Monitoring Dissolved Oxygen in Ground Water: Some Basic Considerations by Seth Rose and Austin Long Abstract Dissolved oxygen (D.O,) concentration has a significant effect upon ground water quality by regulating the valence state of trace metals and by constraining the bacterial metabolism of dissolved organic species. For these reasons, the measurement of dissolved oxygen concentration should be considered essential in most water quality investigations. 1D.O. measurements have been frequently neglected in ground water monitoring. This is because O, has often been assumed absent below the water table; measurement of concentrations is not mandated by drinking water standards; and the redox potential has previously been considered an adequate and encompassing electrochemical measurement. Redox potentials, however, cannot adequately predict dissolved oxygen concentrations nor can D.O. concentrations be used to ealeulate redox potentials. D.O. concentrations can be measured precisely in the field by titration or electrode methods. The best methods of sample recovery are those that use positive pressure displacement devices. A fully adequate sampling procedure will isolate ground water from the atmosphere and and pressure. collect samples at restricted depth intervals at ambient temperature Introduction Oxygen is acolorless, tasteless, odorless gas, which in its dissolved state in water, does not directly affect human health, Oxygen concentration limits have therefore usu- ally not been specified in drinking water standards (c.g., U.S. EPA 1975). Although DO. can be precisely mea- ‘sured, concentrations are not monitored as part of many ground water quality investigations. This is unfortunate in that D.O. concentration can be used to assess the stability of various trace metals, radionuclides, toxic ani- onic complexes, and organic contaminants in ground water. ‘The occurrence and distribution of dissolved oxygen has probably been most systematically investigated in lakes and rivers. Here, well-defined patterns have been established with respect to oxygen concentration, depth and season, This detailed understanding of D.O. sys- tematics has evolved primarily because the presence of free molecular oxygen (O,) provides the key biochemical constraint upon these ecosystems. Before the present emphasis upon ground water con- tamination, hydrologists have not been greatly concerned with these ecological factors and have often assumed ground water deep below the water table was anoxie (Winograd and Robertson 1982). As a result, our under- standing of the behavior of D.O. systematics within the subsurface remains somewhat lacking. This paper reviews some of the significant chemical, geochemical and hydrogeological aspects of dissolved oxygen, particularly as they relate to ground water contamination. Various sampling and measurement considerations will also be briefly discussed. Chemical and Geochemical Considerations Molecular oxygen, which constitutes approximately 20 percent of the earth's atmosphere, is one of the impor- tant natural gases dissolved in ground water. Oxygen’s limited solubility, as described by Henry’s aw, is directly related to atmospheric pressure and inversely related to water temperature and salinity. The solubility of oxygen increases proportionately with hydrostatic pressure, hence depth. In dilute solutions at sea level, the solubility of O> ranges between 10.0 and 7.0 mg/ Lat temperatures ranging between 15 to 31 C (APHA 1981). ‘The most important chemical characteristic of mole- cular oxygen is its ability to accept electrons from (ox- idize) other species in water. Both electrons and energy ‘Winter 1988 GWMR 93are transferred in biological and geochemical oxidation- reduction (redox) reactions. No other naturally occurring constituent of water is a more energetic or biologically reactive oxidant than molecular oxygen (Stumm and Morgan 1981); therefore, aerobic bacteria utilize D.O. as part of their metabolism. This results in the oxidation of organic carbon, hydrogen sulfide, ammonium, molecular nitrogen and other reductants (Champ et al. 1979). The ‘most important aspect of these biochemical redox reac- tionsis their irreversibility; therefore, dissolved oxygen is always consumed and never produced as a result of bacterial metabolism. Dissolved oxygen is also an important geochemical oxidant, D.O. is consumed as the result of the oxidation of the ferrous silicates, an important low-temperature ‘weathering mechanism (e.g., Siever and Woodford 1979) Dissolved oxygen concentration, in large part, controls the solubility of many naturally occurring, polyvalent trace elements in ground water. For example, iron con- centrations are usually below maximum drinking water standards in oxic water due to the precipitation of iron oxyhydroxides. The oxyhydroxides, in turn, are impor- tant adsorbents of heavy metals (Stumm and Morgan 1981). Hydrogeological and Ground Water Contamination Considerations ‘The atmosphere isthe source of oxygen dissolved in ‘most ground water. It has often been assumed that oxy- zen derived from the atmosphere is rapidly consumed in the soil and the unsaturated zone by microbial respiration and the decomposition of organic matter (Winograd and Robertson 1982). Contrary to this prevailing notion, appreciable concentrations of D.O. (> 1.0 mg/L) have bbeen measured in samples representative of relatively deep ground water in alluvial basins (DeWald 1984, Rose 1987) and other diverse hydrogeological settings (see ‘Winograd and Robertson 1982). This probably indicates that (1) the microbial reduetion of , is limited in many aquifers, or (2) oxygen can be effectively transported to the phreatic zone from the overlying vadose zone, or (3) both of the preceding Dissolved oxygen concentration should be considered a critical parameter in any investigation of ground water contamination, particularly those involving the migration of landfill leachate or mining wastes. As previously men- tioned, D.O, often controls the fate of dissolved organic contaminants by constraining the types and numbers of microorganisms present within an aquifer. In turn, bac- teria can either decompose or, in some cases, produce organic contaminants 2s part of their metabolism, For example, most alkyl benzene and chlorobenzene groups are probably biodegradable in aerobic water while stable in anaerobic water. Conversely, trichloroethylene (TCE) is stable in oxygenated water while possibly biodegrada- ble in anoxic water (Wilson and McNabb 1983).. A detailed investigation of contaminant migration from landfills, tailings piles, and retention