Molecular Oxygen (O2)

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Water

The "Earth" Surface is 70% Ocean

ocean channel marker

Of the earth's surface, 70.8% is covered by water from the world's oceans. It is of consideration then why Earth was not called "Ocean". Probably it should have been. As for this body of water; the oceans contain 97.24% of the water on earth and this water is of course salty. The salt concentrations is variable: at most it is 4.0% in regions of high evaporation, averages at about 3.5% in the deep ocean, and drop to 1.0% in regions diluted with fresh water (4% = 40‰). The oceans contain a number of dissolved species and the O2 is vital for life in the water and varies with salinity and temperature.

 

 

Dissolved [Oxygen] SEAWATER

 
Oxygen in seawater is distributed throughout the ocean. Surface oxygen concentrations determine the rest of the water column as this water with dissolved oxygen is mixed down. The oxygen concentration in the ocean have been empirically determined and the following equation defines a relationship for (DO) dissolved oxygen vs (T) temperature and (S) salinity. The DO in ml/L; T in °K (= °C+ 273.15); and S in ‰ (= mg/g).
 

Equation for oxygen Determination

Where: ln(DO) = A1 + A2•(100/T) + A3•ln(T/100) + A4•(T/100)

+ S [B1 + B2•(T/100) + B3•(T/100)2 ]

A1 = -173.4292
B1 = - 0.033096
A2 = 249.6339
B2 = 0.014259
A3 = 143.3483
B3 = - 0.001700
A4 = - 21.8492

 

oxygen and salinity in surface water
Weiss, R.F. 1970. The solubility of nitrogen, oxygen and argon in water and seawater. Deep-Sea Res., 17: 721-735.

 

 

The DO as a concentration of ppm is equal to ml/L. Multiplying by 1.4276 and you have mg/L. The above equation is simplified in fresh water: i.e. S = 0 and the second line drops out.

 

coast victoria

Ocean Oxygen Concentrations vs Temperature

O2 (ml/L)
Salinity ( ‰)
Temperature (°C)
0‰
10‰
20‰
30‰
40‰
0
10.22
9.54
8.91
8.32
7.77
5
8.93
8.36
7.83
7.33
6.86
10
7.89
7.41
6.95
6.52
6.12
15
7.05
6.63
6.24
5.84
5.52
20
6.35
5.99
5.64
5.32
5.02
25
5.77
5.45
5.15
4.86
4.59
30
5.28
4.99
4.73
4.47
4.24
35
4.85
4.60
4.36
4.14
3.93

The above figure shows the oxygen concentration as measure of the salinity of the ocean. The salinity is influenced by evaporation and by freshwater dilution. The ocean also contains dissolved Nitrogen and Argon, 445 and 11.5 µM concentrations at 25C..

Oxygen Concentration with Depth

 

oxygen concentration and temperature in deep ocean

The concentration of Oxygen in the ocean is not constant at all depths, but rather changes due to the combination of mixing, and oxygen enrichment and consumption pathways. The figure above shows the characteristics of this behaviour although it is region specific. Oxygen enrichment of water is provided either by direct exchange with the atmosphere at the ocean surface, or from photosynthesis in the photic zone. The photic zone can produce >100% oxygen saturated concentrations if conditions are optimal (nutrients, sunlight). The surface oxygenated layers of water water are then mixed down. However, a strong oxygen consumption is also present with the biological degradation (oxidation) of organic material and detritus. The oxygen minimum zone occurs not in the deepest part of the ocean but at intermediate depths. The reason for this is postulated to be due to a number of possibilities: a region of minimal mixing (resting boundary); a region where density and specific gravity of the organic detritus are such that detritus accumulation takes place at this depth and maximises oxygen consumption; the density of water laden with organic material is such that it descends to intermediate depth where maximal biological consumption facilitates a depleted zone.

