Carbonate

Sedimentology
& Petrography
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

QAB2033
9. Carbonate Diagenesis
 Carbonate Minerals
• 3 main minerals:
– ARAGONITE: CaCO3, orthorhombic, brown to
colorless. Reacts to acid (HCl). Chemically
metastable
– CALCITE: CaCO3, rhombohedral, colorless to white.
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Reacts to acid (HCl). Chemically stable. CALCITE

Exists as Low-Magnesium (stable) and High-
Magnesium (metastable) varieties.
– DOLOMITE: CaMg(CO3)2, rhombohedral, white to
yellow. Does not react to HCl. Chemically stable.
 Carbonate Diagenesis
• “The diagenesis of carbonate sediments
encompasses all the processes which affect the
sediments after deposition until the realms of
incipient metamorphism at elevated
temperatures and pressures.”
• Diagenetic processes include:
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

– cementation
– micritisation
– neomorphism
– dissolution
– compaction / fracturing
– dolomitisation
 QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

carbonate rocks
Impact of diagenesis on porosity in

From Pierson 1982

 Relevance of Diagenetic Studies in
Reservoir Characterization
• Diagenesis often overprints the sedimentary architecture
and produces changes in Porosity and Permeability.
• Diagenesis changes the pore type, size and geometry,
affecting not only reservoir quality but also petrophysical
properties.
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

• The effects of diagenesis are commonly linked to the

depositional facies.
• To predict the effects of diagenesis on reservoir quality,
it is important to know where diagenetic processes
occur.
 Diagenetic Zones

Freshwater
Vadose
Lake Marine Vadose
Sea Level
Freshwater
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Phreatic
Little Circulation Active
Hydrothermal

Circulation

Marine Phreatic Deep

Deep Burial Marine
 Diagenetic Processes

Dissolution
Cementation
Karst
Lake
Sea Level
Cementation
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Dissolution
Cementation
Dolomitization Micritisation
Dissolution Cementation
Dolomitization Neomorphism Aragonite
Dissolution
Compaction
Fracturing
 Paragenesis
Relative time
Sedimentation
Acicular cement
Blocky cement
Early dissolution
Fracturing
Fracture calcite I Oil emplace-
Saddle Dolomite ment??
Stylolite form.
Fracturing
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Fracture calcite II
Fluorite
Sec. Porosity
Karst dissolution Eogenetic
geopetal infill Mesogenetic
Telogenetic
speleothem cem.
only in uplifted areas (exposure)
 Analytical Techniques
• Petrography:
– Polarizing microscope: mineral and crystal
shape identification (info on fluid
composition), paragenetic sequence
– Cathodo-luminescence: refine paragenetic
sequence, info on fluid chemistry
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

– Scanning Electron Microscope (SEM): Crystal

shape and surface, 3-D crystal distribution,
Refine paragenesis.
– Transmitted Electron Microscope (TEM)
– CT-Scan: Pore type, shape, geometry
 Staining Methods
• Cut and polish sample or thin section
• Etch (30 sec. in HCL) to obtain micro-relief
• Dip ½ in staining solution:
– Alizarine Red-S: Identify calcite and dolomite
– K-Ferrycyanide: Distinguish Fe-rich from Fe-poor
– Clayton Yellow: Identify High-Mg calcite
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Dolomite Calcite Fe-Dolo Fe-Calc

Alizarine Red-S - red - red
K-ferrycyanide - - blue blue
Aliz. + K-ferry. - red blue purple
deep blue
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Cathodo-luminescence
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Cathodo-luminescence
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Scanning Electron Microscope

QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

3-D visualisation of pore network

CT-Scan
 Analytical Techniques
• Geochemistry:
– X-Ray diffraction: mineral composition, grain
and cement chemistry.
– Atomic Absorption: quantitavie info on grain
and cement chemistry.
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

– Microprobe: Focused chemical composition.

