Introduction
Unlike most geologic processes, the origin of dissolution porosity lends itself
readily to analytical solutions. Four salient "laws" govern the process:
two mass balances (water balance and chemical mass balance) and two kinetic
equations (which describe the dissolution rate and the flow rate of water),
and in combination they provide a theoretical basis for quantifying the solutional
history of karst aquifers. The greatest difficulty is in applying these clean-cut
analytical tools to the complex and rather disordered world of geology. It is
impossible to model a karst aquifer in all its details, because most of the
details are unknown.
However, a great deal can be learned about the origin and distribution of
dissolution porosity by using the analytical approach to obtain a battery of
governing concepts that can be applied to all karst aquifers. This paper summarizes
the evolution of a conceptual model whose details were first developed on the
basis of field observation and hydraulics, and only later substantiated by chemical
kinetics. It applies specifically to carbonate rocks, although the general approach
can be modified to fit any geologic setting by substituting the appropriate
expressions for kinetics and fluid flow.
General distribution of karst porosity
The appropriate first step relies on concepts that are well known to everyone.
Water, where if first enters a soluble rock, is undersaturated with respect
to the minerals in that rock. Its saturation ratio (C/Cs) with respect to these
minerals is at, or close to, zero. (C = concentration of dissolved mineral,
e.g. calcite; Cs = saturation concentration, which is greatly enhanced by acids.
Cs for calcite in typical groundwater is about 2-3 mmol/L.) Dissolution is most
rapid where C/Cs is lowest, and its rate diminishes as the dissolved load increases.
The greatest dissolution occurs where the water first enters the soluble rock
and diminishes with flow distance. Thus most of the water's solutional aggressiveness
is usually squandered at and near the bedrock surface, simply lowering the surface
and widening the upstream ends of fissures that penetrate the rock (Fig. 1).
Underground water circulating through the rock has greatly diminished aggressiveness,
but unless Cs decreases (e.g. by CO2 degassing, rising temperature, or common-ion
effects) the water will never quite reach saturation. Since the flow of water
is continuous from recharge source to outlet, and the relatively high C/Cs allows
dissolution to proceed only at a slow rate, the dissolution porosity is drawn
out along the entire length of the flow paths. Aggressiveness can be maintained
by a gradual rise in Cs for example by oxidation of organic compounds. Aggressiveness
can also undergo a local burst because of mixing of different waters or by oxidation
of hydrogen sulfide. However, in a typical karst aquifer the solutional porosity
tends to form continuous conduits rather than isolated voids (Fig. 1). The diminution
of dissolution porosity with depth in karst aquifers is well documented by borehole
data (Fig. 2).
Introductory geology textbooks typically portray karst porosity in cross sections
that resemble blocks of Tilsit cheese, with the holes elongated along beds and
fractures as a gratuitous nod to the influence of geology. This portrayal would
be amusing, were it not for the fact that many scientists and engineers, perhaps
subconsciously, use the same conceptual view of karst when attempting to solve
environmental problems. The real distribution of karst porosity is more complex,
but also more predictable.

Fig. 1. Generalized cross section of a karst aquifer formed
by meteoric water, showing relative distribution of dissolution voids. The apparent
porosity is exaggerated in the diagram for clarity. Below the epikarst the total
dissolution porosity rarely exceeds a few percent and is commonly far less (see
paper by Worthington in this volume).

Fig. 2. An example of the variation in karst porosity with
depth, as observed in deep boreholes in Herzegovina (Modified from Milanovic,
1981).
Within karst aquifers, most of the dissolution porosity consists of conduits,
usually arranged in dendritic patterns in which tributaries join each other
to produce fewer but larger conduits in the downstream direction. When we visit
a cave of this kind, our conception of dissolution porosity can easily be-skewed.
The impression is that the overall dissolution porosity must be enormous. However,
it is concentrated in only a relatively few conduits, which, if compared to
the overall rock volume, yield only a tiny porosity, usually less than a percent
(see Worthington, in this volume, for representative examples). In the most
complex part of Mammoth Cave, Kentucky, Palmer (1995) calculated the total dissolution
porosity to be only 4%, even though the figure includes many more inactive relict
passages than active ones. Most accessible caves are surrounded by rock in which
the vast majority of openings have hardly enlarged at all. The conduits are
not surrounded by porous zones, with walls like a sponge, where progressively
smaller openings extend indefinitely into the cave wall. The conduits are quite
discrete.
