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Clastic Diagenesis

Definition
Many definitions

The way in which a sediment adjusts to changing conditions


of increasing pressure (mechanical or chemical
compaction), increasing temperature, changing
composition of interstitial pore fluids (cementation and
compaction).

All occur during subsidence and burial.


General trend:
Compaction and cementation: earlier
Replacement: later
What processes play a role in
sandstone diagenesis?
• Original depositional environment
• Compaction
• Mineral reactions
• Diagenetic environment
• Fluid flow
• Organic matter evolution
• Precipitation, replacement and destruction of
cements
• Tectonic setting and basin evolution
• Etc……..
Why bother?
• Nature and distribution of porosity &
permeability determines extent of oil
recovery
• How will secondary recovery fluids interact
with the reservoir?
Section 1: Processes of
Diagenesis
Processes
• Physical
– Compaction
– Fluid migration
– Pressure solution
• Chemical
– Mineral reaction
– Mineral replacement
– Cementation
– Dissolution
• Physical and chemical processes are
interdependent and cannot be easily separated.
Effect of compaction & cementation
on primary porosity
• Reduction of bed thickness during
compaction reduces porosity (surprise!)
• Two ways to do this:

– Mechanical compaction
– Chemical compaction

Scherer, M. (Bulletin of the American


Association of Petroleum Geologists, 1987)
Mechanical Compaction
Mechanical compaction
• Occurs at shallow burial depths
(overburden).
– Graton & Fraser (1935):
– Tightest packing of spheres is rhombohaedral (26% φ)
» Loosest is cubic (48% φ)
– Most ssts= mix of shapes and sizes (not
therefore a true representation)
Scherer 1987
• Assuming normal random packing in sands,
under wet surface conditions:
• Primary porosity = 20.91 + (22.9/sorting)
• N.B. roundness, sphericity, grain size only
of secondary importance.
Mechanical compaction generally
more effective in mudrocks than
sandstones:

• shales have a higher H20 content than sandstones:


this is expelled rapidly by compaction.
Chemical compaction
Chemical compaction
• Mainly achieved by reprecipitation of
minerals in remaining pore spaces
• Cementation more obvious in coarse
clastics than mudrocks.
• Main process is pressure solution
Pressure Solution
• P3>P2>P1 > PW
– where PW = pore fluid
pressure
• Overgrowth forms (grey) by
diffusion of silica from the
grain contact to the pore
spaces.
Pressure Solution
• Development of sutured contact enhanced by
presence of clays: enhance transport of ions away
from site of pressure solution (diffusion network)
• Much more difficult to produce P.S. in clean ssts.
• Quartz cementation tends to be pre-pressure
solution: Silica imported into the rock early in
diagenesis; exported later.

• Ref: Houseknecht, 1988


Pressure solution
• Coarse clastics: high pressure contacts
• Fine clastics (sandstones): higher surface
area in contact: fewer nucleation sites

• Thus:
– Coarse clastics: rapid porosity loss early in
burial slowing down rapidly
– Fine clastics rapid porosity loss at depth.
Authigenic cementation
• Allogenic: during deposition
• Authigenic grown in situ during diagenesis

• Rarely sufficient material in the rock to account


for all cements present:
• Scavenges from fluids for cement formation:
– Connate saline water (seawater)
– Dissolution of soluble rocks (e.g. evaporites)
– Percolating groundwater
– Expulsion from shales
– Mineral and organic reactions
The effect of cementation on
porosity
• Fabric of the cement depends on how much
of the mineral was present in soluble form
at time of cementation: the degree of
supersaturation of the pore fluid.
e.g. silica:
High levels of supersaturation, soluble forms precipitate
• opal, chalcedony form thin crusts and mosaics on grains
Low levels,
•quartz precipitates (low solubility) and slowly forms
monocrystalline overgrowths

•Other common cements:


•Carbonates
•Sulphates
•Haematite
•Clay minerals
Determining relative timing of
cementation

