Water Quality Ambient Water Quality Guidelines for Dissolved Oxygen
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Water Quality Ambient Water Quality Guidelines for Dissolved Oxygen 1.0 Introduction Oxygen is the single most important component of surface water for self-purification processes and the maintenance of aquatic organisms which utilize aerobic respiration. This document is largely biased towards the effects of minimum oxygen levels on aquatic life, as dissolved oxygen has relatively little or no consequence for other water uses. Categories of water uses given cursory consideration include drinking water, recreation and aesthetics, and industry. A discussion of dissolved oxygen in the context of criteria (acceptable levels for specifies uses) is anomalous relative to most other water quality variables in that critical oxygen levels are expressed as minimum rather than maximum values. An exception is required for industry because of the corrosive properties of oxygen. Dissolved oxygen standards and criteria from other agencies and jurisdictions are reviewed along with information available from the literature. The objective or the review was to incorporate the most applicable information which could be used to formulate defensible criteria to protect aquatic life in British Columbia waters. Criteria for other water uses have not been proposed. 2.0 Forms and Transformations 2.1 Physical Properties Oxygen is the most abundant element of the earth's crust and waters combined. The combination of the divalent oxygen atom with single valent hydrogen atom comprises the extremely stable H2O molecule. Under natural conditions water exists in several physical states, but the molecule itself dissociates to a very limited extent as ions (H+ and OH-). Two OH- molecules can, by covalent bonding, combine to form H2O2 or hydrogen peroxide. Holm et al. (1986) state that there is evidence that hydrogen peroxide is formed and accumulates in the photo-oxidation of organic compounds in surface and ground waters and in precipitation. The decomposition of water to yield dissolved oxygen normally would be outside the realm of ambient conditions; an endothermic reaction such as provided by electrolysis is required to produce O2 and H2 gas. Photosynthesis is the only natural process that oxidizes water to oxygen. Another reaction of oxygen atoms is the formation of ozone (O3), which occurs naturally when mediated by absorption of ultraviolet light, or can be manufactured artificially using high electrical voltage. Ozone is highly unstable and is normally confined to the upper atmosphere. Here, there is sufficient intensity of ultraviolet light to split the stable oxygen molecules, freeing oxygen atoms and promoting recombination with other molecules to form ozone. Substantial qualities of ozone are increasingly being found in areas where air quality is degraded. Ground-level ozone is formed by the reaction of byproducts from fossil fuel combustion (hydrocarbons and nitrogen oxides) in the presence of sunlight. The double bonded, two-atom molecule is the single form of oxygen which has relevance to this discussion. Air contains approximately 20.9 percent oxygen gas by volume; however, the proportion of dissolved oxygen in air dissolved in water is about 35 percent, because nitrogen (the remainder) is less soluble in water. Oxygen is considered to be moderately soluble in water and this solubility is governed by a complex set of physical conditions that include atmospheric and hydrostatic pressure, turbulence, temperature and salinity (Wetzel, 1983). A brief description follows of how these conditions relate to and influence dissolved oxygen. Atmospheric and hydrostatic pressure-Henry's Law states that the amount of oxygen which will remain dissolved in a volume of water, at constant temperature, is proportional to the ambient pressure of oxygen gas with which it is in equilibrium (CREM, 1987). Air pressure at sea level under standard conditions (fully saturated with oxygen and water vapour, 0 degrees Celsius) is equal to 760 mm Hg (or 101.325 kilopascals) and the proportion of this pressure attributable to oxygen is directly related to the fraction of oxygen in air. Oxygen tension or partial pressure (PO2) is equivalent to atmospheric pressure minus a compensation factor for water vapour pressure (the latter is available in tables as in Colt, 1984), multiplied by the oxygen fraction in air: PO2 = (Atmos. Press. - Water Vapour Press.) x % O2 Davis (1975) presented the following example at 10 degrees Celsius and one atmosphere (sea level): PO2 = (760 mm Hg - *9.2 mm Hg) x 