04 DJL - KarstProcess

Teaching resources for
Speleology and Karst 2009
THE KARST
PROCESS
by
Jo De Waele
In collaboration with: Paolo Forti

Leonardo Piccini
Ugo Sauro
Ponte di Veja, Lessini Mountains, Veneto, Italy (photo J. De Waele)
THE KARST PHENOMENON: DEFINITIONS
Definitions of karst
Various forms of rock weathering in which the dominant process is the
dissolution of rock in water.
The word Carso can be

derived from the pre-
Indo-European word
karra or gara, which
means “stone”, and is
still present in many
European and Middle
Eastern languages and
dialects. The Slovene
word Kras, indicating the
rocky region around
Trieste and in Western
Slovenia (Classical Karst)
has the same origin. Ancient print from Valvasor (1689) Die Ehre dess Hertzogthums Crain
The karst process – Società Speleologica Italiana 2009

WHERE DOES THE KARST PROCESS OCCUR?
In the presence of potentially soluble rocks:

- evaporites (gypsum, rock salt, etc);
- carbonate rocks (limestones, dolostones, marbles …).
In the presence of solvent water:

- temperate or tropical areas, etc … (past or present).
In the presence of appropriate structural and textural conditions:

- secondary porosity (fissures, fractures, bedding planes ...);
- permeability (the capacity of transmitting water).

THE COMMON FACTOR: DISSOLUTION
In a sense all rocks are soluble in water
but
only some of them support, in certain
morpho-climatic conditions, the
establishment of typical hydrological
advantages and the development of
karst landforms:
- carbonate rocks
(composed of calcite, dolomite, etc …);
- evaporites
(composed of halite, gypsum, anhydrite,
etc…);
- quartzites or sandstones (dominantly
silica, or with a carbonate matrix).
Vertical beds in limestone, Sisteron, France
(photo J. De Waele)

SOLUBILITY OF MINERALS IN WATER
In the presence of small quantities of CO2 dissolved in water
(Pco2 = 0.001 bar), at temperatures of 25°C,
several minerals are more or less soluble:
- calcite: 60 mg/L
- dolomite: 50 mg/L
- quartz: 12 mg/L
- gypsum: 2400 mg/L
- halite: 360,000 mg/L

Frasassi Cave, Genga, Marche, Italy (photo J. De Waele)

SOLUBILITY OF MINERALS IN WATER
When Pco2 is much higher (0.1 bar), at the same temperature,

the solubility of carbonates increases significantly:
- calcite: 400 mg/L
- dolomite: 300 mg/L
whereas that of the

other minerals
hardly varies.
Tufa waterfall on the Verdon, France (photo J. De Waele)

THE KARST PROCESS AND EVAPORITES
The most important evaporite rocks from a karstic point of view are
gypsum and halite. Dissolution is direct, with the dissociation of the
salt in pure water, independent of the CO2 concentration.
Karst in both these rocks is described in greater detail in the lecture
on Karst in evaporite rocks.
Hypogean bend in Tanone Grande della Gacciolina Cave, Val di Secchia, Emilia Romagna, Italy (photo
M. Chiesi)

THE KARST PROCESS IN HALITE
At outcrop rock salt

deposits are so soluble
that they are normally
destroyed rapidly by
meteoric water.
Thus, karst in rock salt

is important, especially
in arid regions (such as
Mount Sedom, Israel
and Queshm Island,
Iran) or in salt mine
waste heaps (such as
at Cardona, Spain).
Collapse doline in a salt mine waste heap, Caltanissetta, Sicily, Italy (photo U. Sauro)

THE KARST PROCESS
AND GYPSUM
In contrast, gypsum
is commonly found
at outcrop and,
because of its high
solubility, it rapidly
exposes both surface
and subsurface karst
forms.
Cupola in the marly roof of the gypsum cave of Monte Conca, Sicily,
Italy (photo M. Vattano)