• Calculate the Minus Cement Porosity


– High MCF = suggests early cementation
– Low MCF = suggests later cementation

Why? Because compaction continues until


stopped by cementation.
Sources of cement
• Silica
– During early diagenesis:
• skeletal remains of diatoms and radiolaria
(amorphous silica),
• glass shards,
• quartz dust abraded during transportation
– Later
• Mainly pressure solution
Sources of cement
• Carbonate
– Dissolution of shelly material in sediments
– Dissolution of nearby limestones
Sources of cement
• Sulphates
– Primarily from evaporites
– Usually find sulphate cements near these
• Gypsum
• Anhydrite
• Halite
• Barytes
• Celestite etc….
Replacement during diagenesis
• Mainly a later occurrence: deep burial
• Pseudomorphs form (shape preserved)
• Termed alteration when the replacement
mineral was part of the original mineral
• E.g. K-feldspar Æ Albite
Replacement of quartz
• High depths of burial
• Calcite replaces quartz in alkaline
conditions of precipitation (quartz is more
soluble in these conditions)
Shallow burial replacement
• Replacement can occur at shallow depths
• E.g. surface weathering
• Feldspar Æ kaolinite (oxygen required)
The Diagenetic Sequence
• Succession of diagenetic events with increasing
depth determined by the primary components
available.
• In many cases, there is a regular sequence of
cementation near surface:
– Precipitation of silica cements, clay minerals and
feldspars
– Quartz continues to precipitate for a long period
– Carbonates and sulphates precipitate
Remember this!
• As rocks are buried, the evolve FLUIDS.
• Hydrocarbons, gases, water

• Generally migrate through the most


permeable units and fractures.
• Sandstones = most permeable units.
Porosity Loss
Enhancement of Porosity Loss
• Increasing temperature (increasing
geothermal gradient accelerates diagenetic
alteration)
• Increasing pressure
• Amount of fluid flow
• Amount of matrix present
Porosity Gain
The development of Secondary
Porosity
• Secondary φ critical in oilfields
• Fracturing, shrinkage, dissolution
• Dissolution of carbonates very important

• CaCO3 + H+ = HCO3- + Ca2+


• Assuming the dominant aqueous species is
HCO3-
Dissolution of carbonate
• Two possibilities
– Organic/ inorganic diagenesis produces CO2
– If pH fixed by mineral reactions (organics also) with
fluid
• CO2 generates H2CO3 which dissociates, lowering the pH.
• HCO3- increases and the reaction favours precipitation
– If pH not fixed
• H2CO3 dissociates releasing H+ which decreases the pH,
favouring dissolution of carbonate.
Both are likely contributors
Section 2: Diagenetic Regimes
Near surface sandstone
diagenesis
Near surface sandstone
diagenesis
• Particularly occurs in semi-arid climates
– Water table very low
– Sediments are oxygenated for long period
– Sparse vegetation : rapid erosion
– Produces an immature sediment
• Large amount unstable minerals (feldspars,
amphiboles etc)
Processes active near surface
• Clay infiltration
• Intrastratal mineral dissolution
• Replacement
• Authigenic mineral growth
Clay Infiltration
• Sand near surface suffers a flood event:
– Water is full of wash-load clays
– These percolate through the sand and deposit
on grain surfaces
– Clay plates arrange tangentially to the grain
surface
– Produces a matrix-supported sediment: can
look like a debris flow, which it is not.
Intrastratal mineral dissolution
• Partial or complete dissolution of instable
minerals
• Shows as solution pits on the grain surface
• Occasionally, whole grain is removed.
• If grain had a clay rim, the hollow rim often
remains visible in thin section.
Replacement
• Minerals with a dominant cleavage:
– Clays replace along the cleavage planes, twin
planes and ultimately the whole grain
– Tend to be Mixed Layer Clays (see later)_
Authigenic mineral growth
• Dissolution of unstable minerals releases ions:
• K+, Fe3+, Mg2+, Si4+, Al3+, Ca2+
• May migrate from system OR precipitate as new
minerals
• Commonest are:
– K-feldspar
– Zeolites
– Quartz
– Calcite
– M.L.C’s
– Iron minerals
• Form growths in pore spaces and dissolution voids
Special Case: Red Beds
• A product of a more restricted form of near
surface diagenesis
• In this case, the unstables dissolved are Fe-
rich silicates such as:
– biotite,
– Amphibole
– Pyroxene
– olivine
• Near surface: these release Fe3+
•reprecipitated on grain surfaces as haematite: hence the
red colour

•Fe3+ reduces near surface to Fe2+


•More mobile

•Fe2+ can be incorporated into carbonates


•Ferroan calcite, ferroan dolomite, siderite (FeCO3)

•Also clays
•Chlorite, smectite
Timing of reprecipitation is
important:
• First mineral to form = limonite (yellow)
which matures to become crystalline
haematite Fe2O3
• Once formed, red colour may be leached
by later fluids unless protected from
further diagenesis: best is quartz
overgrowths.
Aeolian Red Beds
• Infiltration of wind-blown dust (mainly
siliceous but contains iron oxides)
• A lot of fine silica abrasion dust is
generated in deserts:
– Good source of silica for precipitation of
protective quartz overgrowths.
Subsurface sandstone diagenesis
Subsurface sandstone diagenesis
• Sand horizons: fluid pathways especially for
fluids from compacting mudstones
• Fluids carry dissolved ions (cements)
• The compacting sands can be a long distance
from shales (10’s of km)
As sand compacts…

