1
This standard is issued under the fixed designation D888; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope E200 Practice for Preparation, Standardization, and Storage

1.1 These test methods cover the determination of dissolved of Standard and Reagent Solutions for Chemical Analysis
oxygen in water. Three test methods are given as follows: 3. Terminology
Range, mg/L Sections
Test Method A—Titrimetric Procedure– >1.0 8 to 15 3.1 Definitions—For definitions of terms used in these test
High Level methods, refer to Terminology D1129.
Test Method B—Instrumental Probe Procedure— 0.05 to 20 16 to 25
Electrochemical
3.2 Definitions of Terms Specific to This Standard:
Test Method C—Instrumental Probe Procedure— 0.05 to 20 26 to 29 3.2.1 amperometric systems, n—those instrumental probes
Luminescence-Based Sensor that involve the generation of an electrical current from which
1.2 The precision of Test Methods A and B was carried out the final measurement is derived.
using a saturated sample of reagent water. It is the user’s 3.2.2 instrumental probes, n—devices used to penetrate and
responsibility to ensure the validity of the test methods for examine a system for the purpose of relaying information on its
waters of untested matrices. properties or composition.
1.3 The values stated in SI units are to be regarded as 3.2.2.1 Discussion—The term probe is used in these test
standard. No other units of measurement are included in this methods to signify the entire sensor assembly, including
standard. electrodes, electrolyte, membrane, materials of fabrications,
1.4 This standard does not purport to address all of the and so on.
safety concerns, if any, associated with its use. It is the 3.2.3 potentiometric systems, n—those instrumental probes
responsibility of the user of this standard to establish appro- in which an electrical potential is generated and from which the
priate safety and health practices and determine the applica- final measurement is derived.
bility of regulatory limitations prior to use. For a specific
4. Significance and Use
precautionary statement, see Note 17.
4.1 Dissolved oxygen is required for the survival and
2. Referenced Documents growth of many aquatic organisms, including fish. The con-
2.1 ASTM Standards:2 centration of dissolved oxygen may also be associated with
D1066 Practice for Sampling Steam corrosivity and photosynthetic activity. The absence of oxygen
D1129 Terminology Relating to Water may permit anaerobic decay of organic matter and the produc-
D1193 Specification for Reagent Water tion of toxic and undesirable esthetic materials in the water.
D2777 Practice for Determination of Precision and Bias of
5. Purity of Reagents
Applicable Test Methods of Committee D19 on Water
D3370 Practices for Sampling Water from Closed Conduits 5.1 Purity of Reagents—Reagent grade chemicals shall be
D5847 Practice for Writing Quality Control Specifications used in all tests. Unless otherwise indicated, it is intended that
for Standard Test Methods for Water Analysis all reagents shall conform to the specifications of the Commit-
tee on Analytical Reagents of the American Chemical Society.3
Other grades may be used if it is first ascertained that the
reagent is of sufficiently high purity to permit its use without
1
These test methods are under the jurisdiction of ASTM Committee D19 on lessening the accuracy of the determination.
Water and are the direct responsibility of Subcommittee D19.05 on Inorganic
Constituents in Water.
Current edition approved March 1, 2012. Published March 2012. Originally
3
approved in 1946. Last previous edition approved in 2009 as D888 – 09. DOI: Reagent Chemicals, American Chemical Society Specifications , American
10.1520/D0888-12. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or listed by the American Chemical Society, see Analar Standards for Laboratory
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.

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 D888 – 12
5.1.1 Reagent grade chemicals, as defined in Practice E200, collection or by water sealing (inverting bottle in water) and
shall be used unless otherwise indicated. It is intended that all maintaining at a temperature of 10 to 20°C. Complete the
reagents conform to this standard. determination as soon as possible, using the appropriate
5.2 Unless otherwise indicated, reference to water shall be procedure for determining the concentration of dissolved
understood to mean reagent water conforming to Specification oxygen.
D1193, Type I. Other reagent water types may be used
provided it is first ascertained that the water is of sufficiently TEST METHOD A
high purity to permit its use without adversely affecting the TITRIMETRIC PROCEDURE—HIGH LEVEL
bias and precision of the test method. Type II water was
8. Scope
specified at the time of round robin testing of this method.
8.1 This test method is applicable to waters containing more
6. Sampling than 1000 µg/L of dissolved oxygen such as stream and sewage
6.1 Collect the samples in accordance with Practices D1066 samples. It is the user’s responsibility to ensure the validity of
and D3370. the test method for waters of untested matrices.
6.2 For higher concentration of dissolved oxygen, collect 8.2 This test method, with the appropriate agent, is usable
the samples in narrow mouth glass-stoppered bottles of with a wide variety of interferences. It is a combination of the
300-mL capacity, taking care to prevent entrainment or solu- Winkler Method, the Alsterberg (Azide) Procedure, the Rideal-
tion of atmospheric oxygen. Stewart (permanganate) modification, and the Pomeroy-
6.3 With water under pressure, connect a tube of inert Kirshman-Alsterberg modification.
material to the inlet and extend the tube outlet to the bottom of 8.3 The precision of the test method was carried out using a
the sample bottle. Use stainless steel, Type 304 or 316, or glass saturated sample of reagent water.
tubing with short neoprene connections. Do not use copper
tubing, long sections of neoprene tubing, or other types of 9. Interferences
polymeric materials. The sample line shall contain a suitable 9.1 Nitrite interferences are eliminated by routine use of
cooling coil if the water being sampled is above room sodium azide. Ferric iron interferes unless 1 mL of potassium
temperature, in which case cool the sample 16 to 18°C. When fluoride solution is used, in which case 100 to 200 mg/L can be
a cooling coil is used, the valve for cooling water adjustment tolerated. Ferrous iron interferes, but that interference is
shall be at the inlet to the cooling coil, and the overflow shall eliminated by the use of potassium permanganate solution.
be to a point of lower elevation. The valve for adjusting the High levels of organic material or dissolved oxygen can be
flow of sample shall be at the outlet from the cooling coil. The accommodated by use of the concentrated iodide-azide solu-
sample flow shall be adjusted to a rate that will fill the sampling tion.
vessel or vessels in 40 to 60 s and flow long enough to provide
a minimum of ten changes of water in the sample vessel. If the 10. Apparatus
sampling line is used intermittently, flush the sample line and 10.1 Sample Bottles, 250 or 300 mL capacity with tapered
cooling coil adequately before using. ground-glass stoppers. Special bottles with pointed stoppers
6.4 Where samples are collected at varying depths from the and flared mouths are available from supply houses, but regular
surface, a special sample bottle holder or weighted sampler types (tall or low form) are satisfactory.
with a removable air tight cover should be used. This unit may 10.2 Pipettes, 10-mL capacity, graduated in 0.1-mL divi-
be designed to collect several 250 or 300 mL samples at the sions for adding all reagents except sulfuric acid. These
same time. Inlet tubes extending to the bottom of each bottle pipettes should have elongated tips of approximately 10 mm
and the water after passing through the sample bottle or bottles for adding reagents well below the surface in the sample bottle.
displaces air from the container. When bubbles stop rising from Only the sulfuric acid used in the final step is allowed to run
the sampler, the unit is filled. Water temperature is measured in down the neck of the bottle into the sample.
the excess water in the sampler.
6.5 For depths greater than 2 m, use a Kemmerer-type 11. Reagents
sampler. Bleed the sample from the bottom of the sampler 11.1 Alkaline Iodide Solutions:
through a tube extending to the bottom of a 250 to 300 mL 11.1.1 Alkaline Iodide Solution—Dissolve 500 g of sodium
biological oxygen demand (BOD) bottle. Fill the bottle to hydroxide or 700 g of potassium hydroxide and 135 g of
overflowing and prevent turbulence and the formation of sodium iodide or 150 g of potassium iodide (KI) in water and
bubbles while filling the bottle. dilute to 1 L. Chemically equivalent potassium and sodium
salts may be used interchangeably. The solution should not
7. Preservation of Samples
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give a color with starch indicator when diluted and acidified.

