OXYGEN (DISSOLVED) (4500-O)/Membrane-Electrode Method

4500-O E. Alum Flocculation Modification

1. General Discussion b. Ammonium hydroxide: (NH4OH) conc.

Samples high in suspended solids may consume appreciable
quantities of iodine in acid solution. The interference due to 3. Procedure
solids may be removed by alum flocculation.
The QC practices considered to be an integral part of each Collect sample in a 500- to 1000-mL, glass-stoppered bottle,
method are summarized in Table 4020:I. using the same precautions as for regular DO samples. Add
10 mL alum solution and 1 to 2 mL conc NH4OH. Stopper and
2. Reagents
invert gently for about 1 min. Let sample settle for about 10 min
All the reagents required for the azide modification and siphon clear supernate into a 250- to 300-mL DO bottle until
(4500-O.C.2) as well as: it overflows. Avoid sample aeration and keep siphon submerged
a. Alum solution: Dissolve 10 g aluminum potassium sulfate at all times. Continue procedure as in 4500-O.C.3 or an appro-
[AlK(SO4)2 䡠 12H2O] in distilled water and dilute to 100 mL. priate modification.

4500-O F. Copper Sulfate-Sulfamic Acid Flocculation Modification

1. General Discussion (CuSO4 䡠 5H2O) in 500 mL distilled water. Mix the two solu-
tions and add 25 mL conc acetic acid.
This modification is used for biological flocs (e.g., activated
sludge mixtures), which have high oxygen utilization rates.
The QC practices considered to be an integral part of each 3. Procedure
method are summarized in Table 4020:I.
Add 10 mL CuSO4 䡠 NH2SO2OH inhibitor to a 1-L glass-stop-
pered bottle. Insert bottle in a special sampler designed so
2. Reagents bottle fills from a tube near bottom and overflows only 25 to
50% of bottle capacity. Collect sample, stopper, and mix
All the reagents required for the azide modification by inverting. Let suspended solids settle and siphon rela-
(4500-O.C.2) as well as: tively clear supernatant liquor into a 250- to 300-mL DO
Copper sulfate-sulfamic acid inhibitor solution: Dissolve 32 g bottle. Continue sample treatment as rapidly as possible via
technical-grade sulfamic acid (NH2SO2OH) without heat in the azide procedure (4500-O.C.3) or other appropriate
475 mL distilled water. Dissolve 50 g copper sulfate modification.

4500-O G. Membrane-Electrode Method

1. General Discussion membrane that serves as a diffusion barrier against impuri-

ties.4 – 6 Under steady-state conditions, the current is directly
Although researchers have developed various modifications of proportional to the DO concentration.*
the iodometric method to eliminate or minimize certain interfer- Polarographic4 and galvanic5 membrane electrodes have been
ences, the method is still inapplicable to various industrial and used to measure DO in lakes and reservoirs7 for stream survey
domestic wastewaters.1 Moreover, the iodometric method is not and industrial-effluent control,8,9 continuous DO monitoring in
suited for field testing and cannot be easily adapted for contin- activated sludge units,10 and estuarine and oceanographic stud-
uous monitoring or determining DO in situ. ies.11 Being completely submersible, membrane electrodes are
Polarographic methods using either dropping-mercury or suited for analysis in situ. Their portability and ease of operation
rotating-platinum electrodes have been unreliable for DO
and maintenance make them particularly convenient for field
analysis in domestic and industrial wastewaters because im-
applications. In laboratory investigations, membrane electrodes
purities in the test solution can cause electrode poisoning or
other interferences.2,3 These problems are minimized when
using membrane-covered electrode systems because the sens-
ing element is protected by an oxygen-permeable polymer * Fundamentally, the current is directly proportional to molecular-oxygen activity.

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 OXYGEN (DISSOLVED) (4500-O)/Membrane-Electrode Method

Figure 4500-O:2. Effect of temperature on electrode sensitivity.