As shown by the morphology of cave passages, the flow of aggressive water
through karst aquifers takes place mainly along fractures and bedding-plane
partings, and much less so along primary pores. It is important to note that
fractures and partings diminish in width and number with depth (see Ford and
Ewers, 1978, and Ford in this volume). Provided the openings are too small to
admit turbulent flow, the flow is described by the Hagen-Poiseuille equation:
 |
(1) |
where Q = discharge, w = fissure width, b = fissure
breadth (long dimension of fissure cross section), =
specific weight of water, µ = dynamic viscosity of water, and dh/dL
= hydraulic gradient. Although groundwater can pass through all openings in
varying amounts, note the strong dependence of flow on fissure width. Since
w diminishes downward, one can assume that the water will preferentially
follow shallow paths, far more so than in aquifers whose pore size does not
decrease so significantly with depth (for example, gravel). This applies to
fractured bedrock aquifers of all types, but especially in soluble rocks where
the initial openings are enlarged by the flow. As these openings grow, some
will enlarge more rapidly than others. They are the ones that grow to cave size
and which eventually dominate the flow pattern within the aquifer. The onset
of turbulent flow is often used to distinguish the birth of a karst conduit.
This discussion applies mainly to phreatic water. Gravitational vadose water
is easily perched for some distance on resistant or relatively insoluble beds,
providing a strong lateral component to the flow, interrupted by shafts where
the perching beds are breached by fractures.
The tendency for conduits not to penetrate far below the potentiometric surface
is disrupted to some extent by faulting and folding. In tectonically disturbed
areas it is possible for certain flow paths to extend to considerable depths,
especially along faults. For example, in a catalog of solutional voids encountered
beneath river beds during drilling by the Tennessee Valley Authority (Moneymaker,
1941), the deepest voids are encountered in the folded and faulted Appalachians
and in the fault zone of western Kentucky. Ford (1971) emphasized low fissure
frequency as the main criterion for why certain caves extend deep beneath the
potentiometric surface, whereas Palmer (1969) emphasized fissure width. The
two contrasting views are nevertheless compatible.
Despite this disruption, the shallowest paths are still the most favorable,
even in tectonically disturbed areas, and deep conduits are relatively rare.
Pervasive deep flow is likely only in confined settings, or where favorable
stratigraphic boundaries allow deep dissolution (for example, along sulfate-carbonate
interfaces). Worthington (1991) cites many examples of sulfate-rich springs
fed by groundwater that follows deep basin-wide paths.
Rates of conduit growth
In a fissured aquifer with myriad flow paths, which ones are most likely to
enlarge into solution conduits? This is not a trivial question, because the
presence and distribution of conduits is one of the most important variables
in the assessment of a karst aquifer. Phreatic conduits form potentiometric
lows and are the main paths of groundwater discharge, as well as the major paths
of contaminant transport. The configuration of vadose channels determines how
sources at the surface relate to the points of recharge at the underlying water
table.
In most carbonate aquifers only a small percentage of flow routes enlarge
into turbulent-flow conduits. Early in the flow history of the aquifer, fissures
are narrow and the flow is dispersed among many different routes, each with
its own overall hydraulic gradient, mean fissure width, total flow length, and
mean discharge. Groundwater discharge and velocity are so small that the water
becomes nearly saturated with dissolved bedrock long before it emerges at the
surface. This can be verified by measuring the chemistry of inflowing seepage
through narrow openings into accessible caves. Even some substantial flows of
several cm3/sec arrive essentially at C/Cs =1.0 after less than 50
m of flow. Therefore, in any single flow route, the rate of dissolutional enlargement
depends simply on the chemical mass balance. The mass of material removed from
the walls of the opening is equal to the mass removed in solution by the groundwater
flow. This rule is independent of the shape of the opening (tube, fissure, etc.).