• Some grains particularly susceptible to


alteration by dissolution in acid waters:
feldspars and volcanic lithic fragments
(VLF’s)

• Feldspar Æ illite Æ kaolinite (releases K+, Si2+ for


cements, e.g. authigenic illite)

• VLF’s Æ smectite
Result
• Thus:
– Any sand rich in feldspars and VLF’s generates
a lot of clay generated in diagenesis.
– Clays flatten to form a matrix: reduces
permeability of the sedimentary rock.
– Micas and mudstone clasts also flatten and
deform to reduce permeability (bend around
grains)
Brief review of cements
• Silica
• Clays
• Carbonates
Silica
• Dissolution of quartz
• Dissolution of feldspars
• Clay transformation (Smectite Æ Illite)

• Reprecipitates as quartz overgrowths as long as


the detrital quartz has NO CLAY COATINGS
(nucleation problem)
• NB Clays good for silica dissolution; poor for
reprecipitation.
• Formation of quartz overgrowths inhibits pressure
solution and help to preserve remnant porosity
Clays
• SiO2 tetrahaedra in sheet form
• Layers bound by OH-, Na, K, Ca, Mg
• Base Exchange responsible for variations
• Small g.s. / Large surface area
• Surface charges cause coagulation/ dispersion
• Charge proportional to grain size
• Generally +ve at end points, -ve on flat surfaces
Clays in sandstones
• Common (90% ssts contain authigenic clays)
• The commonest clays are:
– Shallow depth:
• Smectite, montmorillonite, mixed layer clays (smectite-illite,
chlorite)
– Deeper levels
• Illite and some chlorite
– Acid conditions: Kaolinite predominates, when pore
water becomes more alkaline kaolinite transforms to
illite (K+ from waters required)
What are mixed layer clays?
• Interlayered clays
• E.g. smectite-illite (S/I) clays
• There is a sequence of development:

• Progresses through increasing burial


• Transformation begins at 70-100°C
The North Sea
• Oil migration into ssts predates illite
formation
To convert Kaolinite to Illite : need K+
Pore space plugged with hydrocarbons
Thus, No K+ migration and no illite.
Hydrocarbon emplacement has
prevented illitization
This imparts a Thixotropic
property to clays: liquid when
disturbed, solid at all other
times.
Clay Diagenesis
• Compaction: expulsion of fluids: mudrock is
reduced to 10% original thickness.
• Stage 1: by 1km burial, only 30%vol H2O left:
– Not free water: either crystal lattice water or adsorbed
onto crystal surface.
• Stage 2: To remove structural H2O – need 100°C+
(3km)
– At this point H2O is removed and clay structure and
chemistry is changed.
Clay diagenesis
• Stage 3: Last H2O removed @ 150°C (even
then a little remains: only sustained deep
burial removes the last of the water
N.B. Temperature is the primary cause of
clay mineral transformation.
Water loss from
compacting
mudrocks
Changes of clay minerals with
increasing depth of burial and
into metamorphism.

•Illite: no conversion but becomes


more crystalline with burial
•Subvarieties of kaolinite convert to
illite & chlorite with burial
•Phyllosilicates replace clay minerals
during metamorphism:
•Laumontite, pyrophyllite replace clays
•Illite & chlorite can survive
Change in clay mineralogy of fine
grained sediments through time
• Lower Palaeozoics/ Pre-Cambrian
dominated by illite & chlorite (more stable).
• Upper Palaeozoic – present : wider mix of
clays
• Temporal variation also enhanced by:
– Land plants: changed the soil forming process,
surface weathering: reflected in a change of
clay formation
So why study clays?
• Give a good overview of thermal alteration
in a basin
• Illite crystallinity measurements: main tool
for thermal examination
• Clays in pores very important in assessment
of poroperm characterisation of sandstones
Poroperm
• Kaolinite
– Forms booklets
– Greatly reduces
porosity but
spaces between
layers allow flow:
do not reduce
permeability

Kaolinite booklets in pore spaces of


sandstone. Note significant φ between
layers
Poroperm

• Illite
– Forms hair-like
threads
– Low overall
volume: porosity
not reduced much
– Form matted webs:
permeability
reduced
Authigenic illite cement in Lower
Permian Rotliegendes sandstone,
North Sea: c. 1.9km
Poroperm

• Smectite
(montmorillonite)
– Forms honeycombe
structures
– Some reduction of
both porosity and
permeability

Typical authigenic smectite showing


honeycombe structure. Smooth fusing of
edges distinguishes from chlorite
Poroperm
• Chlorite
– Many forms:
platy,
honeycombe,
roseatte…
– Some reduction
of both porosity
and permeability