Figure 4500-O:3. The salting-out effect at different temperatures.

have been used for continuous DO analysis in bacterial cultures,
including the BOD test.5,12
Membrane electrodes provide an excellent method for DO log Ø ⫽ log Ø0 ⫹ 0.43 m 共t ⫺ t0 兲
analysis in polluted waters, highly colored waters, and strong
waste effluents. They are recommended for use especially when Nomographic charts for temperature correction can be con-
conditions are unfavorable for the iodometric method, or when structed easily13 and are available from some manufacturers. An
that test and its modifications are subject to serious interference- example is shown in Figure 4500-O:2, in which sensitivity is
related errors. plotted versus temperature on semi-logarithmic coordinates.
a. Principle: Oxygen-sensitive polarographic or galvanic Check one or two points frequently to confirm original calibra-
membrane electrodes are composed of two solid metal electrodes tion. If calibration changes, the new calibration should be par-
in contact with supporting electrolyte separated from the test allel to the original if the same membrane material is used.
solution by a selective membrane. The basic difference between Thermistors in an electrode circuit can automatically provide
the galvanic and polarographic systems is that in the former the temperature compensation,4 but they may not compensate fully
electrode reaction is spontaneous (similar to that in a fuel cell), over a wide temperature range. If accuracy is critical, use cali-
while the latter requires an external source of applied voltage to brated nomographic charts to correct for temperature effect.
polarize the indicator electrode. Polyethylene and fluorocarbon To use the DO membrane-electrode method in estuarine wa-
membranes are commonly used because they are permeable to ters or in wastewaters with varying ionic strength, correct for the
molecular oxygen and are relatively rugged. salting-out effect on electrode sensitivity.6,13 This effect is par-
Membrane electrodes are commercially available in some ticularly significant for large changes in salt content. Electrode
variety. In all these instruments, the “diffusion current” is lin- sensitivity varies with salt concentration according to the fol-
early proportional to the molecular-oxygen concentration. The lowing relationship:
measured current can be converted easily to concentration units
(e.g., mg/L) by a number of calibration procedures. log ØS ⫽ 0.43 mS CS ⫹ log Ø0
Membrane electrodes have a relatively high temperature co-
efficient largely due to changes in membrane permeability.6 The where:
effect of temperature on electrode sensitivity, Ø (␮A/mg/L), can
ØS, Ø0 ⫽ sensitivities in salt solution and distilled water, respectively,
be expressed by the following simplified relationship:
mS ⫽ constant (salting-out coefficient), and
CS ⫽ salt concentration (preferably ionic strength).
log Ø ⫽ 0.43 mt ⫹ b
If Ø0 and mS are determined, then the sensitivity for any value
where: of CS can be calculated. Conductivity measurements can be used
to approximate salt concentration (CS). This is particularly ap-
m ⫽ constant that depends on the membrane material,
plicable to estuarine waters. Figure 4500-O:3 shows calibration
t ⫽ temperature, °C, and
b ⫽ constant that largely depends on membrane thickness.
curves for the sensitivity of varying salt solutions at different
temperatures.
If Ø and m values are determined for one temperature (Ø0 and b. Interference: Polymer films used with membrane-electrode
t0), the sensitivity at any desired temperature (Ø and t) can be systems are permeable to various gases besides oxygen, although
calculated as follows: none is depolarized easily at the indicator electrode .

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 OXYGEN (DISSOLVED) (4500-O)/Membrane-Electrode Method