The chemical mass balance can be stated as follows: Mass removed from the
walls of the opening = mass carried away in solution. Change in mass with time
= ,
where
= rock density,
= change in volume with time, and
= change in dissolved load over the length of the conduit. A conduit of circular
cross section is assumed for convenience; the actual conduit shape is not important,
since the functional relationships are the same. Thus, within any single conduit
segment of rather uniform dimensions, the rate of wall retreat (S) can be stated
[cm/yr] |
(2) |

Fig. 3. Mean rate of wall retreat (cm/yr) as a function of
discharge (Q), flow distance (L,), hydraulic gradient (i), and tube radius (r)
in tubular conduits at 10° C and PCO2 = 0.01 atm (CS = 212 mg/L CaCO3). Values
of i/L are valid only for laminar flow. A = region of varied growth rates (Q/rL
< 0.001 cm/sec); B = maximum possible solutional growth rate, limited by
chemical kinetics. (From Palmer, 1981).
where C0 = initial concentration of dissolved
bedrock (mg/L), r = conduit radius (cm), and L = conduit length
(cm). All other terms are in cgs units. The numerical coefficient converts the
result to cm/yr. A uniform radius is not required, since we are concerned
only with mean values of S, Q, and r, and again the functional
relationships are not affected.
Early in the evolution of a karst aquifer, when the water emerges from each
opening essentially at saturation, if we assume that C0
= 0, then
= CS, which is constant at a given temperature and CO2
partial pressure. Under these conditions, the mean rate of wall retreat within
each conduit is therefore a linear function of Q/rL.
The mean S values plot as the family of lines shown in group A of
Fig. 3 (10° C, PCO2 = 0.01 atm). At any value of r, the larger the Q/L
ratio, the greater the rate of enlargement. Large Q and/or small L
favor rapid enlargement. Dashed lines show the corresponding values of i/L,
where i = hydraulic gradient, are also shown on Fig. 3, valid only
for laminar flow (derived from the tubular version of eq. 1, where
is replaced by ).
The numerical values for S in Fig. 3 are misleading, because (1)
they assume that the water enters each conduit at zero saturation; (2) most
of the dissolution is concentrated in the upstream end of the conduit, so that
the rate throughout the majority of the conduit is less than the mean; and (3)
they do not consider mixing or branching between different conduits. However,
it is the relative values - the general relationships among the terms - that
concern us here, not the specific numerical values. Actual growth rates are
best determined with finite-difference calculations or analytical methods (e.g.
Palmer, 1984, 1991;Dreybrodt, 1990,1996; Groves and Howard, 1994a and b; Clemens
et al, 1996; Hanna and Rajaram, 1998).
The earliest conduit growth usually begins somewhere in (or beyond) the lower
left portion of Fig. 3. Growth rates are far too low to allow turbulent-flow
conduits to develop in a geologically feasible time. Within any given conduit,
the growth rate can increase only if Q increases, since L does not change. If
Q does not increase, the enlargement rate will remain static or actually decrease,
as shown by the negative slope of the lines in group A as the conduit radius
increases. (Conduits of non-circular cross section would have more gently sloping
lines in group A.)
But the growth rate reaches an upper limit beyond which it cannot rise. This
is typically about 0.001-0.01 cm/yr, depending on the chemical conditions. So
far the analysis has been focused on narrow openings in which the water emerges
near saturation. Now consider a conduit with such a large Q/L ratio
that water is able to pass through the conduit while retaining nearly all its
aggressiveness. The entire conduit enlarges at a nearly uniform rate (shown
as B in Fig. 3), which is a function of the dissolution kinetics, rather than
of the mass balance. Rates of wall retreat are almost uniform and independent
of Q/L.
Experiments by Berner and Morse (1974), Plummer and Wigley (1976), Plummer
et al. (1978) show that in turbulent flow the dissolution rate for calcite is
governed mainly by the chemical reactions at the wall, rather than by mass transfer
within the fluid, and that turbulence and flow velocity have little effect on.