7.1 Do not delay the determination of dissolved oxygen. Store the solution in a dark rubber-stoppered bottle. This
Samples for Test Method A may be preserved 4 to 8 h by solution may be used if nitrite is known to be absent and must
adding 0.7 mL of concentrated sulfuric acid (sp gr 1.84) and be used if adjustments are made for ferrous ion interference.
1.0 mL of sodium azide solution (20 g/L) to the bottle 11.1.2 Alkaline Iodide-Sodium Azide Solution I—This solu-
containing the sample in which dissolved oxygen is to be tion may be used in all of these submethods except when
determined. Biological activity will be inhibited and the adjustment is made for ferrous ion. Dissolve 500 g of sodium
dissolved oxygen retained by storing at the temperature of hydroxide or 700 g of potassium hydroxide and 135 g of

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 D888 – 12
sodium iodide or 150 g of potassium iodide in water and dilute equate. Some commercial laundry starches have also been found to be
to 950 mL. To the cooled solution add 10 g of sodium azide usable.
dissolved in 40 mL of water. Add the NaN3 solution slowly NOTE 6—If the indicator is not prepared as specified or a proprietary
starch indicator preparation is used, the report of analysis shall state this
with constant stirring. Chemically equivalent potassium and deviation.
sodium salts may be used interchangeably. The solution should
not give a color with starch indicator solution when diluted and 11.6 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid.
acidified. Store the solution in a dark rubber-stoppered bottle. One millilitre neutralizes about 3 mL of the alkaline iodide
11.1.3 Alkaline Iodide-Sodium Azide Solution II—This so- reagent.
lution is useful when high concentrations of organic matter are NOTE 7—Sulfamic acid (3 g) may be substituted.
found or when the dissolved oxygen concentration exceeds 15
11.7 Potassium Fluoride Solution (400 g/L)—Dissolve 40 g
mg/L. Dissolve 400 g of sodium hydroxide in 500 mL of
of potassium fluoride in water and dilute to 100 mL. This
freshly boiled and cooled water. Cool the water slightly and
solution is used in the procedure for eliminating ferric ion
dissolve 900 g of sodium iodide. Dissolve 10 g of sodium azide
interference. Store this solution in a plastic bottle.
in 40 mL of water. Slowly add, with stirring, the azide solution
11.8 Potassium Oxalate Solution (20 g/L)—Dissolve 2 g of
to the alkaline iodide solution, bringing the total volume to 1 L.
potassium oxalate in 100 mL of water. One millilitre of this
11.2 Manganous Sulfate Solution—Dissolve 364 g of man-
solution will reduce 1.1 mL of the KMnO4 solution. This
ganous sulfate in water, filter, and dilute to 1 L. No more than
solution is used in the procedure for eliminating ferrous ion
a trace of iodine should be liberated when the solution is added
interference.
to an acidified potassium iodide solution.
11.9 Potassium Permanganate Solution (6.3 g/L)—Dissolve
11.3 Potassium Biiodate Solution (0.025 N)—Dissolve
6.3 g of potassium permanganate in water and dilute to 1 L.
0.8125 g of potassium biiodate in water and dilute to 1 L in a
With very high ferrous iron concentrations, solution of KMnO4
volumetric flask.
should be stronger so that 1 mL will satisfy the demand. This

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NOTE 1—If the bottle technique is used, dissolve 1.2188 g of biiodate solution is used in the procedure for eliminating ferrous ion
in water and dilute to 1 L to make 0.0375 N. interference.
11.4 Phenylarsine Oxide Solution (0.025 N)—Dissolve
2.6005 g of phenylarsine oxide in 110 mL of NaOH solution 12. Procedure
(12 g/L). Add 800 mL of water to the solution and bring to a 12.1 Elimination of Ferrous Ion Interference, if necessary:
pH of 9.0 by adding HCl (1 + 1). This should require about 2 12.1.1 Add to the sample (collected as in 6.2) 0.70 mL of
mL of HCl. Continue acidification with HCl (1 + 1) until a pH H2SO4, followed by 1.0 mL of KMnO4 solution. Where high
of 6 to 7 is reached, as indicated by a glass-electrode system. iron is present, also add 1.0 mL of KF solution. Stopper and
Dilute to 1 L. Add 1 mL of chloroform for preservation. mix by inversion. The acid should be added with a 1-mL
Standardize against potassium biiodate solution. pipette graduated in 0.1-mL divisions. Add sufficient KMnO4
NOTE 2—Phenylarsine oxide is more stable than sodium thiosulfate. solution to maintain a violet tinge for 5 min. If the color does
However, sodium thiosulfate may be used. The analyst should specify not persist for 5 min, add more KMnO4 solution, but avoid
which titrant is used. For a stock solution (0.1 N), dissolve 24.82 g of excess. In those cases where more than 5 mL of KMnO4
Na2S2O3·5H2O in boiled and cooled water and dilute to 1 L. Preserve by solution is required, a stronger solution of this reagent may be
adding 5 mL of chloroform. For a dilute standard titrating solution (0.005 used to avoid dilution of the sample.
N) transfer 25.00 mL of 0.1 N Na2S2O3 to a 500-mL volumetric flask.
12.1.2 After 5 min, completely destroy the permanganate
Dilute to the mark with water and mix completely. Do not prepare more
than 12 to 15 h before use. color by adding 0.5 to 1.0 mL of K2C2O4 solution. Mix the
NOTE 3—If the full bottle technique is used, 3.9007 g must be used to sample well, and allow it to stand in the dark. Low results are
make 0.0375 N. caused by excess oxalate so it is essential to add only sufficient
NOTE 4—If sodium thiosulfate is used, prepare and preserve a 0.1 N oxalate to completely decolorize the permanganate without
solution as described in Note 1. Determine the exact normality by titration having an excess of more than 0.5 mL. Complete decoloriza-
against 0.025 N potassium biiodate solution. Dilute the appropriate tion should be obtained in 2 to 10 min. If the sample cannot be
volume (nominally 250 mL) of standardized 0.1 N Na2S2O3 solution to 1
decolorized without a large excess of oxalate, the dissolved
L. One millilitre of 0.025 N thiosulfate solution is equivalent to 0.2 mg of
oxygen. If the full bottle technique is followed, use 37.5 mL of sodium oxygen results will be of doubtful value.
thiosulfate solution and standardize to 0.0375 N. 12.2 Add 2.0 mL of MnSO4 solution to the sample as
collected in a sample bottle, followed by 2.0 mL of alkaline
11.5 Starch Solution—Make a paste of 6 g of arrowroot iodide-sodium azide solution well below the surface of the
starch or soluble iodometric starch with cold water. Pour the liquid (see Note 8 and Note 9). Be sure the solution tempera-
paste into 1 L of boiling water. Then add 20 g of potassium ture is below 30°C to prevent loss due to volatility of iodine.
hydroxide, mix thoroughly, and allow to stand for 2 h. Add 6 Carefully replace the stopper to exclude air bubbles and mix by
mL of glacial acetic acid (99.5 %). Mix thoroughly and then inverting the bottle several times. Repeat the mixing a second
add sufficient HCl (sp gr 1.19) to adjust the pH value of the time after the floc has settled, leaving a clear supernatant
solution to 4.0. Store in a glass-stoppered bottle. Starch solution. Water high in chloride requires a 10-min contact
solution prepared in this manner will remain chemically stable period with the precipitate. When the floc has settled, leaving
for one year. at least 100 mL of clear supernatant solution, remove the
NOTE 5—Powdered starches such as thyodene have been found ad- stopper, and add 2.0 mL of H2SO4, allowing the acid to run