4) Salt water containing pollutants or interferences—Calibrate

with a sample of clean water with the same salt content as the
sample. Add a concentrated potassium chloride (KCl) solution
(see Section 2510 and Table 2510:I) to distilled water to produce
the same specific conductance as that in the sample. For polluted
ocean waters, calibrate with a sample of unpolluted seawater.
5) Estuary water containing varying quantities of salt—Cali-
brate with a sample of uncontaminated seawater or distilled or
tap water. Determine sample chloride or salt concentration and
revise calibration to account for change of oxygen solubility in
the estuary water.13
b. Sample measurement: Follow all precautions recommended
by manufacturer to ensure acceptable results. Change membrane
carefully to avoid contaminating sensing element or trapping
minute air bubbles under membrane, which can lead to lowered
response and high residual current. Provide enough sample flow
Figure 4500-O:4. Typical trend of effect of stirring on electrode
response.
across membrane surface to overcome erratic response (see
Figure 4500-O:4 for a typical example of stirring’s effect).
c. Validation of temperature effect: Check one or two points
Prolonged use of membrane electrodes in waters containing frequently to verify temperature-correction data.
such gases as hydrogen sulfide (H2S) tends to lower cell sensi-
tivity. Eliminate this interference by frequently changing the 4. Precision and Bias
electrolyte and membrane and calibrating the membrane
electrode. Most commercially available membrane-electrode systems
c. Membrane fouling: Membrane fouling is an issue due to can obtain an accuracy of 0.1 mg DO/L and a precision of
bacterial or algal growth, soaps, foam, polymers, grease, and 0.05 mg DO/L.
non-aqueous-phase liquids.
d. Sampling: Because membrane electrodes provide analysis 5. References
in situ, they eliminate errors due to sample handling and storage.
If sampling is required, use the same precautions suggested for 1. MCKEOWN, J.J., L.C. BROWN & G.W. GOVE. 1967. Comparative
the iodometric method. studies of dissolved oxygen analysis methods. J. Water Pollut.
e. Quality control: The QC practices considered to be an Control Fed. 39:1323.
2. LYNN, W.R. & D.A. OKUN. 1955. Experience with solid platinum
integral part of each method are summarized in Table 4020:I.
electrodes in the determination of dissolved oxygen. Sewage Ind.
Wastes 27:4.
2. Apparatus 3. MANCY, K.H. & D.A. OKUN. 1960. Automatic recording of dissolved
oxygen in aqueous systems containing surface active agents. Anal.
Oxygen-sensitive membrane electrode, polarographic or gal- Chem. 32:108.
vanic, with appropriate meter. 4. CARRITT, D.E. & J.W. KANWISHER. 1959. An electrode system for
measuring dissolved oxygen. Anal. Chem. 31:5.
3. Procedure 5. MANCY, K.H. & W.C. WESTGARTH. 1962. A galvanic cell oxygen
analyzer. J. Water Pollut. Control Fed. 34:1037.
a. Calibration: Follow manufacturer’s calibration procedure 6. MANCY, K.H., D.A. OKUN & C.N. REILLEY. 1962. A galvanic cell
oxygen analyzer. J. Electroanal. Chem. 4:65.
exactly to obtain guaranteed precision and accuracy. Generally,
7. WEISS, C.M. & R.T. OGLESBY. 1963. Instrumentation for monitoring
calibrate membrane electrodes by reading against air or a sample water quality in reservoirs. American Water Works Assoc. 83rd
of known DO concentration (determined by iodometric method Annual Conf., New York, N.Y.
or see Table 4500-O:II), as well as in a sample with zero DO. 8. CLEARY, E.J. 1962. Introducing the ORSANCO robot monitor. In
[Add excess sodium sulfite (Na2SO3) and a trace of cobalt Proc. Water Quality Meas. Instrum; Pub. No. 108. U.S. Public
chloride (CoCl2) to bring DO to zero.] Preferably calibrate with Health Serv., Washington, D.C.
samples of water to be tested, but avoid iodometric calibration if 9. MACKERETH, F.J.H. 1964. An improved galvanic cell for determination
interferences are suspected. The following illustrate the recom- of oxygen concentrations in fluids. J. Sci. Instrum. 41:38.
mended procedures: 10. SULZER, F. & W.M. WESTGARTH. 1962. Continuous D.O. recording
1) Fresh water—For unpolluted samples without interfer- in activated sludge. Water Sewage Works 109:376.
11. Duxbury, A.C. 1963. Calibration and use of a galvanic type oxygen
ences, calibrate in test solution or distilled water, whichever is
electrode in field work. Limnol. Oceanogr. 8:483.
more convenient. 12. LIPNER, H.J., L.R. WITHERSPOON & V.C. CHAMPEAUS. 1964. Adaptation
2) Salt water—Calibrate directly with samples of seawater or of a galvanic cell for microanalysis of oxygen. Anal. Chem. 36:204.
waters whose salt concentration is constantly ⬎1000 mg/L. 13. MANCY, K.H. & T. JAFFE. 1966. Analysis of Dissolved Oxygen in
3) Fresh water containing pollutants or interferences—Calibrate Natural and Waste Waters; Pub. No. 999-WP-37. U.S. Public
with distilled water because erroneous results occur with sample. Health Serv., Washington, D.C.

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 OXYGEN (DISSOLVED) (4500-O)/Membrane-Electrode Method

TABLE 4500-O:II. DISSOLVED OXYGEN SATURATION IN WATER (MG/L)