Oxygen Measurements in the Ocean

 

breaking wave
The dissolved oxygen concentrations can be experimentally determined a number of ways. Traditionally the simplest and cost effective method is the Winkler method for dissolved oxygen determination. More recently oxygen is determined with a clark type polorgraphic (potentiometric) method using a platinum electrode or a fluorescence assay with Ruthenium. A number of commercial units are available. Some also can be used in the deep ocean. In addition in more recent years it is important to analyse things with a global perspective and accordingly satellite imaging (remote sensing) has been calibrated for oxygen estimation.

 

A example of this is from the National Oceanographic data centre and their World Ocean Atlas

world ocean atlas oxygen

Oxygen Generation by Photosynthesis

 

underwater photosynthesis

Photosynthesis is a mechanism growth by Plants, Cyanobacteria and algae that results from the capture of energy (light) and conversion to chemical energy. This process globally represents the capture of ~1014 W of energy per year, that is used to generate O2 alone (and more if the other chemistry is considered). On earth about 46% of this photosynthesis takes place in the oceans, and the oceans therefore are an extremely vital source of life.

The diversity of photosynthetic organisms chemically is low. That is to say they all perform the chemistry of water splitting to release O2 in the same way. However, the diversity of the pigment antenna systems is high. This is because the photosynthetic organism have evolved to utilise light in aquatic environments. Due to the filtration of light (loss red wavelengths initially then green) the light colour changes with depth. Plants and algae therefore have evolved different pigment antenna complexes to cope with these changes in light "colour". This means specific adaptations are found at specific depths.

Most photosynthesis takes place on the surface waters 0-20 m depth. The general feeling was that the lower limit was ~200 m, however, photosynthesis has been recorded down to 269 m on a seamount. (Littler, MM et al, (1985) Science 227, 57-59.)

Dissolved oxygen concentrations are vital for a sustainable ecosystems. Oxygen depletion of aquatic waterways kills fish and makes for unpleasant stagnant pools and lakes. One of the principle causes is nutrient run off into rivers and lakes (agricultural or domestic lawn fertilizer for example) that cause increased nitrates and phosphate levels in the water. The increased nutrients, that are normally usually limiting, result in algal blooms. This is also a problem in the ocean with the red tides. All is well until the algae begin to die off and their decay consumes [O2] concentrations to practically zero. The process is called eutrophication.

 

Oxygen Equations

 

A number of empirical methods for determining oxygen exist. As seen below not all are equivalent.
 
Truesdale and Downing (1954) Solubility of oxygen in water. Nature 173,1236.
DO = 14.16 - 0.3943•T + 0.007714•T2 -0.0000646•T3
where DO = ppm (mg / L) and T = °C
 
Weiss, R.F. 1970. The solubility of nitrogen, oxygen and argon in water and seawater. Deep-Sea Res., 17: 721.
ln (DO) = -173.4292 +249.6339•(100/T) + 143.3483•ln(T/100) - 21.8492•(T/100)
where DO = ml / L and T = °K
 
CRC handbook
ln (X1) = -66.7354 + 87.4755/(T/100) + 24.4526•ln(T/100)
where X1 is mole fraction: X1 x 55.5 x 0.20946 = O2 M(olar)
[water] = 55.5M, O2 = 0.20946%
 
The preceding three equations provide empirical determinations of oxygen in water. Be careful with the use of equations at higher temperatures. It is recommended that the equation based on the oxygen partial mole fraction is used from the CRC handbook.
oxygen concentration in water µM

 

 

 

Sea Water Composition The chemical composition of sea water is intriguing and contains traces of most elements. These locations <site1> <site2> outline some information about what is in seawater.

Dissolved Oxygen Apparatus Hansatech-Instruments UK, Cole-Palmer USA, Ocean Optics, Mettler Toledo, and for the deep ocean Sea-Bird electronics.

Corrosion in Seawater is Strongly Controlled by O2 Corrosion in seawater is often quite a problem, particularly with structures that are there for the long term <link>. Strategies exist to prevent this corrosion by using sacrificial anodes. Oxygen is usually a critical determinant for the rate of corrosion.

Global Photosynthesis Remote imaging is used to determine the productivity of the earth. Animations of MODIS satellite imaging <link> reveal the changing patterns of photosynthesis on earth.

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