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 D888 – 12
down the neck of the bottle. Restopper and mix by inversion 14. Precision and Bias 5
until the iodine is uniformly distributed throughout the bottle. 14.1 The precision of the test method was determined by six
Titrate without delay 203 mL of original sample. A correction operators in three laboratories, running three duplicates each
is necessary for the 4 mL of reagents added (2 mL of MnSO4 (not six laboratories as required by Practice D2777) using a
solution and 2 mL of alkaline iodide-sodium azide solution: saturated sample of reagent water. The mean concentration was
200 3 [300/(300 − 4)] = 203 mL (see Note 10)). 9.0 mg/L, and the pooled single operator precision in these
NOTE 8—Take care to use the correct alkaline iodide solution (11.1.1) samples was 0.052 mg/L.
if no nitrite is present or ferrous ion was oxidized, (11.1.2) for normal use, 14.2 Precision and bias for this test method conforms to
or (11.1.3) if there is a high organic or dissolved oxygen concentration. Practice D2777 – 77, which was in place at the time of
NOTE 9—Two millilitres of the alkaline iodide-sodium azide solution collaborative testing. Under the allowances made in 1.4 of
are used to ensure better contact of the iodide-azide solution and sample Practice D2777 – 08, these precision and bias data do meet
with less agitation. With 250-mL bottles, 1 mL of the iodide-azide solution
may be used if desired. In this procedure, as in the succeeding ones, all
existing requirements for interlaboratory studies of Committee
reagents except the H2SO4 are added well below the surface of the liquid. D19 test methods.
NOTE 10—In the case where ferrous ion interference has been elimi-
nated, a total of 6.7 mL of reagents were added (0.7 mL of acid, 1 mL of 15. Quality Control
KMnO4 solution, 2 mL of MnSO4 solution, and 3 mL of alkaline iodide 15.1 In order to be certain that analytical values obtained
solution). The volume of sample for titration is 203 mL. A slight error using these test methods are valid and accurate within the
occurs due to the dissolved oxygen of the KMnO4 solution, but rather than
confidence limits of the test, the following QC procedures must
complicate the correction further, this error is ignored.
be followed when analyzing dissolved oxygen.
12.3 Rapidly titrate the 203 mL of sample with 0.025 N 15.2 Calibration and Calibration Verification
titrating solution to a pale, straw yellow color. Add 1 to 2 mL 15.2.1 Standardize the titrating solution against the potas-
of starch indicator. Continue the titration to the disappearance sium biiodate solution.
of the blue color. 15.2.2 Verify titrating solution by analyzing a sample with a
NOTE 11—If the full bottle technique is used, transfer the entire known amount of the dissolved oxygen, if possible. The
contents of the bottle, 300 6 3 mL, to a 500-mL Erlenmeyer flask and amount of the sample should fall within 615 % of the known
titrate with 0.0375 N titrating solution. concentration.
NOTE 12—At the correct end point, one drop of 0.025 N KH(IO3)2 15.2.3 If standardization cannot be verified, restandardize
solution will cause the return of the blue color. If the end point is overrun, the solution.
continue adding 0.025 N KH(IO3)2 solution until it reappears, noting the
volume required. Subtract this value, minus the last drop of
15.3 Initial Demonstration of Laboratory Capability
KH(IO3)2(0.04 mL) from the volume of 0.025 N titrating solution used. 15.3.1 If a laboratory has not performed the test before, or if
Disregard the late reappearance of the blue color, which may be due to the there has been a major change in the measurement system, for
catalytic effect of organic material or traces of uncomplexed metal salts. example, new analyst, new instrument, and so forth, a precision
and bias study must be performed to demonstrate laboratory
13. Calculation capability.
13.1 Calculate the dissolved oxygen content of the sample 15.3.2 Analyze seven replicates of the same solution. Each
as follows: replicate must be taken through the complete analytical test
T 3 0.2 method including any sample preservation and pretreatment
Dissolved oxygen, mg/L 5 200 3 1000 (1) steps.
15.3.3 Calculate the mean and standard deviation of the
where: seven values and compare to the acceptable ranges of bias in
T = 0.025 N titrating solution required for titration of the 14.1. This study should be repeated until the recoveries are
sample, mL. within the limits given in 14.1. If an amount other than the
13.2 Use Eq 2 to convert to a standard temperature and recommended amount is used, refer to Practice D5847 for
pressure measurement. information on applying the F test and t test in evaluating the
A acceptability of the mean and standard deviation.
Dissolved oxygen, mg/L 5 0.698 (2)
15.4 Laboratory Control Sample (LCS)
15.4.1 Air-saturated reference water samples may be used
where: for laboratory control samples. The value obtained must fall
A = oxygen at 0°C and 760 mm Hg, mL.
within the control limits established by the laboratory.
NOTE 13—Each millilitre of 0.0375 N titrant is equivalent to 1 mg/L O2 15.5 Method Blank
when the full bottle technique is used. 15.5.1 Analyze a reagent water test blank with each batch.
NOTE 14—If the percentage of saturation at 760-mm atmospheric The amount of dissolved oxygen found in the blank should be
pressure is desired, the dissolved oxygen found is compared with
less than the analytical reporting limit. If the amount of
solubility data from standard solubility tables,4 making corrections for
barometric pressure and the aqueous vapor pressure, when necessary. See dissolved oxygen is found above this level, analysis of samples
Appendix X1. is halted until the contamination is eliminated, and a blank