Mass transfer does have an effect at low flow rates in limestone conduits (Curl,
1968; Buhmann and Dreybrodt, 1985a and b, Dreybrodt, 1988), and in evaporites
at any flow rate, but the pattern of lines in group A in Fig. 3 is not affected.
For carbonate rocks, the dissolution rate is expressed by
[mg/L-sec]
|
(3) |
where
= surface area of rock in contact with water, V = water volume, k
= reaction coefficient, and n = reaction order. It is more common for
the parenthetical term to be expressed as (CS - C), but the form shown
in eq. 3 avoids the problem of having to adjust the units of k whenever n changes.
Values of k and n depend on the acid content of the water (for example, PCO2),
and k also varies with temperature and lithology (Palmer, 1991, derived from
the original lab measurements of Plummer et al., 1978, Plummer and Wigley, 1976,
Rauch and White, 1977, and other sources). The reaction order (n) increases
rather abruptly from 1-2 to 4 or more at C/CS values that range from
about 0.6 to 0.9, depending on temperature and PCO2
(Palmer, 1991; Dreybrodt et al. in this volume). In typical groundwater, n
= 2 (or 1, in narrow conduits) and k = 0.01 at C/CS <=0.65.
At greater C/CS n=4 (occasionally more; see Dreybrodt et al., 1999)
and k = 0.1.
Because C/CS < 1, an increase in reaction order represents a decrease
in dissolution rate. Ironically, this decrease appears to be essential to the
origin of nearly all solution conduits (Palmer, 1984). If the low-order (rapid)
kinetics were to prevail throughout the initial opening, virtually all the aggressiveness
would be consumed within a few meters of flow, except in usually wide fissures,
and the growth rate would be so slow in the rest of the conduit that it would
never achieve turbulent flow within a geological feasible time. On the other
hand, the high-order (slow) kinetics alone are too slow to enlarge the conduits
to the size of traversable caves. White (1977) called the change from slow to
rapid dissolution a "kinetic trigger" that represents the beginning
of true cave development. Thus cave origin enjoys the best of both worlds: slow
growth when the aggressiveness must persist for long distances through narrow
fissures, and later rapid growth to achieve large size.
Combining eqs. 2 and 3, and substituting
and ,
gives the following general equation for dissolutional wall retreat in carbonate
rocks:
[cm/yr]
|
(4) |
which is valid for all types of flow and conduit geometries (Palmer, 1991).
The maximum rate of wall retreat (aside from occasional mechanical erosion during
floods in large conduits) can be determined by this equation, where C/CS
= saturation ratio where the water enters the conduit. In Fig. 3, the maximum
rate at B is for C/CS = 0. Higher saturation ratios, even as high as
0.9, still provide enlargement rates that are rapid by geological standards,
and the overall shape of the graph in Fig. 3 remains valid.
The composite graph in Fig. 3 shows both the early laminar flow (S dependent
on Q/L) and the late-stage flow (S independent of Q/L).
The curvature of the lines where Zone A meets Zone B was determined by finite-difference
analysis.
It is not realistic to assume that water can pass through an entire aquifer
without changing its saturation ratio. The water acquires most of its solute
load at the upstream end, especially where it accumulates in small openings
that feed the main conduits. The maximum enlargement rate in a conduit is thus
limited in part by the value of C0 at its upstream
end, which is rarely less than 0.5. High-Q flow can pass through a
cave-size conduit for great distances while gaining only a few mg/L
of dissolved load. Because of the large Q, this still represents a
substantial rate of mass flux.
Competition between enlarging flow paths: unitary conduits and branchworks
The specific configuration of conduits within the aquifer is determined by
the relative growth rates of competing flow paths. The most common situation,
where meteoric groundwater passes through a carbonate unit from an upland recharge
surface to outlets at lower elevation, can be described as follows:
1. Early in the flow history of the aquifer, the many alternate flow routes
have low Q/L ratios and plot in or beyond the lower left comer of Fig.
3. Their Q/L values and rates of conduit growth span a wide range of
many orders of magnitude. All growth rates are small, but some will be much
greater than others. The dots on Fig. 4 show some representative flow paths
early in the aquifer development. These are idealizations, because no single
flow path behaves entirely independently.
