2810 Supersaturação de Gás Dissolvido

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2810

Dissolved Gas Supersaturation

Approved by Standard Methods Committee, 2010. Editorial revisions, 2021. Joint Task Group: 20th Edition—John E. Colt (chair), Larry E. Fidler, John O. Jensen, John W.
Sweeney, Barnaby J. Watten.

2810 A. Introduction

Water can become supersaturated with atmospheric gases by Gas bubbles form only when the total dissolved gas pressure is
various means; heating and air entrainment in spilled or pumped greater than the sum of compensating pressures. Compensating
water are the most common. The primary sign of gas supersatura- pressures include water, barometric, and tissue or blood pressure
tion is the formation of bubbles on submerged surfaces or within for organisms. The total dissolved gas pressure is equal to the
the vascular systems and tissues of aquatic organisms. sum of the partial pressures of all the dissolved gases, includ-
Gas supersaturation can limit aquatic life and interfere with ing water vapor. Typically, only nitrogen, oxygen, argon, car-
water treatment processes. Levels of supersaturation lethal to bon dioxide, and water vapor pressures need to be considered in
aquatic organisms have been found in springs, rivers, wells, lakes, most natural waters. Gas bubble disease, of fish or other aquatic
estuaries, and seawater. Gas supersaturation can be produced in organisms, is a result of excessive uncompensated gas pressure.
pumped or processed water intended for drinking, fish hatchery A single supersaturated gas such as oxygen or nitrogen may not
supply, and laboratory bioassays. Seasonal and other temporal necessarily result in gas bubble disease because bubble formation
variations in supersaturation may occur in surface waters as a depends largely on total dissolved gas pressure. The degree of gas
result of solar heating and photosynthesis. Because the rate of saturation should be described in terms of pressures rather than
equilibration may be slow, supersaturation may persist in flowing concentration or volume units.
water for days and excessive dissolved gas levels may persist far
from the source of supersaturation.

2810  B. Direct-Sensing Membrane-Diffusion Method

1. General Discussion units has specific advantages and limitations; the instrument of
choice depends on the specific application. All these instruments
a. Principle: This method requires an instrument with a variable are portable so that data collection is completed in the field.
length of gas permeable tubing, connected to a pressure-measur- Test the instrument for leaks according to the manufacturer’s
ing device. Dimethyl silicone rubber tubing often is used because recommendation. Even a very small leak, difficult to detect and
it is highly permeable to dissolved gases, including water vapor. locate, will result in useless data. Calibrate the pressure-measuring
At steady state, the gauge pressure inside the tubing is equal to device with a mercury manometer or certified pressure gauge. If
the difference in gas pressure (∆P) between the total dissolved a manometer is used, include fresh mercury that flows freely in
gas pressure and the ambient barometric pressure. When the the tubing. An alternative method for directly testing membrane-
water is in equilibrium with the atmosphere, ∆P equals zero. If diffusion instruments in a small, closed chamber where induced ∆P
∆P is greater than zero, the water is supersaturated. Conversely, if levels can be compared against observed ∆P levels is available.2
∆P is negative the water is undersaturated. Van Slyke-Neill4 or gas chromatography methods1 are inappro-
b. Working range: The working range of this method depends priate for calibration but they may be used to verify results. These
on the pressure-sensing device used, but typically will range from methods measure individual gas concentrations and require fur-
−150 to +600 mm Hg. Dissolved solids in wastewater do not ther conversion to ∆P or partial pressure and suffer from sampling
interfere with this method. The practical depth range for these and sample handling problems.5–7
instruments is 1 to 10 m.
3. Procedure
2. Apparatus
At the start of each day, test the instrument for leaks and recal-
Several types of membrane-diffusion instruments are available ibrate. At a monitoring site, completely submerge the sensing ele-
commercially. Alternatively, construct a unit from commercially ment in the water, preferably below the hydrostatic compensation
available parts. Several units have been described, including a depth. This is the depth where the hydrostatic and total gas pres-
direct-reading instrument using pressure transducers and a digital sures are equal and as a result, bubbles do not form on the tubing.
readout,1 an on-line unit that can activate an alarm system,2 and Bubble formation on the silicone rubber tubing seriously reduces
an early model of the Weiss saturometer.3 Each of these described accuracy. Compute hydrostatic compensation depth5 as follows:

https://doi.org/10.2105/SMWW.2882.037 1
2810 DISSOLVED GAS SUPERSATURATION - B. Direct-Sensing Membrane-Diffusion Method

Total gas pressure also has been reported as a percentage of


local barometric pressure:

 P + ∆P 
TGP % =  b  ×100

 Pb 

where:
Pb = true local barometric pressure (mm Hg).