4 5
Carpenter, J. H., “New Measurement of Oxygen Solubility in Pure and Natural Supporting data have been filed at ASTM International Headquarters and may
Water,” Limnology and Oceanography, Vol 11, No. 2, April 1966, pp. 264–277. be obtained by requesting Research Report D19–1070.
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shows no contamination at or above this level, or the results chemical reactions. Under steady-state conditions, the current
must be qualified with an indication that they do not fall within or potential can be correlated with dissolved oxygen concen-
the performance criteria of the test method. trations.
15.6 Matrix Spike (MS) NOTE 15—Steady-state conditions necessitate the probe being in ther-
15.6.1 Dissolved oxygen is not an analyte that can be mal equilibrium with the solution, this typically taking 20 min for
feasibly spiked into samples. nonlaboratory conditions.6
15.7 Duplicate
17.1.1 Probes that employ membranes normally involve
15.7.1 To check the precision of sample analyses, analyze a
metals of different nobility immersed in an electrolyte that is
sample in duplicate with each batch. The value obtained must
retained by the membrane. The metal of highest nobility (the
fall within the control limits established by the laboratory.
cathode) is positioned at the membrane. When a suitable
15.7.2 Calculate the standard deviation of the duplicate potential exists between the two metals, reduction of oxygen to
values and compare to the precision determined by the labo- hydroxide ion occurs at the cathode surface. An electrical
ratory or in the collaborative study using an F test. Refer to current is developed that is directly proportional to the rate of
6.4.4 of Practice D5847 for information on applying the F test. arrival of oxygen molecules at the cathode.
15.7.3 If the result exceeds the precision limit, the batch 17.1.2 The thallium probe, which does not utilize a mem-
must be reanalyzed or the results must be qualified with an brane, exposes a thallium electrode to the water sample.
indication that they do not fall within the performance criteria Reaction of oxygen with the thallium establishes a potential
of the test method. between the thallium electrode and a reference electrode. The
15.8 Independent Reference Material (IRM) potential is related logarithmically to dissolved oxygen con-
15.8.1 Independent reference water samples may be ob- centration. The cell output decreases (theoretically 59 mV/
tained from commercial sources. The value obtained from decade at 25°C) with increased oxygen concentration.
these samples must fall within the control limits established by
the laboratory. NOTE 16—The thallium probe has utility in waste treatment monitoring
systems; it has limited application under conditions of high dissolved
oxygen (>8 mg/L) and low temperature (<10°C).
TEST METHOD B
INSTRUMENTAL PROBE PROCEDURE— 17.1.3 The electronic readout meter for the output from
ELECTROCHEMICAL dissolved oxygen probes is normally calibrated in convenient
scales (0 to 10, 0 to 15, or 0 to 20 mg/L) with a sensitivity of
16. Scope approximately 0.05 mg/L. More sensitive dissolved oxygen
ranges are practical through amplification in the electronic
16.1 This test method is applicable to waters containing
readout (including µg/L readings in boiler feed waters).
dissolved oxygen in the range from 50 to 20 000 µg/L. It is the
17.2 Interfacial dynamics at the probe-sample interface are
user’s responsibility to ensure the validity of this test method
a factor in probe response. Turbulence should be constant or
for waters of untested matrices.
above some minimum level as recommended by the instrument
16.2 This test method describes procedures that utilize
manufacturer.
electrochemical probes for the determination of dissolved
17.3 Response rates of dissolved oxygen probes are rela-
oxygen in fresh water and in brackish and marine waters that
tively rapid, often as fast as 99 % in 15 s. Probe outputs may
may contain dissolved or suspended solids. Samples can be
be recorded for continual monitoring or utilized for process
analyzed in situ in bodies of water or in streams, or samples
control (see Note 15).
can be collected and analyzed subsequent to collection. The

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electrochemical probe method is especially useful in the 18. Interferences
monitoring of water systems in which it is desired to obtain a 18.1 Dissolved organic materials normally encountered in
continuous record of the dissolved oxygen content. water are not known to interfere in the output from dissolved
16.2.1 This test method is recommended for measuring oxygen probes.
dissolved oxygen in waters containing materials that interfere 18.2 Dissolved inorganic salts are a factor in the calibration
with the chemical methods, such as sulfite, thiosulfate, poly- of dissolved oxygen probe.
thionate, mercaptans, oxidizing metal ions, hypochlorite, and 18.2.1 Solubility of oxygen in water at a given oxygen
organic substances readily hydrolyzable in alkaline solutions. partial pressure changes with the kind and concentration of
16.3 Electrochemical dissolved oxygen probes are practical dissolved inorganic salts. Conversion factors for seawater and
for the continuous monitoring of dissolved oxygen content in brackish waters may be calculated from dissolved oxygen
natural waters, process streams, biological processes, etc., saturation versus salinity data if internal compensation is not
when the probe output is conditioned by a suitably stable included in the instrument. Conversion factors for specific
electronic circuit and recorded. The probe must be standard- inorganic salts may be developed experimentally. Broad varia-
ized before use on samples free of interfering materials, tions in the kinds and concentrations of salts in samples can
preferably with the azide modification of Test Method A. make the use of a membrane probe difficult.
17. Summary of Test Method
6
D’Aoust, B. G., Clark, M. J. R., “Analysis of Supersaturated Air in Natural
17.1 The most common instrumental probes for determina- Waters and Reservoirs,” Transactions of the American Fisheries Society, Vol 109
tion of oxygen dissolved in water are dependent upon electro- , 1980, pp. 708–724.

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18.2.2 The thallium probe measures ionic activity instead of 19.1.2 Accessory Equipment may involve apparatus to
concentration as do all ion selective electrodes. Gross changes move the sample past the probe and to provide suitable
in the concentration of dissolved salts will affect the activity turbulence at the membrane-sample interface.
coefficient of the thallous ion and thus shift the span (see 19.2 Potentiometric Probes—The commonly used potentio-
20.2.1). The thallium probe may be calibrated and operated in metric probe employs a thallium-measuring electrode and a
water of any conductivity above 100 µS, but a ten-fold change suitable reference half cell such as a saturated calomel. At 25°C
in conductivity will produce an error of approximately 20 %. and 0.1 mg/L of dissolved oxygen, the cell establishes a
Since the thallium requires a conducting path through the negative potential of approximately 817 mV. The potential
sample to the reference electrode, the response will become decreases logarithmically in absolute value with increased
sluggish at very low conductivity. It is therefore desirable to dissolved oxygen concentration (theoretically, 59 mV/decade
calibrate the sensor in solutions having a conductivity greater change in dissolved oxygen concentration) to approximately
than 100 µS. 688 mV at 15 mg/L of dissolved oxygen. An external milli-
18.3 Reactive compounds can interfere with the output or voltage source that opposes the output of the electrometer is
the performance of dissolved oxygen probes. used to adjust the net readout of output to the desired range.
18.3.1 Membrane probes are sensitive to reactive gases that
may pass through the membrane. Chlorine will depolarize the NOTE 17—Thallium and its salts are toxic. Avoid contact with the skin.
cathode and cause a high probe output. Long-term exposure to
chlorine can coat the anode with the chloride of the anode 20. Apparatus Standardization
metal and may eventually desensitize the probe. Hydrogen 20.1 Under equilibrium conditions, the partial pressure of
sulfide will interfere with membrane probes if the applied oxygen in air-saturated water is equal to that of the oxygen in
potential is greater than the half-wave potential of the sulfide the water-saturated air. Consequently, a probe may be cali-
ion. If the applied potential is less than the half-wave potential, brated in air as well as water. Consider carefully the manufac-
an interfering reaction will not occur, but coating of the anode turer’s recommended procedure. If it is necessary to zero the
metal can occur. instrument, immerse the probe in water containing 1 g of
18.3.2 The thallium probe is affected by interference from sodium sulfite and two drops of saturated cobalt chloride
soluble sulfur compounds, such as hydrogen sulfide or mer- solution (as deoxygenation catalyst) per litre of water and