THE KARST PROCESS AND SILICEOUS ROCKS
Other rocks can display forms due to dissolution processes, such as the
siliceous rocks and the silicate rocks. Among the first are quartzites and
quartz sandstones; among the others are the granites.
Quartz dissolution is due to the

hydration process, in which SiO2
reacts with water (H2O) forming
silicic acid (H2SiO4), a soluble
substance.
The process affecting granites is

not true dissolution, but a form of
hydrolysis during which some
minerals (feldspars) alter by
reaction with water. The (clay
mineral) alteration products are
then easily removed by running The Auyantepuy plateau, Venezuela (photo Arch. La Venta)
water or by wind.
THE KARST PROCESS AND SILICEOUS ROCKS
Quartzite and quartz sandstone at
outcrop only develop dissolutional
features under favourable sets of
conditions. The affected rocks are
generally very old and have been
subjected to abundant rainfall at high
temperatures (hot tropical climate)
for long periods.
This type of karst is explained in

greater detail in the lecture
on Karst in quartzites.
Sima Auyantepuy Noroeste, Venezuela (photo Arch. La Venta)

THE KARST PROCESS IN
CARBONATE ROCKS
Carbonate rocks constitute the great majority of
soluble rocks at outcrop on the Earth’s surface.
1. about 12% of the Earth’s land surface is made up of carbonate

rocks (much more than gypsum, salt and quartzite);
2. about 25% of the Earth’s population lives on carbonate karst;
3. about 25% of mankind’s drinking water comes from carbonate
karst.
For all these reasons the karst process in carbonate rocks

is by far the most studied and best understood.
CARBONATE MINERALS
The main carbonate minerals are:
- calcite (CaCO3);
- aragonite (CaCO3);
- magnesite (MgCO3);
- dolomite (CaMg(CO3)2);
- siderite (FeCO3);
- ankerite (Ca (Mg,Fe)(CO3)2);
and others, less common:

- strontianite (SrCO3);
- kutnahorite (CaMn(CO3)2);
- witherite (BaCO3);
- rhodochrosite (MnCO3) etc... Scalenoedric calcite in a cave at Barega, Iglesias, Sardinia, Italy
(photo J. De Waele)
The present carbonate sediments generally consist of aragonite, calcite

and, to a lesser extent, dolomite.
CARBONATE MINERALS
Generally these minerals are divided in three groups based on their
crystalline structure:
- the calcite group (hexagonal) comprises calcite (CaCO3), magnesite

(MgCO3), siderite (FeCO3) and rhodochrosite (MnCO3);
- the dolomite group (hexagonal), characterized by two cations that

substitute each other in the crystalline structure, comprises dolomite
(CaMg(CO3)2), ankerite (Ca(Mg,Fe)(CO3)2) and kutnahorite
(CaMn(CO3)2);
- the aragonite group (orthorhombic) comprises aragonite (CaCO3),

strontianite (SrCO3) and witherite (BaCO3).

CLASSIFICATION
OF CARBONATE ROCKS
Limestones are sedimentary rocks that contain at least 50% of calcite
or calcium carbonate: limestones with more than 90% calcite almost
always contain caves and show
surface karst landforms.
Dolostones, in contrast, contain
the mineral dolomite in variable
amounts. There is a complete
series of rocks of intermediate
compositions, known broadly as
dolomitic limestones
One popular classification scheme

for carbonate rocks, proposed by
Leighton and Pendexter (1962),
is based on their percentages of
calcite, dolomite and impurities.

THE ROLE OF CO2
IN THE DISSOLUTION PROCESS
The solubility of calcite in pure water at 25°C is around 14 mg/L, which

is only slightly higher than the solubility of quartz in water (ca. 8 mg/L).
In nature the high solubility of carbonate rocks reflects the presence of

carbon dioxide (CO2) that, dissolved in water, forms carbonic acid
(H2CO3), which dissociates in turn, contributing to the acidity of the
solution with the production of protons (H+).
Carbon dioxide is present in the atmosphere and in the air trapped

inside the soil. Its concentration in a gas mixture is normally expressed
as the partial pressure of CO2 (in percent).

CARBON DIOXIDE (CO2) IN SOILS
The higher the partial pressure of CO2 in the air and at the air-water
interface, the more CO2 will be dissolved in the water.
Without any doubt the CO2 in a soil is the most important source of the
gas in terms of making percolating waters aggressive towards the
underlying carbonate rocks.
The quantity of CO2 in a soil depends on a series of factors:

- the porosity of the soil;
- the level of biological activity within the soil;
- the soil temperature;
- the presence of water in the soil;
- the soil thickness and hence the depth within it.