– Mass Spectrometer: Stable isotope
composition. Info on fluid chemistry.
– Fluid inclusions analysis; fluid composition
 Diagenetic Processes

Dissolution
Cementation
Karst
Lake
Sea Level
Cementation
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Dissolution
Cementation
Dolomitization Micritisation
Dissolution Cementation
Dolomitization Neomorphism Aragonite
Dissolution
Compaction
Fracturing
 How fast does a marine cement form?
Cementation Experiment

AB
Lee Stocking Island AA
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

BB
 Cementation Experiment
Results Location BB, 100ft

8 months

original
20 months
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Marine Diagenesis
Shallow marine phreatic: Micritic Envelope
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Marine Diagenesis
Shallow marine phreatic: Micritic Envelope
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Marine Diagenesis
Shallow marine phreatic: Micritic Envelope
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Marine Diagenesis
Shallow marine phreatic: Micritic Envelope
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Types of carbonate cements

 Marine Diagenesis
Shallow marine phreatic: Aragonitic cement
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Coating of fibrous aragonite,

Holocene, Bahamas
 Marine Diagenesis
Shallow marine phreatic: Aragonitic cement
Aragonite needles growing in crystalline
continuity in a coral chamber,
Holocene, Bahamas
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
 Marine Diagenesis
Shallow marine phreatic: Aragonitic cement
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Aragonite crystals growing

as needles and as stubby crystals
Holocene, Bahamas
 Marine Diagenesis
Shallow marine phreatic: High-Mg calcite cement
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Rim of bladed High-Mg calcite cement

stained with Clayton Yellow,
Holocene, Bahamas
 Marine Diagenesis
Shallow marine phreatic: High-Mg calcite cement
Rim of bladed High-Mg calcite cement
stained with Clayton Yellow,
Holocene, Bahamas
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
 Freshwater Diagenetic Zones
KARST PROFILE

Upper
Dissolution, biological corrosion
Moon-milk deposits
Infiltration zone
Lower

Vadose
Percolation zone
Perched water-table
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Precipitation
Collapse Speleothems

Capillary fringe
Dissolution and Upper

After Scholle & James, 1999

hydraulic erosion Lenticular zone

Phreatic
Cave sediment
Increase hydrostatic pressure
Lower
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Freshwater Cements
 Freshwater Phreatic Cement:
Isopachous calcite
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Isopachous rims
of calcite cement.
Pleistocene, Bahamas
 Freshwater Phreatic Cement:
Dog-Tooth Calcite

Isopachous, dog-tooth
calcite cement,
Pleistocene, Bahamas
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
 Freshwater Phreatic Cement:
Syntaxial calcite
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Calcite cement grows

in optical continuity
with a crinoid fragment.
Jurassic, northern Italy.
 Freshwater Vadose Cement:
Meniscus calcitic cement

Meniscus calcitic cement (concentrated at

points of grain contacts) in Pleistocene dune
sediment, Bahamas
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
 Freshwater Vadose Cement:
Dog-Tooth Calcite

Dog-tooth calcite crystals cementing

carbonate grains. The crystals only
partially cover the grain surfaces.
Pleistocene, Bahamas
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
 Vadose Diagenesis: Karst
• Karst is the result of dissolution of carbonate
rocks by fresh water at the surface and in the
near-subsurface (vadose zone)
• Karst features comprise:
– Caves and channels
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

– Concretions (stalactites, stalagmites, etc.)

– Dolines
– Sinkholes
– Tower topography (Tower Karst)
– Calcrete crusts and horizons
 Karst Features: Caves
Limestone karst dissolution (left)
Is similar to ice melting (right)
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
 Karst Features: Caves
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Subterranean lake in a cave

Indicates aquifer level.
The ceiling of the cave is
covered with stalactites
 Karst Features: Concretions
Stalactites (growing downwards) and
stalagmites (growing upwards).

Large concretions in Kek Lok Thong Cave, Ipoh

QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
 Karst Features: Sinkholes

Blue hole on Long Island, Bahamas

QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Sinkhole in Guatemala
Ambergris Cay, Belize
 Blue Holes in the Bahamas
Large blue holes on Great Inagua, Bahamas

Onshore blue hole

500 m in diameter
Filled with sediments
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Offshore blue hole

300 m in diameter

1 Km
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Exploring a Submerged Cave

QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Exploring a Submerged Cave

 Karst Features: Tower Karst
Tower Karst in Ipoh

Tower karst near Phuket, Thailand

QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Tower Karst Hills in Guilin, China

 Vertical Shaft in Cave
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Vertical shaft in a deep cave

in Tennessee, USA
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Dissolution and collapse in a glacier

