Subsurface Environment

1. Water Origins and Chemistry

ORIGIN OF SUBSURFACE WATERS

Four types of subsurface water can be defined, according to their origin: meteoric, connate,
juvenile, and mixed.
Meteoric water occurs at shallow depth due to the infiltration of rainwater. The salinity of
meteoric water is generally low and this water tends to be oxidizing.
Meteoric water is often acidic due to dissolved humic, carbonic and nitrous acids. However,
these acids can be quickly neutralized in the subsurface, particularly when in contact with
carbonate rocks.
The second type, connate water, is harder to define. Connate water was originally thought to
be ancient sea water, which was trapped in the sediment during burial. Definitions for connate
water now include "interstitial water existing in the reservoir rock prior to disturbance by
drilling" (Case, 1956), and, "waters isolated from the surficial hydrologic cycle for an extended
period" (White, 1957). Connate water differs a good deal from sea water both in
concentration of dissolved salts and in chemical parameters such as pH and Eh, as
discussed below.
Mixed water results from the commingling of meteoric and connate waters. In most
sedimentary basins, a transition zone containing waters of mixed origin is found between the
near surface meteoric water and the deeper, more saline connate water.
Juvenile water is of primary magmatic origin. It Is water that has never before been at or
near the earth's surface and is brought to the near-surface environment dissolved in magma.
Juvenile water is usually mixed in relatively small quantities with either connate or meteoric
water, and is rarely found alone.

OXIDATION/ REDUCTION POTENTIAL AND PH

Connate and meteoric waters—and waters that aremixtures of these two—can be
differentiated based on their chemistry. There are several ways this can be done, one of
which is to use Eh, the oxidation/reduction potential, together with pH, which is a measure of
acidity or alkalinity of the water.
Figure 1 is an Eh-pH diagram summarizing data from Krumbein and Carrels, 1952; Pirson,
1970; and, Friedman and Sanders, 1978.
 Figure 1

Eh, measured in volts, indicates the ability of the water to oxidize or reduce metals. Waters
with Eh values above zero are considered to be oxidizing and waters with Eh values less than
zero are reducing.
pH is a measure of the concentration of hydrogen (H+) ions in the water. At a pH of seven,
hydrogen ions and hydroxyl (OH-) ions are equal in abundance and the water is considered to
be neutral. As pH is reduced below 7, the water becomes increasingly acidic. As pH is
increased above 7 the water is increasingly alkaline.
Figure 1 shows the range in Eh and pH in which the water molecules are stable. Outside
this region, water breaks down Into hydrogen and oxygen.
The Eh-pH range of rain water is both highly oxidizing and fairly acidic. Although subsurface
meteoric water may be largely derived from rain water, it is less oxidizing and less acidic. This
is because subsurface meteoric water contains less dissolved oxygen, nitrous oxides, carbon
dioxide and humic acids than rain water that has just entered the subsurface.
As rain water percolates down into the subsurface it reacts with the rocks through which it
passes, and undergoes a decrease in Eh and an increase in pH. Notice that meteoric ground
water can have pH and Eh values similar to sea water even though compositionally it is quite
different from sea water.
Deep connate waters show a wide range of Eh and pH depending on their history and,
particularly, on how much they've mixed with meteoric waters. Notice that oil field brines tend
to be more alkaline and more strongly reducing than sea water.
The Eh and pH of pore fluids control the precipitation and dissolution of cements, such as the
carbonates and iron oxides, as well as the alterations of clay minerals in subsurface rocks.
Therefore it is extremely important to understand the relationship of Eh and pH to diagenesis
and to the evolution of porosity.
SALINITY
Figure 1 shows that the salinity of subsurface water increases with depth.

Figure 1

The rate of increase varies from basin to basin and even from place to place within a
particular basin.
Sea water typically has a salinity of about 35 parts per thousand (3.5%) dissolved
substances. The salinity values of subsurface waters range from near zero in newly
introduced meteoric water to over 600 parts per thousand (60%) in connate water that is
contained within evaporite formations (Case, 1956). In most connate waters, however, the
content of dissolved solids seldom exceeds 350 parts per thousand (35%).
In the salinity profile of a hole, the salinities of water in the sandstone and shale beds may be
quite different. In sandstone the salinity of connate water generally increases with depth at
rates ranging from 0.08 to 0.3 parts per thousand per meter (Dickey, 1979).
Local reversals of this general trend have been observed and are thought to be due to two
possible causes.
First, meteoric water can be trapped beneath an unconformity and preserved as a
"paleoaquifer" with relatively low salinity as compared with connate water above the
unconformity. An example of this can be found at the sub-Cretaceous unconformity of Israel
 where beds above the unconformity have salinities of 60 parts per thousand. Beneath the
unconformity salinities drop to about 20 parts per thousand before gradually increasing again
to over 40 parts per thousand (Bentor, 1969). A second cause of salinity reversal with depth
is from overpressure, particularly when found in shale sequences, where formation water is
trapped, cannot circulate, and therefore retains a lower salinity than water in strata above it.
In shales, the increase in salinity with depth is less noticeable than in sandstones, and the
salinity of connate water in shale is commonly about a third of the salinity of interbedded
sandstone (Dickey, 1979). This difference along with the tendency for salinity to increase with
depth has been attributed to "salt-sieving" (De Sitter, 1947). In this process as water moves
upwards in compacting sediments, shales act as semipermeable membranes preventing salt
ions from escaping from the sands.
Studies in the Gulf of Mexico and the Mackenzie Delta by Overton, 1973; and, Van Elsberg,
1978, have delineated four major subsurface environments. These zones, as listed by Selley,
1983, are :
Zone 1 (Surface - about 1 km) Zone of circulating meteoric water. Salinity fairly uniform;