2. Growth rate can increase only if the Q/L ratio increases. For
any given path, this can be achieved only by an increase in discharge. As each
opening grows, its discharge tends to increase because more water is able to
pass through. But there is a maximum amount of available infiltration, and eventually
a conduit can acquire additional Q only at the expense of its neighbors.
This is achieved in two ways: (a) As a conduit grows, its hydraulic head decreases
(despite increasing Q) because of the reduced amount of head loss required
to transmit the flow. Water is drawn from neighboring openings in which the
head is greater, which increases the discharge in the major conduits, (b) Sinkholes
develop as the major openings and their tributaries enlarge, especially at the
upstream ends, funneling water into the largest conduits but bypassing lesser
openings. As a result, the openings with the largest initial Q/L or
i/L are those that are most likely to acquire increasing flow and to
increase their enlargement rate. As shown by the arrows in Fig. 4, some openings
are favored over their neighbors and increase rapidly in both Q and
S. Others languish with negligible and generally decreasing Q
and S.

Fig. 4. Varied growth histories of competing flow paths in
the early stages of a karst aquifer. Paths A, B, and C accelerate in growth
and reach the maxium rate by increasing their discharge. These are the routes
that become major dissolution conduits. In contrast, other paths (e.g. D and
E) stagnate at low and usually diminishing enlargement rates.
3. Enhanced discharge is able to increase the enlargement rate only up to a
certain point, beyond which the rate becomes insensitive to further increases
in Q. The enlargement rate is now limited mainly by the dissolution
kinetics. Those relatively few conduits that reach this state grow at approximately
the same rapid rate, with only minor differences caused by local variations
in chemistry, flow, and passage configuration. Traversable caves are formed
by water that has achieved this state.
Single-passage stream caves and branchwork caves are the normal result. Branching
caves are by far the most common, because of the tendency for convergence of
flow toward the relatively low head of the major conduits, and because of fortuitous
intersections between passages. The typical passage pattern is similar to that
in Fig. 5a. This example is located in prominently bedded, low-dip strata. Greater
structural complexity leads to comparable passage complexity, but the overall
cave pattern is usually a branchwork.
Uniform dissolution among many competing flow routes: labyrinthine porosity
Under certain conditions, nearly every competing flow route enlarges at comparable
rates, and a labyrinth of interconnected openings is formed. According to Fig.
3, the only way this can happen is to expose many openings simultaneously to
high values of Q/L or i/L. Beyond a certain threshold (Q/rL
> 0.001 cm/sec in tubes, Q/bL>0.001 cm/sec in fissures),
they will all enlarge at rather similar rates, regardless of size, discharge,
gradient, or flow length. The result is a labyrinth of interconnected passages
consisting of openings that have grown simultaneously to cave size. Caves formed
under these conditions have maze patterns (Fig. 5 b, c, and d). Favorable conditions
include the following:
Where aggressive water first enters the soluble rock (small values of L).
Distances of flow from the entry points are short, and all openings have large
Q/L values regardless of opening size or discharge. The most common
example is the epikarst, the zone of extensive dissolution in the upper few
meters or tens of meters of the soluble rock, located either beneath a soil
cover or exposed directly at the surface (Fig. 1). The same approximate result
is achieved where water passes through a porous, non-soluble rock before entering
the carbonate rock, forming a maze cave. Network caves formed along intersecting
fractures are the most common type (Figure 5b). The flow of water can be downward
from the overlying surface or upward as artesian flow from an underlying formation
(provided the water has not encountered substantial amounts of carbonate rock
beforehand).

Fig. 5. Examples of solutional cave patterns: (a) Crevice
Cave, Missouri, (b) part of Crossroads Cave, Virginia, (c) part of Holoch, Switzerland,
(d) main rooms of Carlsbad Cavern, New Mexico. Maps courtesy of Paul Houck,
H.H. Douglas, Alfred Bogli, and Cave Research Foundation, respectively. E =
entrance.