From these data it can
readily be deduced
that the amount of
CO2 in the soil depends
largely upon the nature
of the substratum and
of the soil itself, and
upon the prevailing
climate and season.
The biological activities

responsible for soil CO2
production are usually
most intense in well-
developed soils, and
especially in Horizon B.

The same biological activities are more intense at temperatures
between 20 and 65°C, and decrease at lower temperatures. CO2 is
thus produced within the soils especially during warm seasons,
becoming less important during cold ones. In the northern
hemisphere maximum concentrations of CO2 in cave air (or in the
epikarst) are reached during summer (July-September), whereas
minima correspond to the months from January to March.

GLOBAL DISTRIBUTION OF CO2 IN SOILS
Furthermore, decomposition processes decrease in soils that are too
dry; CO2 production is optimal at relative humidity values between 50
and 80%. In tropical areas Pco2 values can be very high (between
0.2 and 15%). Values in temperate areas generally range between
0.1 and 6%. In the arctic tundras, just as in the alpine meadows, the
values decrease and, during the short thawing season, they oscillate
between 0.2 and 1%.

CO2 IN THE AIR, SOIL AND CAVES
What are the values of carbon dioxide?
Air
around 0.038%
Soil
0.1-15%
(average 0.3-10%)
Cave
0.5-1%
(2-20 times more
than the average
CO2 concentrations
in the atmosphere!)

THE CHEMICAL REACTIONS OF CALCITE
(CaCO3) DISSOLUTION
CO2 (gas) ↔ CO2 (aq)
CO2 (aq) + H2O ↔ H2CO3
H2CO3 ↔ H+ + HCO 3
- CaCO3 + CO2 + H2O
- 2-
HCO 3 ↔ H+ + CO 3
- 2+ -
H2O ↔ H+ + OH Ca + 2HCO3
2+ 2-
CaCO3 ↔ Ca + CO3
These reactions are all influenced by the CO2 partial pressure,

by temperature and by the acidity or pH.
The underlined reaction is the slowest,

and its rate influences all the other reactions.
OPEN OR CLOSED SYSTEM?
A system is defined as open if all physical phases, solid, liquid and gas,
are free to react simultaneously.
In an ideal open system these conditions persist until thermodynamic
equilibrium is achieved
(for example: a pool on
limestone in a cave,
in contact with the cave air).
In contrast, in a closed
system only two phases
can interact in a certain
place simultaneously (for
example: a water droplet
not touching rock, or water
touching rock but not air in
saturated fissures). River and gours in San Giovanni Cave, Domusnovas, Sardinia, Italy
(photo J. De Waele)

OPEN SYSTEM
ROCK
AIR
-
H+ ↔ H2CO3 ↔ HCO3
CO2 (gas)
Ca2+ CaCO3
CO2 (aq) 2-
-
CO3
OH ↔ H2O ↔ H+
AQUEOUS SOLUTION
In an open system, molecules of CO2 react with water (H2O) and

transform into carbonic acid (H2CO3) that releases bicarbonate ions
(HCO3-) and protons (H+), and these are consumed through reaction
with calcium carbonate (CaCO3), creating molecules of bicarbonate
-
(HCO3 ) in solution. New CO2 molecules can pass from the air to the
solution, thus sustaining the entire process until thermodynamic
equilibrium is reached.

CLOSED AIR-WATER SYSTEMS
AIR
CO2 (gas)
H+ ↔ H2CO3 ↔
-
- HCO 3
OH ↔ H2O ↔ H+ Ca2+ 2-
CO3
AQUEOUS SOLUTION CO2 (aq)
In closed Air-Water systems the two phases interact until the solution
becomes saturated in CO2 and its derived products carbonic acid
H2CO3 and bicarbonate ions HCO3-.
When thermodynamic equilibrium is reached the concentrations
of the components undergo no further change.