Pressure in millimeters and inches Hg
mm
775 760 750 725 700 675 650 625

Temp in.
°F °C 30.51 29.92 29.53 28.45 27.56 26.57 25.59 24.61

32.0 0 14.9 14.6 14.4 13.9 13.5 12.9 12.5 12.0

33.8 1 14.5 14.2 14.1 13.6 13.1 12.6 12.2 11.7
35.6 2 14.1 13.8 13.7 13.2 12.9 12.3 11.8 11.4
37.4 3 13.8 13.5 13.3 12.9 12.4 12.0 11.5 11.1
39.2 4 13.4 13.1 13.0 12.5 12.1 11.7 11.2 10.8
41.0 5 13.2 12.8 12.6 12.2 11.8 11.4 10.9 10.5
42.8 6 12.7 12.4 12.3 11.9 11.5 11.1 10.7 10.3
44.6 7 12.4 12.1 12.0 11.6 11.2 10.8 10.4 10.0
46.4 8 12.1 11.8 11.7 11.3 10.9 10.5 10.1 9.8
48.2 9 11.8 11.6 11.5 11.1 10.7 10.3 9.9 9.5
50.0 10 11.6 11.3 11.2 10.8 10.4 10.1 9.7 9.3
51.8 11 11.3 11.0 10.9 10.6 10.2 9.8 9.5 9.1
53.6 12 11.1 10.8 10.7 10.3 10.0 9.6 9.2 8.9
55.4 13 10.8 10.5 10.5 10.1 9.8 9.4 9.1 8.7
57.2 14 10.6 10.3 10.2 9.9 9.5 9.2 8.9 8.5
59.0 15 10.4 10.1 10.0 9.7 9.3 9.0 8.7 8.3
60.8 16 10.1 9.9 9.8 9.5 9.1 8.8 8.5 8.1
62.6 17 9.9 9.7 9.6 9.3 9.0 8.6 8.3 8.0
64.4 18 9.7 9.5 9.4 9.1 8.8 8.4 8.1 7.8
66.2 19 9.5 9.3 9.2 8.9 8.6 8.3 8.0 7.6
68.0 20 9.3 9.1 9.1 8.7 8.4 8.1 7.7 7.5
69.8 21 9.2 8.9 8.9 8.6 8.3 8.0 7.5 7.4
71.6 22 9.0 8.7 8.7 8.4 8.1 7.8 7.4 7.2
73.4 23 8.8 8.6 8.5 8.2 8.0 7.7 7.2 7.1
75.2 24 8.7 8.4 8.4 8.1 7.8 7.5 7.1 7.0
77.0 25 8.5 8.3 8.3 8.0 7.7 7.4 7.0 6.8
78.8 26 8.4 8.1 8.1 7.8 7.6 7.3 6.9 6.7
80.6 27 8.2 8.0 8.0 7.7 7.4 7.1 6.8 6.6
82.4 28 8.1 7.8 7.8 7.6 7.3 7.0 6.7 6.5
84.2 29 7.9 7.7 7.7 7.4 7.2 6.9 6.6 6.4
86.0 30 7.8 7.6 7.6 7.3 7.0 6.8 6.5 6.2
87.8 31 7.7 7.4 7.4 7.2 6.9 6.7 6.4 6.1
89.6 32 7.6 7.3 7.3 7.0 6.8 6.6 6.3 6.0
91.4 33 7.4 7.2 7.2 6.9 6.7 6.4 6.2 5.9
93.2 34 7.3 7.1 7.1 6.8 6.6 6.3 6. 5.8
95.0 35 7.2 7.0 7.0 6.7 6.5 6.2 6.0 5.7
96.8 36 7.1 6.8 6.9 6.6 6.4 6.1 5.9 5.6
98.6 37 7.0 6.7 6.7 6.5 6.3 6.0 5.8 5.6
100.4 38 6.9 6.6 6.6 6.4 6.2 5.9 5.7 5.5
102.2 39 6.8 6.5 6.5 6.3 6.1 5.8 5.6 5.4
104.0 40 6.7 6.4 6.4 6.2 6.0 5.7 5.5 5.3
105.8 41 6.6 6.3 6.3 6.1 5.9 5.6 5.4 5.2
107.6 42 6.5 6.2 6.2 6.0 5.8 5.6 5.3 5.1
109.4 43 6.4 6.1 6.1 5.9 5.7 5.5 5.2 5.0
111.2 44 6.3 6.0 6.0 5.8 5.6 5.4 5.2 4.9
113.0 45 6.2 5.9 5.9 5.7 5.5 5.3 5.1 4.8
114.8 46 6.1 5.8 5.9 5.6 5.4 5.2 5.0 4.8
116.6 47 6.0 5.7 5.8 5.6 5.3 5.1 4.8 4.7
118.4 48 5.9 5.7 5.7 5.5 5.3 5.0 4.8 4.6
120.2 49 5.8 5.6 5.6 5.4 5.2 5.0 4.7 4.5
122.0 50 5.7 5.5 5.5 5.3 5.1 4.9 4.7 4.4
Courtesy of Hach Co., Loveland, Colo.

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