The reporting of total gas pressure as a percentage is not


encouraged.8
b. Component gas pressures: When information on component
gas supersaturation is needed, express data as partial pressures,
differential pressures, or percent saturation.5,8 This requires addi-
tional measurements of dissolved oxygen, temperature, and salin-
ity at the monitoring site. (Methods for these variables may be
Figure 2810:1 Time response for the membrane-diffusion method. found in Sections 4500-O, 2550, and 2520, respectively.) In a mix-
ture of gases in a given volume, the partial pressure of a gas is the
pressure that this gas would exert if it were the only gas present.
∆P
Z= 1) Oxygen partial pressure—Calculate the partial pressure of
73.42
oxygen as follows:
where:
DO
Z = hydrostatic compensation depth (m), and PO2 = × 0.5318
βo2
∆P = pressure difference between total dissolved gas pressure and
the ambient barometric pressure (mm Hg).
where:
The factor 73.42 is the hydrostatic pressure of fresh water at
20 °C expressed in terms of mm Hg/m water depth. Because the PO2 = partial pressure of dissolved oxygen (mm Hg),
variation of hydrostatic pressure with temperature and salinity is bO2 = Bunsen coefficient for oxygen (Table 2810:1), [L/(L ⋅ atm)],
small, this equation can be used for all natural waters. and
Dislodge formed bubbles on the tubing by gently striking the DO = measured concentration of oxygen (mg/L).
instrument or moving the instrument rapidly in the water. Move- Bunsen coefficients for marine waters are available.5 The factor
ment of water across the silicone rubber tubing also facilitates 0.5318 equals 760/(1000 K), where K is the ratio of molecular
establishing the equilibrium between gas pressure in the water weight to molecular volume for oxygen gas.5
and in the tubing. 2) Nitrogen partial pressure—Estimate the partial pressure of
Operate the instrument in a bubble-free state until a stable ∆P nitrogen by subtracting the partial pressures of oxygen and water
is observed. This may take from 5 to 30 min, depending on the vapor from the total gas pressure.
∆P, water temperature, water flow, and geometry of the system.
The time response of the membrane-diffusion method is shown in
PN 2 = Pb +∆P −PO 2 − PH2O
Figure 2810:1 for bubble-free and bubble conditions.
If the instrument is used in heavily contaminated water con-
taining oil or other organic compounds, clean the silicone tubing where:
with a mild detergent according to the manufacturer’s instruc- PH O = vapor pressure of water in mm Hg from Table 2810:2.
tions. Silicone rubber tubing has been used in uncontaminated 2

natural water for at least 8 years without being adversely affected This term includes a small contribution from argon and any other
by attached algal growth.2 The tubing can be damaged by abra- gases present, including carbon dioxide and methane. The partial
sive grit, diatoms, biting aquatic organisms, certain organic com- pressure of carbon dioxide is negligible in natural waters of pH > 7.0.
pounds, and strong acids.2 3) Nitrogen:oxygen partial pressure ratio—The ratio of the partial
Obtain the barometric pressure with each measurement by using pressure of nitrogen to the partial pressure of oxygen (N2:O2) charac-
a laboratory barometer, a calibrated portable barometer, or pressure terizes the relative contribution of the two gases to the total dissolved
transducer. Barometric pressures reported by weather agencies (or gas pressure. In water in equilibrium with air, this ratio is 3.77.
airports) are unusable because they are corrected to sea level and c. Differential pressures: The differential pressure of a gas is
even if back-corrected for local pressure are for a reading located the difference between the partial pressures of that gas in water
too far away to be considered a true local barometric pressure. and air. The oxygen differential pressure may be calculated as

4. Calculation ∆Po2 = Po2 − 0.20946( Pb − PH2O )

a. Total gas pressure: Preferably report total gas pressure as


and the nitrogen differential pressure as
∆P.2,6,8 Express pressure as millimeters of mercury.

