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 93are 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 anencompassing 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