CLOSED ROCK-WATER SYSTEMS
ROCK H+ ↔ H2CO3 ↔ HCO3
-
ROCK
Ca2+
CaCO3 CO2 (aq)
CaCO3
2-
CO3
-
OH ↔ H2O ↔ H+
AQUEOUS SOLUTION
In closed Rock-Water systems (e.g. a capillary fracture full of water)

the two phases interact until the solution consumes all of the CO2 and
its related products (carbonic acid H2CO3 and bicarbonate ions HCO3-)
through reaction with calcium carbonate (CaCO3).
Relative to open system conditions, where the CO2 that is consumed
is continuously replaced by new CO2 from the air, only 40 % as much
calcite will be dissolved.

THE CHEMICAL REACTIONS OF THE
CALCITE DISSOLUTION
CaCO3 + CO2 + H2O
2+ -
Ca + 2HCO3
To dissolve a molecule of
CaCO3 a molecule of CO2
in solution is consumed.
This makes the CO2 partial

pressure in the solution
decrease, leading to the
solution becoming saturated
with dissolved CaCO3.
Modified from Klimchouk et al., 2000

DISSOLUTION AND CO2: IS THAT ALL?
It is certainly true that high CO2 values increase the dissolving power of
water, but there are other factors that influence, more or less directly,
the solubility of carbonates in water.
These factors are:

- temperature;
- pressure;
- other acids (acid rain, organic acids, oxidation of sulphides, etc …);
- common ion effects;
- ionic forces;
- ionic coupling;
- mixing;
- presence of trace elements.

TEMPERATURE
With Pco2 =
0.03% at 25°C
55 mg/L of
CaCO3 are
dissolved in
water.
Lowering the
temperature
by 25°C this
value increases
to 75 mg/L.
This is due to the
fact that CO2 is
more soluble in
water at low
temperatures.
PRESSURE
An increase in
hydrostatic pressure
increases the solubility
of CO2 and
consequently of
carbonate in water.
This process is
important in the first
few hundred metres of
an aquifer, with
solubility increases of
around 6 mg/L for
every 100 metres of
water column.

PRESSURE AND CUPOLA
In caves that occasionally become flooded, air can remain trapped
and compressed in niches in the roof, leading to CO2 dissolution and
thus to an increase in aggressiveness of the water, with the possible
formation of a cupola and/or ceiling channels.
Cupola in the Revest Cave, France (photo P. Audra)

PRESSURE DECREASE IN RISING WATERS
The effect of the increase in
carbon dioxide solubility at
depth (at high pressure) is
very important, especially
with regard to hypogenic
CO2 of volcanic or tectonic
origin.
The combined effect of a
decrease in temperature
(the closer thermal water
rises to the surface) and the
decrease in pressure (with
release of CO2 bubbles that
immediately dissolve in the
water) can create zones of
enhanced aggressiveness in
the solutions.
Bubble trails in Santa Barbara 2 Cave, Iglesias, Sardinia, Italy
(photo J. De Waele)

SULPHURIC ACID
Another acid that can intervene in dissolution reactions is
sulphuric acid.
This acid can be produced by the oxidation of hydrogen sulphide,
commonly related to organic sources such as hydrocarbon deposits:
H2S + 2 O2  2 H+ + SO42-
Another possible way for sulphuric acid to be produced is by the

oxidation of sulphides such as pyrite within the rock:
2 FeS2 + 7 O2 + 2 H2O  2 Fe3+ + 4 SO42- + 4 H+
and
4Fe2+ + O2 + 10H2O  4Fe(OH)3 + 8H+

OTHER SOURCES OF ACID
Acids other than carbonic and sulphuric, like for example
hydrochloric acid (HCl), can occur in minor quantities locally:
CaCO3 + HCl Ca2+ + HCO3- + Cl-
Acidity can also derive from the oxidation of metals such as

manganese:
Mn2+ + ½O2 + H2O MnO2 + 2H+
Another potential acid source is the oxidation of carbonate

minerals such as siderite:
2 FeCO3 + ½O2 + 5 H2O 2 Fe(OH)3 + 2HCO3- + 2H+

THE COMMON ION EFFECT
Also known as
incongruent dissolution,
the common ion effect
occurs when two different
mineral components
introduce a common ion
to the solution (in this
case water).
This causes a decrease in

solubility of both minerals.