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2810 DISSOLVED GAS SUPERSATURATION - B. Direct-Sensing Membrane-Diffusion Method

Table 2810:1. Bunsen Coefficient for Oxygen in Fresh Water


Bunsen Coefficient [L real gas at STP/(L · atmosphere)] at Given Temperature (to nearest 0.1 °C)
Temperature (°C) 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
 0 0.04914 0.04901 0.04887 0.04873 0.04860 0.04847 0.04833 0.04820 0.04807 0.04793
 1 0.04780 0.04767 0.04754 0.04741 0.04728 0.04716 0.04703 0.04680 0.04678 0.04665
 2 0.04653 0.04640 0.04628 0.04615 0.04603 0.04591 0.04579 0.04567 0.04555 0.04543
 3 0.04531 0.04519 0.04507 0.04495 0.04484 0.04472 0.04460 0.04449 0.04437 0.04426
 4 0.04414 0.04403 0.04392 0.04381 0.04369 0.04358 0.04347 0.04336 0.04325 0.04314
 5 0.04303 0.04292 0.04282 0.04271 0.04260 0.04250 0.04239 0.04229 0.04218 0.04206
 6 0.04197 0.04187 0.04177 0.04166 0.04156 0.04146 0.04136 0.04126 0.04116 0.04106
 7 0.04096 0.04086 0.04076 0.04066 0.04056 0.04047 0.04037 0.04027 0.04018 0.04008
 8 0.03999 0.03989 0.03980 0.03971 0.03961 0.03952 0.03943 0.03933 0.03924 0.03915
 9 0.03906 0.03897 0.03888 0.03879 0.03870 0.03861 0.03852 0.03843 0.03835 0.03826
10 0.03817 0.03809 0.03800 0.03791 0.03783 0.03774 0.03766 0.03757 0.03749 0.03741
11 0.03732 0.03724 0.03716 0.03707 0.03699 0.03691 0.03683 0.03675 0.03667 0.03659
12 0.03651 0.03643 0.03635 0.03627 0.03619 0.03611 0.03604 0.03596 0.03588 0.03581
13 0.03573 0.03565 0.03558 0.03550 0.03543 0.03535 0.03528 0.03520 0.03513 0.03505
14 0.03498 0.03491 0.03448 0.03476 0.03469 0.03462 0.03455 0.03448 0.03441 0.03433
15 0.03426 0.03419 0.03412 0.03406 0.03399 0.03392 0.03385 0.03378 0.03371 0.03364
16 0.03358 0.03351 0.03344 0.03338 0.03331 0.03324 0.03318 0.03311 0.03305 0.03298
17 0.03292 0.03285 0.03279 0.03272 0.03266 0.03260 0.03253 0.03247 0.03241 0.03235
18 0.03228 0.03222 0.03216 0.03210 0.03204 0.03198 0.03192 0.03186 0.03180 0.03174
19 0.03168 0.03162 0.03156 0.03150 0.03144 0.03138 0.03132 0.03126 0.03121 0.03115
20 0.03109 0.03103 0.03098 0.03092 0.03086 0.03081 0.03075 0.03070 0.03064 0.03059