It is also possible to enlarge many alternate flow routes simultaneously where
steep hydraulic gradients are imposed by flooding. This is most noticeable where
soluble rock is exposed adjacent to entrenched rivers that flood severely. Water
enters the ground as bank storage having high i/L ratios because of the steep
gradients and short flow distances. The same effect is achieved in local areas
within preexisting caves where flow constrictions (breakdown, sediment fill,
interference by relatively insoluble beds) cause floodwater to pond upstream
from them. Seasonal or storm-related flooding periodically injects aggressive
water into every available opening, enlarging them rapidly and simultaneously.
Irregular network caves (western part of Fig. 5b) are formed where vertical
or steeply inclined fractures dominate. Anastomotic caves are formed where bedding-plane
partings or low-angle faults are the main cave-forming units. Where matrix porosity
provides the major flow paths, for example in diagenetically young limestones,
breccias, or reef rock, a spongework pattern will form (as illustrated in parts
of Fig. 5d).

Fig. 6. Many alternate routes are able to enlarge simultaneously
at roughly the same rate, regardless of size, if they are all able to sustain
high discharges (e.g. because of steep hydraulic gradients) or short flow distances.
Maze caves, epikarst, and pervasive labyrinthine porosity are produced in this
way. Very small openings, or those with low Q/L or i/L will not be competitive.
Where steep hydraulic gradients are sustained (e.g. beneath dams), growth
rates rise steeply in all conduits as r increases, as shown by the
dashed lines in Fig. 3, until they all reach the maximum rates of wall retreat
at or near the top of the graph. A network of similarly enlarged conduits is
expected (Palmer, 1988; Dreybrodt, 1996; Bauer et al, 1999).
Solutional aggressiveness can be renewed in zones of mixing between chemically
contrasting waters, for example between infiltrating high-CO2,
freshwater and low-CO2 seawater. Local network
and spongework patterns are produced, not only because the flow distances from
the source of aggressiveness are short, but because of the diffuse nature of
most water flow under these circumstances. Carbonate aquifers in coastal and
island settings are noted for this kind of porosity (Back and others, 1984;
Mylroie and Carew, 1990; Mylroie and Vacher, 1999).
Mixing between rising (often thermal) waters and meteoric water is capable
of producing considerable aggressiveness. Caves formed in this way tend to have
network or irregular ramiform patterns (Fig. 5 b and d). Oxidation of rising
hydrogen sulfide rising from depth into oxygen-rich zones at or near the water
table produces a burst of localized dissolution. This process usually results
in network and ramiform caves, consisting of large irregular rooms with sequential
branches exiting to the surface (Fig. 5d). The outflow usually coalesces into
discrete conduits as aggressiveness is lost and flow length increases.
Summary
This simplified view of the distribution of karst porosity leads to several
conclusions, which are summarized below:
Karst porosity is greatest near the land surface in areas of groundwater recharge
(for example, in the epikarst). It diminishes in the downflow direction but
coalesces into relatively few major conduits that are continuous through the
entire aquifer. Except in mixing or redox zones, karst porosity rarely occurs
as isolated voids. Branching conduit patterns are the most common.
Conduits form only where the setting is favorable for certain flow paths to
gain discharge at the expense of their neighbors, e.g. by development of sinkholes.
Dissolution labyrinths, in which every accessible opening is enlarged to comparable
amounts, form in several settings: (a) within short distances of flow from where
aggressive water first enters a soluble rock, or where mixing or redox reactions
produce local zones of undersaturated water within a karst aquifer; (b) in areas
of steep hydraulic gradient, where Q/L and i/L are large.
Dissolution porosity diminishes greatly at depths beneath the local base level
because of the very strong influence of fissure widths on resistance to flow.
Use of these concepts can aid in the prediction of porosity distribution and
geometry. However, it must be recognized that relict karst porosity can also
occur where conditions favorable to its origin are no longer present. Also,
details of geologic structure must be considered. These ideas are developed
further in the literature.
The concepts described here have not changed significantly since their first
brief publication in 1981, although they have been explored at greater length
since by more advanced geochemical and digital models (see Palmer, 1991 and
1995). The model described in Fig. 3 was generalized from the behavior of individual
conduits. However, subsequent digital modeling of multiple-conduit networks
has validated these concepts.
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