COMMON ION EFFECT
IN GYPSUM ROCKS
The classical example is the
dissolution of gypsum in
carbonate waters.
By dissolving more readily the
gypsum introduces Ca2+ ions into
the solution more quickly, thus
decreasing the solubility of the
carbonate (calcite, dolomite or
aragonite). This explains why
speleothems in gypsum caves are
commonly composed of calcite.
Speleothems in dolomite caves
are composed of calcite for the
same reason.
Calcite flowstone in Santa Ninfa Cave, Trapani, Sicily, Italy (photo M.
Vattano)

THE EFFECT OF IONIC STRENGTH
The introduction of ions such as Na+, K+ e Cl- into bicarbonate waters
decreases the ionic strengths of Ca2+, HCO3-, etc … causing an increase
in the solubility of carbonate minerals and of gypsum.
The effect is especially

evident when “fresh”
continental carbonate
water is mixed with a
brackish or salty water
(as in coastal areas).
Marine caves at Cala Luna, Dorgali, Sardinia, Italy (photo J. De Waele)

THE EFFECT OF IONIC COUPLING
Ionic forces related to the anions and cations present in a solution
cause the coupling of a certain number of the ions, while others
remain “free” in the solution. Coupled ions cause a decrease in the
activity of the ions and this leads to an increase in solubility.
The most common ion couples present in karst waters are:
CaHCO3+, CaCO30, MgHCO3+, MgCO30, CaSO40, MgSO40
The phenomenon becomes increasingly relevant in solutions that

reach concentrations of dissolved salts in excess of 100 mg/L.

THE MIXING EFFECT (OR BÖGLI EFFECT)
The mixing of two different
saturated solutions at the
same temperature creates a
new solution that will be
undersaturated at the same
temperature, and thus able
to dissolve more carbonate
rock.
Solution A
20 mg/L CO2 → 200 mg/l
CaCO3
Solution B
150 mg/L CO2 → 400 mg/l
CaCO3
Mix (Solution C)
85 mg/L → 300 mg/l
Able to dissolve around
40 mg of limestone!
THE EFFECT OF TRACE ELEMENTS
Theoretically the presence of small quantities of certain metals can

lower the solubility of calcium carbonate.
This appears to be due to the adsorption of these metals by calcite

in a position in which the dissolution of the carbonate would have
been easier, thus inhibiting the dissolution of the carbonate.
In general this effect, described under laboratory conditions at high

CO2 pressure (1 atm) and at relatively high metal concentrations
(some mg), has not yet been shown to be important in nature.
Ions that can have a slight influence on the solubility of calcite

appear to be phosphate (PO43+), Mn2+ e Mg2+.

INTENSITY OF KARST CORROSION
To evaluate the intensity
and thus the velocity of
karst evolution some
authors use the concept
of denudation rate
expressed in m3/km2 per
year or mm/1000 years.
This value depends upon

the climatic conditions
(rainfall, temperature,
evapo-transpiration) and
the CO2 partial pressure.
Karrentische under an erratic block, Berchtesgaden, Germany (photo L. Piccini)

The intensity of karst corrosion can be calculated on the basis of a
formula proposed by Marian Pulina:
Dm = 12.6 . (Cu – Ci) . Q . y

A
where:
Dm = denudation rate (mm/year)

Cu = average mineralization of the exiting water (rivers and/or springs) (mg/L)
Ci = average mineralization of the entering water (rain, allochthonous river,…)
(mg/L)
Q = average quantity of water leaving the karst area (L)
A = hydrographic drainage basin surface area (km2)
y = a variable, related to the climatic and environmental conditions (between
0.3-3, on average equal to 1)

The greatest values
are found in areas
with high rainfall,
e.g.
Norway 400 mm/ka
(where ka = 1000
years);
Papua New Guinea
450 mm/ka.
At our latitudes the

rate varies between
20-70 mm/ka, while
in areas with much
lower rainfall rates
can approach 0 (e.g.
7 mm/ka in Algeria).