Dissolution and Collapse
 Dissolution and Collapse
Dissolution, collapse and concretions,
Iron Hoop Cave, Tennessee, USA
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Cave and Dissolution Notches

 Dissolution
Notches
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Multi-level dissolution notches,

Kinta Valley, Malaysia
 Karst Surface
Jagged peaks and pinnacles,
razor-sharp irregular rock surface
are typical features of karstified limestone
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Karst lansdcape in Langkawi Kilim Geopark, Malaysia

QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Sinkhole in the Ardennes, Belgium

Karst surface: Sinkhole
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Karst surface in Southern France

Karst Surface
 Karst Topography
Karst topography in the
Everglades, Florida
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Series of sinkholes, Kentucky, USA

 Mapping Karst Topography

1. LIDAR points after filtering 3. Contour lines generated from GRID

QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

2. GRID calculated from LIDAR points 4. Sinkholes identified from contour lines
 Dolomitization
• Transformation of calcite (CaCO3) into dolomite
(CaMg(CO3)2) by addition of Mg++
• Several theories are proposed to explain
dolomitization:
– Seawater:
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

• Evaporative
• Seepage-reflux
• Classical seawater
– Mixing zone
– Burial
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Models of Dolomitization
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Texture-Preserving Dolomite
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Texture-Destroying Dolomite
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Zoned Dolomite and Dedolomite

 Porosity in Dolomite
• Several origins proposed:
– evolution of density: theoretically, a given volume of
pure calcite (Ø = 10.0%) if transformed into pure
dolomite, will acquire Ø = 12.5% (dolomite is more
dense) - problem: only true in a closed system!
– porosity linked to density of nucleation: the more
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

intense the nucleation, the faster the crystal growth,

the smaller the preserved Ø ! Consistent with
observations: large crystals in reservoirs, no porosity
in microcrystalline dolomites
 Burial Diagenesis
• Compaction: At depths, the weight of the overburden
mechanically compacts sediments and rocks. Cemented
carbonates will form a solid framework that will decrease
the effects of compaction.
• Pressure-solution: The pressure applied to carbonate
rocks at depths will dissolve the rock along planes of
weakness, leaving seams of insolubles, called “stylolites”
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

• Fracturing: Cementation protects carbonates from

compaction but makes them less competent – more
brittle - and prone to fracturing. Fractures may remain
open but are commonly healed by calcite cement.
• Hydrothermal fluids will affect carbonates: dissolution,
dolomitization and mineral replacement will occur.
 Compaction
Compaction may result in grain dissolution
and interpenetration. Jurassic of N. Italy

Compaction may lead to grain

deformation and breaking. Jurassic of N. Italy
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson
 Pressure-solution
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Dissolution under high pressure

is immediately followed by
calcite precipitation

Stylolites represent interpenetration

of limestone layers and are typically
cm to dm in scale
 Fracturing
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Healed fractures in limestone,

Jurassic, Northern Italy

Fractured Upper Cretaceous Limestone

Oman Mountains
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Karstified faulted limestone

QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Faulted
Karstified

Limestone
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Hydrothermal Fluids

Baroque or “Saddle” dolomite

 Diagenetic Zones

Freshwater
Vadose
Lake Marine Vadose
Sea Level
Freshwater
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Phreatic
Little Circulation Active
Hydrothermal

Circulation

Marine Phreatic Deep

Deep Burial Marine
 Diagenetic Processes

Dissolution
Cementation
Karst
Lake
Sea Level
Cementation
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

Dissolution
Cementation
Dolomitization Micritisation
Dissolution Cementation
Dolomitization Neomorphism Aragonite
Dissolution
Compaction
Fracturing
 Carbonate Paragenesis:
Succession of diagenetic events
1. Marine cement:
Aragonite rim

5. Freshwater
phreatic
cement:
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

blocky
2. Vadose leaching: calcite
dissolution of
aragonitic particle
4. Vadose silt:
Infill of cavity

3. Freshwater cement:
calcitic rim
 Carbonate Paragenesis:
Succession of diagenetic events
1. Marine aragonitic
rim cement

3. Freshwater
Blocky calcite
cement
QAB2033 Carbonate Sedimentology & Petrography/Dr. Bernard Pierson

2. Compaction:
Spalling of ooids