Zone 2 (about 1-3 km) Salinity gradually increases with depth. Saline
formation water is ionized;

Zone 3 ( 3 km) Chemically reducing environment, in which hydrocarbons

form. Salinity uniform with increasing depth; may even decline if
overpressured;

Zone 4 Incipient metamorphism with recrystallization of clays to micas.

Figure 2 is a map showing lateral variations in salinity in the Illizi sedimentary basin
in eastern Algeria.
 Figure 2

The salinity contours, or isocons, are from a Devonian-Silurian sandstone formation, which
indicates that salinity increases northwards into the deeper parts of the basin. Such trends
are common in sedimentary basins where the margins of the basin are more susceptible to
circulating meteoric water than the deeper parts of the basin. In the centers of basins the flow
of subsurface water is commonly slow, and the original connate waters can be preserved with
very little mixing.
Regional isosalinity maps can be very useful exploration tools. Figure 3 is an isosalinity map
of the Ellenburger formation in a large region of west Texas.
 Figure 3

Areas of high salinity on the map may possibly indicate stagnant regions that are unaffected
by meteoric flushing and where oil or gas accumulations may be preserved. The relationship
between subsurface water salinity and oil occurrence is complicated, and must be worked out
in each basin.

COMPOSITION
Meteoric water differs from connate water not only in salinity but also in proportions of
dissolved ions. Meteoric waters are divided into those with relatively high proportions of
sulphate and sodium and those which are high in bicarbonate and sodium.
Connate waters are divided into those that are enriched in chloride and magnesium ions, and
those enriched in chloride and calcium ions. In comparison to connate waters, meteoric
waters have higher concentrations of bicarbonate and sulphate ions and relatively low
amounts of calcium and magnesium ions. In comparison to sea water, connate water
contains much higher concentrations of the highly soluble chlorine and sodium as shown by
the average compositions of Tertiary and Cretaceous oil-field brines ( Figure 1 ).
 Figure 1

Dissolved sodium and chlorine, taken together, account for the largest share of the elevated
salinities we noted earlier. Sulfate, magnesium, and potassium are much less abundant, but
are still very important, because their proportions give indications of important diagenetic
reactions.
Also, note that bromine is more abundant in connate water than in sea water.
Sulfate is almost always much less abundant in connate water than in sea water. This is due
to precipitation of calcium sulfate ( Ca++ + SO4-2 CaSO4 ) and to sulfate reduction by

bacterial action, producing hydrogen sulfide gas ( 2H + SO4 = H2S+ 2O2 ).

Sulfate concentrations higher than that of sea water may be present in connate water if
evaporite rocks are present in the stratigraphic sequence.
Connate water may be depleted in both magnesium and potassium with respect to sea water,
as indicated in the analyses shown in Figure 1 , but exceptions to this generalization are
common.
Depletion of magnesium in connate water is thought to be caused by dolomitization, a
process in which calcite in limestone layers is converted to dolomite by an exchange of
magnesium for one half of the calcium in calcite, and a reordering of the crystal structure
[ 2CaCO3 + Mg++ CaMg(CO3)2 + Ca++].
Typically, calcium is more concentrated in connate water than in sea water. The increased
calcium abundance is due to the release of calcium during dolomitization [ 2CaCO3 + Mg+
+
CaMg(CO3)2+ Ca++], dissolution of calcium sulfates ( CaSO4 Ca++ + SO4= ), the
release of calcium during clay diagenesis ( montmorillonite + K+ illite + Ca++ + Na+ + H2O ),
and the low rate of calcite precipitation due to the low bicarbonate levels in connate water.
Depletion of potassium probably results from the uptake of that element by clay minerals.
Connate waters also contain traces of dissolved hydrocarbons which are not common in
normal sea water (Buckley et al., 1958). This is significant for two reasons. First, it raises the
possibility of regionally mapping dissolved hydrocarbons as a key to locating new oil and gas
fields. Second, it has some bearing on the migration of both oil and gas.