--`,`,,``,,,,`,,,`,`,,``,,`-`-`,,`,,`,`,,`---
captans. Ten milligrams of hydrogen sulfide per litre of water adjust the instrument to read zero. If a water-saturated air
will produce a negative error corresponding to approximately 1 calibration is necessary, follow the manufacturer’s directions
mg/L of dissolved oxygen. Free halogens also will interfere for its preparation.
with the thallium probe if present in appreciable concentra-
20.2 To calibrate the probe in water, carefully obtain ap-
tions, such as above 2 mg of chlorine per litre of water.
proximately 1 L of the type of water to be tested and saturate
18.4 At dissolved oxygen concentrations below 2 mg/L, pH
it with oxygen from the atmosphere by passing clean air
variation below 4 and above 10 interfere with the performance
through it. Carefully draw three replicate samples from the
of the thallium probe (approximately 60.05 mg/L dissolved
well-mixed sample and immediately determine the dissolved
oxygen per pH unit). The performance of membrane probes is
oxygen concentration by Test Method A in duplicate. In the
not affected by pH changes.
third replicate sample, immerse the probe and provide for
18.5 Dissolved oxygen probes are temperature sensitive and
suitable turbulence in the sample. Standardize the probe by
temperature compensation is normally provided by the manu-
adjusting the meter reading to the dissolved oxygen value as
facturer. The thallium probe has a temperature coefficient of
determined by the chemical procedure. If substances that
1.0 mV/°C, membrane probes have a temperature coefficient of
interfere with the chemical method are present in the natural
4 to 6 %/°C dependent upon the membrane employed.
water or wastewater sample, standardize the probe using
18.6 Insoluble organic or inorganic materials that can coat
reagent water or a synthetic sample as indicated below.
the surface of dissolved oxygen probes will affect the perfor-
mance of either the thallium or membrane probes. 20.2.1 Fresh Water Samples (less than 1000 mg/L of dis-
solved salts)—If chemical interferences are absent, use a test
19. Apparatus sample as indicated above. If interferences are present, use
19.1 Amperometric Probes—Oxygen-sensitive probes of reagent water for membrane probes. With thallium probes, the
the amperometric type are normally composed of two solid greatest accuracy can be obtained from calibrating in a sample
metal electrodes of different nobility in contact with a support- of the water to be tested or a synthetic sample similar to the test
ing electrolyte that is separated from the test solution by a sample.
selective membrane. The current generated by the reduction of 20.2.2 Salt Water Samples and Membrane Probes (greater
oxygen at the cathode is measured through an electronic circuit than 1000 mg/L of dissolved salts)—Use a sample of clean
and displayed on a meter. Typically, the anode is constructed of water having the same salt content as the test material. If a
metallic silver or lead and the cathode of gold or platinum. sample free from substances that interfere with the azide
Probes are generally not affected by hydraulic pressure and can method is not available, prepare a synthetic standardization
be used in the temperature range from 0 to 50°C. sample by adding the same salts contained in the sample until
19.1.1 Semipermeable Membranes of Polyethylene or TFE- the two solutions have the same electrical conductance within
fluorocarbon permit satisfactory oxygen diffusion and limit 5 %. High concentrations of dissolved salts are not a problem
interference from most materials. with the thallium probe.

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20.3 Temperature Coeffıcient—Systems are available with A5O/R
automatic temperature compensation that permit direct mea- (5)
surements in milligrams per litre of dissolved oxygen. The where:
temperature compensation of membrane probes corrects for O = actual dissolved oxygen concentration, mg/L, as deter-
changes in membrane characteristics including boundary-layer mined by Test Method A, and
effects at the membrane-water interface and the changes in R = reading of the probe meter.
solubility of oxygen in water. The temperature compensation For the reagent water control to which the probe is cali-
of thallium probes corrects for the changes characteristic of brated, the value of A is 1.0. Prepare a plot with salt
oxidation/reduction systems (see Note 15). It is necessary that concentration as abscissa and the ratio A as ordinate. Use the
the probe is in thermal equilibrium with the solution to be developed curve for calculation of the dissolved oxygen
measured for satisfactory temperature correction. content of salt waters.
20.3.1 For those instrumental systems using membrane
probes that are not temperature-compensated, the following 21. Sampling
procedure is recommended to obtain the temperature coeffi- 21.1 Bottle Samples—Collect a bottle sample by the proce-
cient. Measure the oxygen content in water samples for five dure described in Practice D1066 or Practices D3370. Collect
temperatures over a 610°C range greater and less than the the samples in 300-mL BOD bottles or other suitable glass-
expected sample temperature. By a least-squares procedure, or stoppered bottles, preventing entrainment or solution of atmo-
graphically in a semilog plot of Y versus T, calculate the slope spheric oxygen. If analysis is delayed beyond 15 min, cool the
and intercept constant as follows: sample below 5°C and hold at this temperature until analyzed.
Log y 5 B / T 1 A Make the dissolved oxygen determination without further
(3) temperature adjustment using the appropriate temperature
where: coefficient. It will be necessary to have the probe at the
y = scale factor, milligrams of dissolved oxygen per litre temperature of the sample or otherwise compensate for insta-
per microampere of electrode current, bility due to heat flow from probe to sample.
B = slope constant, 21.2 In Situ Samples—An effective use of the instrumental
T = temperature, °C, and probes is for the direct, in situ determination of dissolved
A = intercept constant. oxygen. By this means, sample handling problems are avoided,
This relationship is linear on a semilog plot only over a range and data may be obtained quickly at various locations in a body
of 610°C. Over larger ranges an equation of higher degree is of water without concern for the change in oxygen during
necessary to reflect the curvature of the relationship. storage or handling.
20.3.2 If the thallium probe is utilized in a circuit without
22. Procedure
temperature compensation, the observed output in millivolts
must be corrected for the temperature sensitivity of the 22.1 Consider carefully the manufacturer’s recommenda-
measuring cell that has a temperature coefficient of 1.0 mV/°C. tions on the use of equipment to obtain satisfactory operation.
The measuring cell’s output will increase (apparent dissolved 22.2 Provide for suitable turbulent flow past the membrane
oxygen concentration decrease) with an increase in tempera- of membrane probes or past the thallium probe. This may,
ture, under some circumstances, be achieved adequately in flowing
streams. However, in large bodies of water, it may be necessary
MVR 5 MV0 2 1.0 ~To 2 TR!
(4)
to employ mechanical stirring or pumping of water past the
probe. For accurate results, it is important that comparable
where: degrees of turbulence be employed both for calibration and
MVR = millivolts of output at reference temperature, utilization.
MV0 = millivolts of output observed, 22.3 If the probe is not automatically compensated for
TR = reference temperature, °C, and temperature changes, record the temperature of the water at the
To = temperature at the observed output, °C. sample probe at the time of dissolved oxygen measurement. To
20.4 Correction for Content of Dissolved Salts—If the avoid heat-flow effects, it is important that temperature equi-
concentration of salts is above 1000 mg/L, it will be necessary librium be established between sample and probe.
to correct for the effect of the salts in the relationship between 22.4 Recalibrate the probe whenever the comparison with
oxygen partial pressure and concentration and also for the reference samples (20.2) indicates an absolute error of more
activity of thallium ion. For any given salt, a series of than 60.2 mg/L of dissolved oxygen or other value that is
experimental data should be obtained in which solutions are compatible with the desired accuracy.
prepared by dissolving varying weights of the salt in reagent 22.4.1 Careful handling is required with membrane probes
water in the range of interest. The solutions plus a reagent to avoid rupturing the thin membrane.
water control are aerated at constant temperature until oxygen 22.4.2 Recalibrate the probe after replacing the membrane
saturation is achieved. Determine the oxygen concentration of or cleaning the probe in accordance with the manufacturer’s
each solution by the chemical method and, at the same time, directions. For a period of a few hours after a membrane
obtain probe readings. Determine the ratio A for each solution replacement, the probe output may drift, and frequent recali-
as follows: bration may be required.
--`,`,,``,,,,`,,,`,`,,``,,`-`-`