21 0.03053 0.03048 0.03042 0.03037 0.03031 0.03026 0.03020 0.03015 0.03010 0.03004
22 0.02999 0.02994 0.02989 0.02983 0.02978 0.02973 0.02968 0.02963 0.02958 0.02952
23 0.02947 0.02942 0.02937 0.02932 0.02927 0.02922 0.02917 0.02912 0.02907 0.02902
24 0.02897 0.02893 0.02888 0.02883 0.02878 0.02873 0.02868 0.02864 0.02859 0.02854
25 0.02850 0.02845 0.02840 0.02835 0.02831 0.02826 0.02822 0.02817 0.02812 0.02808
26 0.02803 0.02799 0.02794 0.02790 0.02785 0.02781 0.02777 0.02772 0.02768 0.02763
27 0.02759 0.02755 0.02750 0.02746 0.02742 0.02737 0.02733 0.02729 0.02725 0.02720
28 0.02716 0.02712 0.02708 0.02704 0.02700 0.02695 0.02691 0.02687 0.02683 0.02679
29 0.02675 0.02671 0.02667 0.02663 0.02659 0.02655 0.02651 0.02647 0.02643 0.02639
30 0.02635 0.02632 0.02628 0.02624 0.02620 0.02616 0.02612 0.02609 0.02605 0.02601
31 0.02597 0.02594 0.02590 0.02586 0.02582 0.02579 0.02575 0.02571 0.02568 0.02564
32 0.02561 0.02557 0.02553 0.02550 0.02546 0.02543 0.02539 0.02536 0.02532 0.02529
33 0.02525 0.02522 0.02518 0.02515 0.02511 0.02508 0.02504 0.02501 0.02498 0.02494
34 0.02491 0.02488 0.02484 0.02481 0.02478 0.02474 0.02471 0.02468 0.02465 0.02461
35 0.02458 0.02455 0.02452 0.02448 0.02445 0.02442 0.02439 0.02436 0.02433 0.02429
36 0.02426 0.02423 0.02420 0.02417 0.02414 0.02411 0.02408 0.02405 0.02402 0.02399
37 0.02396 0.02393 0.02390 0.02387 0.02384 0.02381 0.02378 0.02375 0.02372 0.02369
38 0.02366 0.02363 0.02360 0.02358 0.02355 0.02352 0.02349 0.02346 0.02343 0.02341
39 0.02338 0.02335 0.02332 0.02329 0.02327 0.02324 0.02321 0.02318 0.02316 0.02313
40 0.02310 0.02308 0.02305 0.02302 0.02300 0.02297 0.02294 0.02292 0.02289 0.02286
Based on Benson and Krause.1,2 β = 9.9902 × 10−4[exp(9.7265 − 5.26895 × 103/T + 1.00417 × 106/T2)], where T = 273.15 + °C.
References
1. Benson BB, Krause D. The concentration and isotopic fractionation in freshwater in equilibrium with the atmosphere. 1. Oxygen. Limnol Oceanogr. 1980;25:662.
2. Benson BB, Krause D. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol Ocean-
ogr. 1984;29:620.