TO KNOW MORE
KLIMCHOUK A.B., FORD D.C.,
PALMER A.N., DREYBRODT W.
(eds 2000), Speleogenesis
Evolution of Karst Aquifers,
National Speleological Society,
Huntsville Usa, 496 pp;
FORD D.C. & WILLIAMS P. (2007),
Karst Hydrogeology and
Geomorphology. John Wiley &
Sons, Chichester, 562 pp;
PICCINI L. (1999), Geomorfologia
e Speleogenesi carsica. Quaderno
didattico della Società Speleologica
Italiana n°1, 40 pp;
SAURO U. (1991), Morfologia
carsica. In: Castiglioni G.B.
Geomorfologia, Utet, 436 pp;
WHITE W.B. (1988),
Geomorphology and Hydrology
of Karst Terrains, Oxford University
Press, New York, 464 pp.
CREDITS
This lecture has been prepared by Jo De Waele
in collaboration with Paolo Forti, Leonardo Piccini and Ugo Sauro.
Translation to English by Jo De Waele and David J. Lowe.
Photographs were provided by Mauro Chiesi, Jo De Waele, Leonardo Piccini,

Ugo Sauro, Marco Vattano.
The pictures of Auyantepuy are from the Associazione di esplorazioni

geografiche “La Venta”.
The figures were prepared by Jo De Waele.
Special thanks to Mauro Kraus, Mario Parise and Maria Luisa Perissinotto
for their corrections and some useful suggestions.
© Società Speleologica Italiana
Any part of this presentation may be reproduced at your own responsibility, as long as the contents
remain unaltered.
If reproducing the presentation (or parts of it) you should acknowledge this project as the source of
the information.

04 DJL - KarstProcess

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

04 DJL - KarstProcess

Uploaded by

Copyright:

Available Formats

Teaching resources for

Speleology and Karst 2009

In collaboration with: Paolo Forti

The word Carso can be

The karst process – Società Speleologica Italiana 2009

In the presence of potentially soluble rocks:

In the presence of solvent water:

In the presence of appropriate structural and textural conditions:

The karst process – Società Speleologica Italiana 2009

The karst process – Società Speleologica Italiana 2009

- gypsum: 2400 mg/L

- halite: 360,000 mg/L

The karst process – Società Speleologica Italiana 2009

When Pco2 is much higher (0.1 bar), at the same temperature,

- calcite: 400 mg/L

- dolomite: 300 mg/L

whereas that of the

Tufa waterfall on the Verdon, France (photo J. De Waele)

The karst process – Società Speleologica Italiana 2009

The karst process – Società Speleologica Italiana 2009

At outcrop rock salt

Thus, karst in rock salt

The karst process – Società Speleologica Italiana 2009

The karst process – Società Speleologica Italiana 2009

Quartz dissolution is due to the

The process affecting granites is

This type of karst is explained in

Sima Auyantepuy Noroeste, Venezuela (photo Arch. La Venta)

The karst process – Società Speleologica Italiana 2009

1. about 12% of the Earth’s land surface is made up of carbonate

For all these reasons the karst process in carbonate rocks

and others, less common:

The present carbonate sediments generally consist of aragonite, calcite

- the calcite group (hexagonal) comprises calcite (CaCO3), magnesite

- the dolomite group (hexagonal), characterized by two cations that

- the aragonite group (orthorhombic) comprises aragonite (CaCO3),

The karst process – Società Speleologica Italiana 2009

One popular classification scheme

The karst process – Società Speleologica Italiana 2009

The solubility of calcite in pure water at 25°C is around 14 mg/L, which

In nature the high solubility of carbonate rocks reflects the presence of

Carbon dioxide is present in the atmosphere and in the air trapped

The karst process – Società Speleologica Italiana 2009

The quantity of CO2 in a soil depends on a series of factors:

The karst process – Società Speleologica Italiana 2009

The biological activities

The karst process – Società Speleologica Italiana 2009

The karst process – Società Speleologica Italiana 2009

The karst process – Società Speleologica Italiana 2009

The karst process – Società Speleologica Italiana 2009

These reactions are all influenced by the CO2 partial pressure,

The underlined reaction is the slowest,

The karst process – Società Speleologica Italiana 2009

In an open system, molecules of CO2 react with water (H2O) and

The karst process – Società Speleologica Italiana 2009

The karst process – Società Speleologica Italiana 2009

In closed Rock-Water systems (e.g. a capillary fracture full of water)

The karst process – Società Speleologica Italiana 2009

This makes the CO2 partial

The karst process – Società Speleologica Italiana 2009

These factors are:

The karst process – Società Speleologica Italiana 2009

The karst process – Società Speleologica Italiana 2009