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22.5 Probes can become fouled by oil, grease, biological 25.3 Initial Demonstration of Laboratory Capability
growths, etc., and cleaning may be required. Some of the 25.3.1 If a laboratory has not performed the test before, or if
techniques currently in use include air-blasting, brush cleaning, there has been a major change in the measurement system, for
and ultrasonic cleaning systems. example, new analyst, new instrument, and so forth, a precision
22.6 The probe may be utilized in situ or the sample may be and bias study must be performed to demonstrate laboratory
transferred to a sampling station that houses the probe and capability.
associated equipment. 25.3.2 Analyze seven replicates of the same solution. Each
22.6.1 In situ placement of the probe is preferable from the replicate must be taken through the complete analytical test
consideration that sample handling is not involved. However, method including any sample preservation and pretreatment
in situ installations may be impractical because of problems steps.
with vandalism, severe climate conditions (freezing, etc.), and 25.3.3 Calculate the mean and standard deviation of the
difficulty in probe recovery for maintenance. seven values and compare to the acceptable ranges of bias in
22.6.2 The use of sample transfer systems is practical when 24.1. This study should be repeated until the recoveries are
proper consideration is given to design features such as line within the limits given in 24.1. If an amount other than the
size, rates of transfer, kind of pump and location, practicality recommended amount is used, refer to Practice D5847 for
for cleaning the transfer system, and other maintenance. information on applying the F test and t test in evaluating the
22.6.3 Examine unattended probes at least once per week acceptability of the mean and standard deviation.
and recalibrate when required depending upon condition and 25.4 Laboratory Control Sample (LCS)
service. Recalibration may be accomplished by using a por- 25.4.1 Air-saturated reference water samples may be used
table probe that has been placed into position next to the for laboratory control samples. The value obtained must fall
unattended probe and that has been properly calibrated as within the control limits established by the laboratory.
outlined in 20.2. 25.5 Method Blank
25.5.1 Analyze a reagent water test blank with each batch.
23. Calculation The amount of dissolved oxygen found in the blank should be
23.1 For uncompensated probes, correct the observed meter less than the analytical reporting limit. If the amount of
reading for the difference of the observed temperature from the dissolved oxygen is found above this level, analysis of samples
standardization temperature by the factors developed in 20.3. is halted until the contamination is eliminated, and a blank
23.2 For wastewaters with varying salt contents, make shows no contamination at or above this level, or the results
corrections utilizing the data developed in 20.4. must be qualified with an indication that they do not fall within
the performance criteria of the test method.
24. Precision and Bias 25.6 Matrix Spike (MS)
24.1 The precision of this test method was determined by 25.6.1 Dissolved oxygen is not an analyte that can be
six operators in three laboratories running three duplicates each feasibly spiked into samples.
(not six laboratories as required by Practice D2777) using a 25.7 Duplicate
saturated sample of reagent water. The mean concentration was 25.7.1 To check the precision of sample analyses, analyze a
9.0 mg/L, and the pooled single-operator precision in these sample in duplicate with each batch. The value obtained must
samples was 0.029 mg/L. fall within the control limits established by the laboratory.
24.2 Precision and bias for this test method conforms to 25.7.2 Calculate the standard deviation of the duplicate
Practice D2777 – 77, which was in place at the time of values and compare to the precision determined by the labo-
collaborative testing. Under the allowances made in 1.4 of ratory or in the collaborative study using an F test. Refer to
Practice D2777 – 08, these precision and bias data do meet 6.4.4 of Practice D5847 for information on applying the F test.
existing requirements for interlaboratory studies of Committee 25.7.3 If the result exceeds the precision limit, the batch
D19 test methods. must be reanalyzed or the results must be qualified with an
indication that they do not fall within the performance criteria
25. Quality Control of the test method.
25.1 In order to be certain that analytical values obtained 25.8 Independent Reference Material (IRM)
using these test methods are valid and accurate within the 25.8.1 Independent reference water samples may be ob-
confidence limits of the test, the following QC procedures must tained from commercial sources. The value obtained from
be followed when analyzing dissolved oxygen. these samples must fall within the control limits established by
25.2 Calibration and Calibration Verification the laboratory.
25.2.1 Standardize the titrating solution against the potas-
sium biiodate solution. TEST METHOD C
25.2.2 Verify titrating solution by analyzing a sample with a INSTRUMENTAL PROBE PROCEDURE—
known amount of the dissolved oxygen, if possible. The LUMINESCENCE-BASED SENSOR
amount of the sample should fall within 615 % of the known
concentration. 26. Scope
25.2.3 If standardization cannot be verified, restandardize 26.1 This test method is applicable to waters containing
the solution. dissolved oxygen in the range from 50 to 20 000 µg/L. It is the
--`,`,,``,,,,`,,,`,`,,``,,`-`-`,,`,,`,`,,`---