∆PN 2 = ∆P − ∆PO2  PN 2 
N 2 (%) =   ×100

 0.7902( Pb − PH2O ) 
d. Percent of saturation: In older literature, supersaturation
values have been reported as percent saturation. This method of
reporting component gases is discouraged but can be calculated  P02 
as follows: O2 (%) =   ×100

 0.20946( Pb − PH2O ) 

https://doi.org/10.2105/SMWW.2882.037 3
2810 DISSOLVED GAS SUPERSATURATION - B. Direct-Sensing Membrane-Diffusion Method

Table 2810:2. Vapor Pressure of Fresh Water


Vapor Pressure (mm Hg) at Given Temperature (to nearest 0.1 °C)
Temperature (°C) 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
 0 4.58 4.61 4.64 4.68 4.71 4.75 4.78 4.82 4.85  4.89
 1 4.92 4.96 4.99 5.03 5.07 5.10 5.14 5.18 5.21  5.25
 2 5.29 5.33 5.36 5.40 5.44 5.48 5.52 5.56 5.60  5.64
 3 5.68 5.72 5.76 5.80 5.84 5.88 5.92 5.97 6.01  6.05
 4 6.09 6.14 6.18 6.22 6.27 6.31 6.36 6.40 6.44  6.49
 5 6.54 6.58 6.63 6.67 6.72 6.77 6.81 6.86 6.91  6.96
 6 7.01 7.05 7.10 7.15 7.20 7.25 7.30 7.35 7.40  7.45
 7 7.51 7.56 7.61 7.66 7.71 7.77 7.82 7.87 7.93  7.98
 8 8.04 8.09 8.15 8.20 8.26 8.31 8.37 8.43 8.48  8.54
 9 8.60 8.66 8.72 8.87 8.84 8.89 8.95 9.02 9.08  9.14
10 9.20 9.26 9.32 9.39 9.45 9.51 9.58 9.64 9.70  9.77
11 9.83 9.90 9.97 10.03 10.10 10.17 10.23 10.30 10.37 10.44
12 10.51 10.58 10.65 10.72 10.76 10.86 10.93 11.00 11.07 11.15
13 11.22 11.29 11.37 11.44 11.52 11.59 11.67 11.74 11.82 11.90
14 11.98 12.05 12.13 12.21 12.29 12.37 12.45 12.53 12.61 12.69
15 12.78 12.86 12.94 13.05 13.11 13.19 13.28 13.36 13.45 13.54
16 13.62 13.71 13.80 13.89 13.97 14.06 14.15 14.24 14.33 14.43
17 14.52 14.61 14.70 14.80 14.89 14.98 15.08 15.17 15.27 15.37
18 15.46 15.56 15.66 15.76 15.86 15.96 16.06 16.16 16.26 16.36
19 16.46 16.57 16.67 16.77 16.88 16.98 17.09 17.20 17.30 17.41
20 17.52 17.63 17.74 17.85 17.96 18.07 18.18 18.29 18.41 18.52
21 18.64 18.75 18.87 18.98 19.10 19.22 19.33 19.45 19.57 19.69
22 19.81 19.93 20.05 20.48 20.60 20.42 20.55 20.67 20.80 20.93
23 21.05 21.18 21.31 21.44 21.57 21.70 21.83 21.96 22.09 22.23
24 22.36 22.50 22.63 22.77 22.90 23.04 23.18 23.32 23.46 23.60
25 23.74 23.88 24.03 24.17 24.31 24.46 24.60 24.75 24.90 25.04
26 25.19 25.34 25.49 25.64 25.80 25.95 26.10 26.26 26.41 26.57
27 26.72 26.88 27.04 27.20 27.36 27.52 27.68 27.84 28.00 28.17
28 28.33 28.50 28.66 28.83 29.00 29.17 29.34 29.51 29.68 29.85
29 30.03 30.80 30.37 30.55 30.73 30.91 31.08 31.26 31.44 31.62
30 31.81 31.99 32.17 32.36 32.54 32.73 32.92 33.11 33.30 33.49
31 33.68 33.87 34.06 34.26 34.45 34.65 34.85 35.05 35.24 35.44
32 35.65 35.85 36.05 36.25 36.46 36.67 36.87 37.08 37.29 37.50
33 37.71 37.92 38.14 38.35 38.57 38.78 39.00 39.22 39.44 39.66
34 39.88 40.10 40.33 40.55 40.78 41.01 41.23 41.46 41.69 41.92
35 42.16 42.39 42.63 42.86 43.10 43.34 43.58 43.82 44.06 44.30
36 44.55 44.79 45.04 45.28 45.53 45.78 46.03 46.29 46.54 46.79
37 47.05 47.31 47.56 47.82 48.08 48.35 48.61 48.87 49.14 49.41
38 49.67 49.94 50.21 50.49 50.76 51.03 51.31 51.59 51.87 52.14
39 52.43 52.71 52.99 53.28 53.56 53.85 54.14 54.43 54.72 55.01
40 55.31 55.60 55.90 56.20 56.50 56.80 57.10 57.41 57.71 58.02
Based on an equation presented by Green and Carritt.1 This equation is cumbersome to use. The following equation2 is adequate for most applications:
PH2O = 760[exp(11.8571 − 3,840.70/T − 216,961/T2)], where T = 273.15 + °C.5
References
1. Green EJ, Carritt DE. New tables for oxygen saturation of seawater. J Mar Res. 1967;24:140-147.
2. Benson BB, Krause Jr D. The concentration and isotopic fractionation of gases dissolved in freshwater in equilibrium with the atmosphere. 1. Oxygen. Limnol Oceanogr.
1980;25(4):662-671.