20.95/100 = 157.3 mm Hg * saturated water vapour pressure at 10 degrees Celsius (from Table 1) Thus, at any given barometric pressure and temperature (and corresponding water vapour pressure) the oxygen partial pressure can be calculated. At altitudes above sea level the gravitational attraction of gas molecules becomes less and there is a progressive reduction in barometric pressure. Tables are available (e.g. Table 2 from NCASI, 1985) which provide correction factors for computations of oxygen partial pressure at altitude. For criteria purposes it is more common to express oxygen content in terms of concentration rather than partial pressure. This concentration usually is represented by solubility in mg/L (ppm) or mL/L and these units have corresponding pressure equivalents. In the previous example with freshwater at 10 degrees Celsius and 157.3 mm Hg, the air-equilibrated solubility is 7.90 mL/L or 11.29 mg/L from solubility tables (e.g., Table 3 from APHA, 1992-column one for freshwater). If this sample was 50 percent saturated, the concentration and pressure equivalents would simply be halved (Davis, 1975). The oxygen solubility values in Table 3 represent full (100 percent) saturation of oxygen under one set of conditions. For barometric pressures other than 760 mm Hg (sea level), oxygen solubilities can be computed from the following equation: C* = C*760(Pt - p) / (760 - p) (from Colt, 1984) C* = oxygen solubility C*760 = saturation value at 760 mm Hg (Table 3) Pt= barometric pressure (mm Hg) p = vapour pressure of water (Table 1) Example: Give the oxygen solubility at 15 degrees Celsius when the barometric pressure is 29.33 in mm Hg. Pt = 29.33 in Hg (25.4 mm/in) = 745 mm Hg p = 12.79 mm Hg (form Table 1) C* = 10.08 mg/L(745 mm Hg - 12.79 mm Hg) / (760 mm Hg - 12.79) = 9.88 mg/L Table 1. Vapour Pressure of Freshwater in mm Hg as a Function of Temperature Temp.C 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0 4.58 4.62 4.65 4.68 4.72 4.75 4.79 4.82 4.86 4.89 1 4.93 4.96 5.00 5.04 5.07 5.11 5.14 5.18 5.22 5.26 2 5.29 5.33 5.37 5.41 5.45 5.49 5.53 5.57 5.60 5.64 3 5.68 5.73 5.77 5.81 5.85 5.89 5.93 5.97 6.02 6.06 4 6.10 6.14 6.19 6.23 6.27 6.32 6.36 6.41 6.45 6.50 5 6.54 6.59 6.64 6.68 6.73 6.78 6.82 6.87 6.92 6.97 6 7.01 7.06 7.11 7.16 7.21 7.26 7.31 7.36 7.41 7.46 7 7.51 7.57 7.62 7.67 7.72 7.78 7.83 7.88 7.94 7.99 8 8.05 8.10 8.16 8.21 8.27 8.32 8.38 8.44 8.49 8.55 9 8.61 8.67 8.73 8.79 8.85 8.91 8.97 9.03 9.09 9.15 10 9.21 9.27 9.33 9.40 9.46 9.52 9.59 9.65 9.72 9.78 11 9.85 9.91 9.98 10.04 10.11 10.18 10.24 10.31 10.38 10.45 12 10.52 10.59 10.66 10.73 10.80 10.87 10.94 11.01 11.09 11.16 13 11.23 11.31 11.38 11.46 11.53 11.61 11.68 11.76 11.83 11.91 14 11.99 12.07 12.15 12.23 12.30 12.38 12.46 12.55 12.63 12.71 15 12.79 12.87 12.96 13.04 13.12 13.21 13.29 13.38 13.46 13.55 16 13.64 13.73 13.81 13.90 13.99 14.08 14.17 14.26 14.35 14.44 17 14.53 14.63 14.72 14.81 14.91 15.00 15.10 15.19 15.29 15.38 18 15.48 15.58 15.68 15.78 15.88 15.97 16.08 16.18 16.28 16.38 Temp.C 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 19 16.48 16.59 16.69 16.79 16.90 17.00 17.11 17.22 17.32 17.43 20 17.54 17.65 17.76 17.87 17.98 18.09 18.20 18.31 18.43 18.54 21 18.66 18.77 18.89 19.00 19.12 19.24 19.36 19.47 19.59 19.71 22 19.83 19.96 20.08 20.20 20.32 20.45 20.57 20.70 20.82 20.95 23 21.08 21.20 21.33 21.46 21.59 21.72 21.85 21.99 22.12 22.25 24 22.39 22.52 22.66 22.79 22.93 23.07 23.21 23.34 23.48 23.63 25 23.77 23.91 24.05 24.19 24.34 24.48 24.63 24.78 24.962 25.07 26 25.22 25.37 25.52 25.67 25.82 25.98 25.13 26.28 26.44 26.59 27 26.75 26.91 27.07 27.23 27.39 27.55 27.71 27.87 28.03 28.20 28 28.36 28.53 28.69 28.86 29.03 29.20 29.37 29.54 29.71 29.88 29 30.06 30.23 30.41 30.58 30.76 30.94 31.12 31.30 31.48 31.66 30 34.84 32.02 32.21 32.39 32.58 32.77 32.95 33.14 33.33 33.52 31 33.71 33.91 34.10 34.29 34.49 34.69 34.88 35.08 35.28 35.48 32 35.68 35.89 36.09 36.29 36.50 36.70 36.991 37.12 37.33 37.54 33 37.75 37.96 38.18 38.39 38.61 38.82 39.04 39.26 39.48 39.70 34 39.92 40.14 40.37 40.59 40.82 41.05 41.28 41.51 41.74 41.97 35 42.20 42.43 42.67 42.91 43.14 43.38 43.62 43.86 44.10 44.35 36 44.59 44.84 45.08 45.33 45.58 45.83 46.08 46.33 46.59 46.84 37 47.10 47.35 47.61 47.87 48.13 48.40 48.66 48.92 49.19 49.46 38 49.72 49.99 50.27 50.54 50.81 51.09 51.36 51.64 51.92 52.20 39 52.48 52.76 53.04 53.33 53.62 53.90 54.19 54.48 54.78 55.07 40 55.36 55.66 55.96 56.25 56.55 56.86 57.16 57.46 57.77 58.07 Source: Colt, 1984 Tabulated oxygen saturation values are available as a function of barometric pressure and elevation over a range of temperatures (e.g., as in Colt, 1984).