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user’s responsibility to ensure the validity of this test method 29.2 Calibration verification of the sensor is recommended
for waters of untested matrices. as part of the laboratories’ quality control program to ensure
26.2 This method is for an instrumental probe- the internal calibration; point calibration is constant and
luminescence-based sensor using the technology of frequency- invariant during DO measurements.
domain lifetime-based luminescence quenching and signal 29.3 Under equilibrium conditions, the partial pressure of
processing for analysis of dissolved oxygen. This method is oxygen in air-saturated water is equal to that of oxygen in
amenable to all water and wastewater matrices that are free water-saturated air. Consequently, the calibration and verifica-
from interferences at normal water and influent-to-treatment tion of the instrumental probe-luminescence based sensor may
and final effluent wastewater concentrations. be performed in air as well as water. The data presented in this
26.3 Sustained periods of sensor immersion in water con- method was based on instruments with a single-point calibra-
taining high levels of chlorine dioxide may degrade sensor tion.
performance. Refer to manufacturer’s guidelines for specific 29.4 Preparation of Water-saturated Air Sample:
instrument interferences. 29.4.1 Add 1⁄4 in. of reagent water to a clean 300-mL BOD
26.4 Intrumental probeluminescence-based sensors for dis- bottle and seal with stopper.
solved oxygen are practical for the continuous monitoring of 29.4.2 Shake vigorously for approximately 30 seconds.
dissolved oxygen content in natural water, process streams and
29.4.3 Allow 30 minutes for the BOD bottle and its contents
biological processes, etc.
to equilibrate to room temperature.
27. Summary of Test Method 29.4.4 The water-saturated air sample is now ready to use
27.1 The most common method is Frequency Domain for calibration purposes.
Lifetime-based Luminescence Quenching of Dissolved Oxy- 29.5 Preparation of Air-saturated Water:
gen. 29.5.1 Add approximately 1500 mL of reagent water to a
2-L beaker.
28. Apparatus 29.5.2 Allow the water to equilibrate to room temperature
28.1 Lifetime Luminescence-Based Probe—Luminescence- (6 2°C).
based sensor probes that measure luminescence lifetime are 29.5.3 Using a steady stream of clean compressed air
normally composed of a luminophore embedded sensing foil, (approximately 10 to 40 mL per minute flow rate) aerate the
an emitter (Light Emitting Diode - LED) and a photodetector. water for a minimum of 30 minutes.
The pulsed or modulated emitter causes excitation of the 29.5.4 Allow the water to re-equilibrate to room tempera-
luminophore, which is quenched in the presence of oxygen. ture (6 2°C) for 45 to 60 minutes.
The photodetector converts the luminescence emission into an 29.5.5 Transfer aerated water to clean BOD bottles until
electrical signal that can be sampled and processed to compute overflowing, then seal with stopper.
the luminescence phase shift or luminescence lifetime. This
29.5.6 Note the laboratory barometric pressure and sample
phase shift or lifetime is used to quantify dissolved oxygen
temperature and use values from Table X1.1 to calculate the
concentrations.
theoretical dissolved oxygen concentration.
28.2 Probe designs vary in the emitter wavelength and
luminophore that is used in the sensing foil. 29.5.7 Analyze within 4 hours of preparation.
29.6 Provide for suitable turbulent flow past the sensor cap.
29. Calibration and Calibration Verification 29.7 Verify calibration with water-saturated air or air-
29.1 Calibration—Some luminescence-based sensors have saturated water and the completion of matrix samples.
a built-in multipoint calibration and therefore requires no initial 29.7.1 Calibration verification should be within 97 to 104 %
multipoint calibration. of theoretical dissolved oxygen concentration.

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

FIG. 1 Optical Bench or Integrated Probe

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29.7.2 If calibration verification is outside of theoretical TABLE 2 Method Performance of DO Measurements from Air-
recovery range, re-calibrate sensor and re-analyze matrix saturated Water Reference Samples
samples. Lab No. Data Set 1 Data Set 2
29.8 Two-point calibrations are acceptable; however, inter- Method A Method B Method C Method A Method B Method C
laboratory data included in this standard was collected using a Winkler % Rec.Membrane LDO % Rec. Winkler Membrane LDO % Rec.
% Rec. % Rec. % Rec.
single-point calibration.
1 88.2 95.7 96..7 96.1 99.4 96.0
29.8.1 It is the users responsibility to demonstrate accept-
ability of calibration. Data must meet the method requirements 2 97.5 98.9 98.2 97.5 98.9 98.9

in Table 1 and Table 2. 3 97.9 99.0 101.0 98.7 98.9 99.2

29.8.2 Steps and supporting data for a two-point calibration 5 99.9 98.1 99.2 97.4 97.7 99.5
can be found in Appendix X2. 6 96.7 96.6 100.0 91.0 90.6 101.0
29.9 Preparation of nitrogen-saturated water (for 0 point of 7 94.3 94.3 101.0 94.5 94.5 98.4
a two-point calibration): 8 95.0 96.1 101.0 96.2 96.2 99.6
29.9.1 Add approximately 1500 mL of reagent water to a
9 109.0 104.0 107.0 106.0 105.0 104.0
2-L beaker.
10 93.2 90.8 98.6 93.8 94.8 94.8
29.9.2 Using a steady stream of clean compressed nitrogen
(approximately 10 to 40 mL per minutes flow rate) aerate the 11 104.0 104.0 102.0 105.0 97.9 102.0
water for a minimum of 30 minutes. Average 97.5 97.7 101.0 97.6 97.4 99.3
29.10 Preparation of saturated sodium sulfite solution: Stdev 5.6 4.0 2.9 4.7 3.8 2.7
29.10.1 Add approximately 252.08 g/L of sodium sulfite %RSD 5.8 4.1 2.9 4.8 3.9 2.7
(Na2SO3) to reagent water for a 2 M solution. Alternatively, Pooled Data Sets
add approximately 50g of anhydrous sodium sulfite (Na2SO3)
Average 97.6 97.5 100.0
to 1L of reagent water for a solution of about 0.4M.
Stdev 5.0 3.8 2.7
29.10.2 The sodium sulfite sample is now ready to use for
calibration purposes. %RSD 5.2 3.9 2.7

30. Precision and Bias

30.1 The precision of the test method was determined by 31.3 Initial Demonstration of Laboratory Capability:
eight laboratories using four saturated samples of reagent water 31.3.1 If a laboratory has not performed the test before, or if
at a reference dissolved oxygen concentration of 1.74 mg/L. there has been a major change in the measurement system, for
The mean concentration was 1.73 mg/L, and the pooled single example, new analyst, new instrument, and so forth, a precision
operator precision in these samples was 0.02 mg/L. and bias study must be performed to demonstrate laboratory
30.2 Precision and bias for this test method conform to capability.
Practice D2777 – 03, which was in place at the time of 31.3.2 Analyze four replicates of air-saturated water.

--`,`,,``,,,,`,,,`,`,,``,,`-`-`,,`,,`,`,,`---
collaborative testing. Under the allowances made in Section 31.3.3 Calculate the mean and standard deviation of the
1.4 of D2777 – 08, these precision and bias data do meet seven values and compare to the acceptable ranges of bias in
existing requirements for interlaboratory studies of Committee 30.1 and recovery and precision in Table 1. This study should
D19 test methods. be repeated until the recoveries are within the limits given in
30.1.
NOTE 18—The data presented in this method was based on instruments
with a single-point calibration. The calibration was performed in air and 31.4 Laboratory Control Sample (LCS):
verified in water. 31.4.1 Air-saturated reference water samples may be used
for laboratory control samples. The value obtained must fall
31. Quality Control within the control limits established by the laboratory.
31.1 In order to be certain that analytical values obtained 31.5 Matrix Spike (MS):
using these test methods are valid and accurate within the 31.5.1 Dissolved oxygen is not an analyte that can be
confidence limits of the test, the following QC procedures must feasibly spiked into matrix samples.
be followed when analyzing dissolved oxygen. 31.6 Duplicate:
31.2 Calibration and Calibration Verification: 31.6.1 To check the precision of sample analyses, analyze
31.2.1 Use water-saturated air and air-saturated water refer- an air-saturated water reference sample in duplicate with each
ence samples described in 29.4 and 29.5. Calibration values batch. The value obtained must fall within the control limits
should fall within values in Table 1. established by the laboratory.
31.6.2 Calculate the standard deviation of the duplicate
TABLE 1 Pooled Round Robin Recovery and Precision Criteria values and compare to the precision determined by the labo-
for Luminescence-based Sensor ratory or in the collaborative study.
Reference Water DO Conc. 97.5 % Lower 97.5 % Upper 95 % Upper 31.6.3 If the result exceeds the precision limit, the batch
DO Range (mg/L) Limit of Limit of Limit of
Recovery (%) Recovery (%) Precision (%)
must be reanalyzed or the results must be qualified with an
indication that they do not fall within the performance criteria
Low 1.72 – 1.74 95.4 104.0 1.75
High 7.22 – 9.23 96.2 104.0 1.10 of the test method.
31.7 Independent Reference Material (IRM):

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31.7.1 Independent reference water samples may be ob- 32. Keywords
tained from commercial sources. The value obtained from
32.1 analysis; dissolved oxygen; frequency domain;
these samples must fall within the control limits established by
lifetime-based; luminescence; probe; titrimetric; water
the commercial source.
31.8 Table 1 and Table 2 reflect round robin results that a
typical user of this method should achieve.