The following relationships are useful conversions:  O (%)    N (%)  


∆P = 0.20946  2 −1  Pb − PH2O  + 0.7902  2 −1  Pb − PH2O 
 100     100   
TGP (%) = 0.20946 O2 (%) + 0.7902 N 2 (%)

DO
∆P =
βo2
(
(0.5318)(1 + N 2 : O2 ) − Pb − PH2O )

https://doi.org/10.2105/SMWW.2882.037 4
2810 DISSOLVED GAS SUPERSATURATION - B. Direct-Sensing Membrane-Diffusion Method

Use care with these relationships with older data because both behavior and hydrostatic pressure can modify the exposure by hor-
TGP (%) and N2 (%) have been differently defined.5 izontal and vertical movements away from dangers, and captive
environments such as aquaria, hatcheries, or laboratories, where
5. Quality Control conditions not only preclude escape but also include other signifi-
cant stresses. Of these two realms, captive environments are more
The quality control practices considered to be an integral part likely to cause illness or mortality from gas bubble disease and do
of each method are summarized in Tables 2020:1 and 2. so sooner and at the lower ∆P levels.
The precision of the membrane-diffusion method depends pri- In natural environments, the limit of safe levels of gas supersat-
marily on the pressure-sensing instrument. For an experienced uration depends on the depth available to the species, the species
operator it is approximately ±1 to 2 mm Hg with an accuracy of behavior, or both, but this limit usually occurs at a ∆P between 50
±3 to 5 mm Hg.3,6 Air leaks, bubble formation, biofilm develop- and 150 mm Hg. Under captive environment conditions, the ∆P
ment, incomplete equilibration, or condensation produce negative should be as close to zero as possible. For sensitive species and
errors while direct water leaks can result in positive errors in sub- life stages, sublethal and lethal effects have been observed at ∆P
mersible units. of 10 to 50 mm Hg.10
For accurate work, measure water temperature to the nearest
±0.1 °C. References

6. Reporting of Results 1. D’Aoust BG, White R, Siebold H. Direct measurement of total dis-
solved gas pressure. Undersea Biomed Res. 1975;2(2):141–149.
In reporting results, include the following data: 2. Bouck GR. Gasometer: an inexpensive device for continuous moni-
toring of dissolved gases and supersaturation. Trans Amer Fish Soc.
• Sensor depth (m),
1982;111(4):505–516.
• Barometric pressure (mm Hg), 3. Fickeisen DH, Schneider MJ, Montgomery JC. A comparative eval-
• Water temperature (°C), uation of the Weiss saturometer. Trans Amer Fish Soc. 1975;104(4):
• Dissolved oxygen (mm Hg or mg/L), 816–820.
• Salinity (g/kg), and 4. Beiningen KT. A manual for measuring dissolved oxygen and nitro-
• ∆P (mm Hg). gen gas concentrations in water with the Van Slyke-Neill apparatus.
If component gas information is needed add: Portland: Fish Commission of Oregon; 1973.
• Partial pressure of oxygen (mm Hg), 5. Colt J. Computation of dissolved gas concentrations in water as func-
• Partial pressure of nitrogen (mm Hg), and tions of temperature, salinity, and pressure; Special Publication 14.
• Nitrogen: oxygen partial pressure ratio Bethesda (MD): American Fisheries Society; 1984.
6. D’Aoust BG, Clark MJR. Analysis of supersaturated air in natural
or
waters and reservoirs. Trans Amer Fish Soc. 1980;109(6):708–724.
• ∆PO2 (mm Hg) and 7. Pirie WR, Hubert WA, Fickeisen DH, Schneider MJ, Montgom-
• ∆PN2 (mm Hg). ery JC. Assumptions in statistical analysis. Trans Amer Fish Soc.
1977;106(6):646–648.
7. Interpretation of Results 8. Colt J. The computation and reporting of dissolved gas levels. Water
Res. 1983;17(8):841–849.
The biological effects of dissolved gas supersaturation depend 9. Weitkamp DE, Katz M. A review of dissolved gas supersaturation
on the species, age, depth in water column, length of exposure, literature. Trans Amer Fish Soc. 1980;109(6):659–702.
10. Colt J. Gas supersaturation: impact on the design and operation of
temperature, and nitrogen:oxygen partial pressure ratio.9 Safe
aquatic systems. Aquacult Eng. 1986;5(1):49–85.
limits generally are segregated into natural environments, where

Published Online: August 27, 2018


Revised: November 4, 2021
https://doi.org/10.2105/SMWW.2882.037 5

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