ponds should define a three-dimensional D.O. profile within both the contaminant zone(s) and the surrounding region. The 4 Winter 1988 GWMR often-mapped parameters such as dissolved solids con- centrations and electrical conductivity usually cannot be used to infer the presence or concentration of oxygen- sensitive contaminants such as methane or hydrogen sulfide. The dissolved organic carbon (D.0.C) concen- tration in landfill leachate is often hundreds of times higher than that in uncontaminated ground water (€.g., Baedecker and Apgar 1984). When ground water be- comes this polluted, dissolved oxygen is likely absent, even at shallow depths. However, this assumption always, requires site-specific verification. Nine of the 16 inorganic constituents that have speci- fied concentration limits in drinking water have multiple oxidation states (Cherry et al, 1984) and are therefore ‘Sensitive to dissolved oxygen concentration. These are arsenic, chromium, iron, mercury, manganese, selenium, uranium, nitrogen, and sulfur. Other potentially hazard- ‘ous heavy metals such as silver, copper, cadmium and zine form ionic complexes and solid compounds with ‘multivalent elements (notably sulfur, Cherry et al. 1984) Hence, the concentration of these heavy metals are also in part governed by D.O. concentration Uranium, selenium, and arsenic are insoluble under reducing or anoxic conditions (Drever 1982). Conversely, iron and manganese are insoluble in oxygenated water. The pH of the solution and the concentration of inorganic and organic complexing agents need also be considered in determining the fate of these species. Dissolved Oxygen and the Redox Potential Traditionally, the electrochemistry of ground water has been studied using a parameter known as the redox or electrode (Eh) potential. The electrode potential is a ‘measurement of the electrical energy transferred between a water sample and a standard reference electrode cell ‘The higher the redox potential, the more oxidizing the solution. This parameter has been viewed by geochemists, as a more encompassing measurement than the concen- tration of any one redox constituent, such as D.O. con- centration. The electrode potential has been rather extensively used to predict the activity ratio (or relative abundance) of the numerous redox couples dissolved in ‘ground water (e.g, ferrous/ ferric iron, hydrogen sulfide/ sulfate, and nitrte/ nitrate). However, recent studies by Hostettler (1984), Lind- berg and Runnells (1984) and Thorstenson (1984) have seemingly discredited the redox potential as a meaningful and comprehensive electrochemical measurement. A full description of this important and ongoing controversy is, beyond the scope of this paper, however, some important points should be summarized. ‘A meaningful redox measurement can be derived if and only if (1) chemical and electrochemical equilibrium exists within solution (Hostettler 1984), and (2) all redox reactions between the various redox couples occur rever- sibly upon the surface of the redox electrode (e.g., Stumm and Morgan 1981). Unfortunately, these conditions are seldom, if ever, met within natural aqueous systems (Hostettler 1984). This is due in large part to the irre- versibility of biologically mediated redox reactions. In anencompassing survey of ground water redox measure~ ‘ments, Lindberg and Runnels (1984) concluded that elec- trochemical potentials calculated upon the basis of the activity ratio of one or more redox couples seldom agreed with measured redox potentials. Dissolved oxygen concentration in most cases cannot be properly derived from the redox potential in that ‘measured potentials are usualiy 400 to 600 millivolts lower than calculated potentials (Garrels and Christ 1965), Furthermore, itcan be shown that redox potentials calculated upon the basis of electron transfer between O» and HO are more dependent upon the pH of the solution than upon the D.O. concentration, Figure | illustrates a comparison of calculated elec- trode potentials (using the O,/ 1,0 couple) and measured Eh values for the same ground water samples. The area in the box represents a comparison of 45 ground water measurements from production wells within the Tucson, Basin Aquifer (Rose 1987). The redox electrodes were enclosed within a PVC flow cell, thereby isolating the sample from the atmosphere. If electrochemical equili- brium existed, then measured and calculated values would have plotted upon the 1:1 slope shown on the ‘graph. The poor correlation between measured and cal- culated values was likely the result of electrochemical disequilibrium between H,O, O>, and the electrode sur- face. Garrels and Christ (1965) state that D.O, docs not exert its full potential upon the surface of the redox electrode and hence the discrepancy exists between mea- sured and caleulated values, Sampling and Measurement Considerations Dissolved oxygen is commonly measured by the modified Winkler titration method and/or with a dis- solved oxygen electrode. A detailed explanation of these methods s given in APHA (1981). Under field conditions, both the precision and detection limit are approximately 0.2 mg/L (Winograd and Robertson 1982), However, the natural variability of D.O. concentration at a given well site might be appreciably higher—approximately +/-0.5, mg/L about a given mean (Rose 1987) The electrode method is simpler but initially more costly than the titration method. The Winkler titration is time-consuming in that it requires the preparation and application of five reagants as well asthe prestandardiza- tion of the titrant. However, the oxygen electrode can sometimes malfunction (apparently randomly) in the field. Therefore, itis recommended that the field analyst be prepared to perform the Winkler titration as part of the sampling procedure. If an electrode is used, both ‘methods should be used to corroborate one another (APHA 1981). The electrode method has an advantage in that it permits continuous sampling. This helps to ensure that water quality has stabilized within the well casing after it has been purged. a ° 3 is t T 3 QO Ww £400 = ance 3 oF a values < w 2 300F Ww 4 1 1 \ 1 400 500 600 700 800 Ey CALCULATED (mv ) Figure 1. Measured redox potentials vs electrode (Nernst) potentials calculated upon the basis of dissolved oxygen concentration. There is apparently no relationship between the two as can be inferred from the deviation from the 11 slope shown’ ‘The range of values represent samples taken from 45 production wells inthe w the upper lft portion ofthe graph, oxygenated Tucson Basin Aquifer (from Rose 1987) Winter 1988 GWMR 95