APPENDIXES

(Nonmandatory Information)

X1. OXYGEN SATURATION VALUES

X1.1 Oxygen Saturation Values in Water and Elevations— The solubility of oxygen in water exposed to water saturated
The solubility of oxygen in water at various temperatures and air under an atmospheric pressure of 760 mm is shown in Table
elevations under an atmospheric pressure of 760 mm is shown X1.2 at several temperatures and concentrations of sea water to
in Table X1.1. illustrate the effects of salt concentration and temperature. The
solubility versus dissolved salt concentration can vary consid-
X1.2 Oxygen Saturation Values in Water and Salt Waters— erably with the nature of the salts in solution.

TABLE X1.1 Solubility of Oxygen (mg/L) at Various Temperatures TABLE X1.2 Solubility of Oxygen (mg/L) at Various Temperatures
and Elevations (Based on Sea Level Barometric Pressure of 760 and Chlorinity (Based on Sea Level Barometric Pressure of 760
mm Hg) 12 mm Hg)12
Temperature, Elevation, Feet above Sea Level Temperature,° Chlorinity, %
°C 0 1000 2000 3000 4000 5000 6000 C 0 4.0 8.0 12.0 16.0 20.0
0 14.6 14.1 13.6 13.2 12.7 12.3 11.8 0 14.6 13.9 13.2 12.5 11.9 11.3
2 13.8 13.3 12.9 12.4 12.0 11.6 11.2 2 13.8 13.2 12.5 11.9 11.4 10.8
4 13.1 12.7 12.2 11.9 11.4 11.0 10.6 4 13.1 12.5 11.9 11.3 10.8 10.3
6 12.4 12.0 11.6 11.2 10.8 10.4 10.1 6 12.4 11.8 11.3 10.8 10.3 9.8
8 11.8 11.4 11.0 10.6 10.3 9.9 9.6 8 11.8 11.3 10.8 10.3 9.8 9.4
10 11.3 10.9 10.5 10.2 9.8 9.5 9.2 10 11.3 10.8 10.3 9.8 9.4 9.0
12 10.8 10.4 10.1 9.7 9.4 9.1 8.8 12 10.8 10.3 9.8 9.4 9.0 8.6
14 10.3 9.9 9.6 9.3 9.0 8.7 8.3 14 10.3 9.9 9.4 9.0 8.6 8.3
16 9.9 9.7 9.2 8.9 8.6 8.3 8.0 16 9.9 9.4 9.0 8.6 8.3 8.0
18 9.5 9.2 8.7 8.6 8.3 8.0 7.7 18 9.5 9.1 8.7 8.3 8.0 7.6
20 9.1 8.8 8.5 8.2 7.9 7.7 7.4 20 9.1 8.7 8.3 8.0 7.7 7.4
22 8.7 8.4 8.1 7.8 7.7 7.3 7.1 22 8.7 8.4 8.0 7.7 7.4 7.1
24 8.4 8.1 7.8 7.6 7.3 7.1 6.8 24 8.4 8.1 7.7 7.4 7.1 6.9
26 8.1 7.8 7.6 7.3 7.0 6.8 6.6 26 8.1 7.8 7.5 7.2 6.9 6.6
28 7.8 7.5 7.3 7.0 6.8 6.6 6.3 28 7.8 7.5 7.2 6.9 6.6 6.4
30 7.5 7.2 7.0 6.8 6.5 6.3 6.1 30 7.5 7.2 7.0 6.7 6.4 6.2
32 7.3 7.1 6.8 6.6 6.4 6.1 5.9 32 7.3 7.0 6.7 6.5 6.2 6.0
34 7.1 6.9 6.6 6.4 6.2 6.0 5.8 34 7.1 6.8 6.5 6.3 6.0 5.8
36 6.8 6.6 6.3 6.1 5.9 5.7 5.5 36 6.8 6.6 6.3 6.1 5.8 5.6
38 6.6 6.4 6.2 5.9 5.7 5.6 5.4 38 6.6 6.4 6.1 5.9 5.6 5.4
40 6.4 6.2 6.0 5.8 5.6 5.4 5.2 40 6.4 6.2 5.9 5.7 5.4 5.2

X2. TWO-POINT CALIBRATION ZERO POINT STEPS

X2.1 Prepare water saturated air as described in section X2.3 Prepare 0.4 M sodium sulfite solution as described in
29.4. Section 29.10.
X2.2 Prepare nitrogen-saturated air as described in Section
29.9.
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 D888 – 12
TABLE X2.1 Single Operator Recovery and Precision Criteria for Luminescence-based Sensor – Two-point Calibration
Key
ASW (BOD) Single Point Calibration in Air Saturated Water (Saturated solution
placed in BOD bottles and capped)
ASW (BOD) / N2 Two Point Calibration in Air Saturated Water (BOD) and Nitrogen
Saturated Water
ASW (BOD) / Na2SO3 Two Point Calibration in Air Saturated Water (BOD) and Sodium
Sulfite
ASW (Bubbler) Single Point Calibration in Air Saturated Water (Saturated solution in
a bubbler)
ASW (Bubbler) / N2 Two Point Calibration in Air Saturated Water (Bubbler) and Nitrogen
Saturated Water
ASW (Bubbler) / Na2SO3 Two Point Calibration in Air Saturated Water (Bubbler) and Sodium
Sulfite
WSA Single Point Calibration in Water Saturated Air
WSA / N2 Two Point Calibration in Water Saturated Air and Nitrogen Saturated
Water
WSA / Na2SO3 Two Point Calibration in Water Saturated Air and Sodium Sulfite

Calibration Method ASW (BOD) ASW (BOD) / N2 ASW (BOD) / Na2SO3

Test point Temp 100.0% 100.0% 100.0%
Average RDO reading 26.83 99.46% 99.34% 99.27%
Stdev 1.05% 1.02% 1.03%
% RSD 1.05% 1.03% 1.04%
Calibration Method ASW (Bubbler) ASW (Bubbler) / N2 ASW (Bubbler) / Na2SO3
Test point Temp 100.0% 100.0% 100.0%
Average RDO reading 26.83 99.21% 99.17% 99.18%
Stdev 1.02% 1.03% 1.03%
% RSD 1.03% 1.04% 1.04%
Calibration Method WSA WSA / N2 WSA / Na2SO3
Test point Temp 100.0% 100.0% 100.0%
Average RDO reading 26.83 99.18% 99.20% 99.22%
Stdev 1.04% 1.04% 1.02%
% RSD 1.05% 1.05% 1.03%

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