Commonest morphology for authigenic


chlorite. Individual idiomorphic plate-like
crystals.
Carbonate Diagenesis
Carbonates
• Very common cement in sandstones
• Uncommon in quartzose sandstones (i.e clean
quartzites)
• Main cement responsible for φ and K reduction
(fluid flow barriers)

• Remember: Fine grained sediments release ion-


rich fluids (Ca2+, Mg2+,, HCO3- ): reprecipitate as
cement.
• THUS: carbonate cements particularly common
near sst/mst contacts.
Carbonates
• Carbonates are more soluble than silicates:
diagenetic fabrics generally more complex
– Aragonite: very unstable
– Dolomite: CaMg(CO3)2: termed Ankerite when Fe-rich
– Calcite: ferroan and non-ferroan, High Mg and Low
Mg.
– Siderite: rare in a carbonate rock
• Marine calcite: “high” Mg content (Ca90Mg10)CO3
Non-skeletal grains
• Ooids (high wave energy environment)
• Peloids
• Oncoliths (aggregates of debris)
Lime muds (micrite)
• Origin:
– Chemical precipitate
– Disaggregation of shells
– Microbial/ bacterial micritization
Environments of Carbonate
diagenesis
• Subsea
• Subaerial
• Subsurface
(a) Subsea diagenesis: carbonates
• By far the most important process in subsea
diagenesis:
• Micritization of shells.
• A number of mechanisms are suggested for
this
Physical breakdown of material
• Unlikely:
• Tendency would be to recrystallize rather
than break down
Algal action (Bathurst)
• Small-scale borings in shell surface filled
by micrite
• Therefore the action of alga builds up a
“micrite envelope”
Bacterial action (Purdy)
• Algae aren’t present in areas where
micritization is identified most (10-15 cm
under surface)
• Hence bacterial breakdown of shelly
material is more likely
• Micritization is known to happen early in burial (2-300yr
after settling)
• Almost all skeletal material undergoes this to some degree
• No connection between composition and degree of
micritization

Material Composition
← Increasing micritization
Corraline algae High Mg calcite

Halimeda Aragonite

Foraminifera High Mg calcite


Gastropods Aragonite + Low Mg calcite

Corals Aragonite

Echinoidea High Mg calcite


Ease of micritization probably
related to size (echinoids: large
plates)
Subsea cementation
• Thought impossible until Ginsbruck &
Shim found cemented material in coral reef
a few hundred years old. Bermuda, 1970
• Persian Gulf: large areas of sea floor
cemented 1-60m deep.
– Layering occurs
– Beer bottles etc in cemented crust (probably
mapping students)
Main cement: aragonite – acicular crystals in porosity
Also: High Mg calcite – blocky crystals
Problem: The sea here is saturated with
aragonite, why does Mg calcite
precipitate?
• Most likely: aragonite → calcite conversion
– Aragonite: tighter lattice – conversion would
release 8% CaCO3 to maintain volume
• Hard limestone crusts are buckled:
supporting evidence for volume increase

Aragonite → High Mg Calcite + 8% CaCO3


Different classes of cement
occur: can be used to map
environments

• Shallow Marine
• Supertidal
– Phreatic environment
– Vadose environment
Shallow Marine cementation
• Forms ISOPACHOUS/ SYNTAXIAL CEMENT
– Crystals have same orientation as fossil on which they
grow

• Common in crinoids, resulting in:

single calcite crystal


Supertidal Phreatic
• Below the water table
• MENISCUS CEMENT
Supertidal Vadose
• Above the water table
• MICROSTALACTITIC CEMENT

droplets of cement
Concretions
• Carbonate concretions common in shales
• Form before compaction (bedding visible within
them)
• Oriented parallel to bedding
• Uncertain origin:
– Organic material common in concretions
– Disintegration produces alkaline conditions locally
(NH3) decreasing CaCO3 solubility
– No depletion of CaCO3 ever demonstrated around
concretions: dubious theory
(b) Subaerial carbonate
diagenesis
• Second largest area of carbonate diagenesis
• Most important process is cementation
• Occurs when calcareous muds elevate
above water and meteoric waters attack it
METEORIC WATER

HUMIC ACID
SOIL

CALCAREOUS
MUD

Meteoric H2O collects humic acid in soil zone


Humic acid dissolves CaCO3 in mud zone
High Mg CaCO3 and aragonite preferentially removed

i.e. Dissolution of fossils and cavities


• Low Mg becomes saturated in the meteoric fluids:
• Replaces High Mg calcite and aragonite
• Thus: any ascending water in dry periods will be Low
Mg calcite-rich
– causes deposition of low Mg calcite at higher levels
at later stages
Distinguishing subaerial and
subsurface cementation
• Isotopic analysis
• 13C/12C and 18O/16O ratios (δ13C , δ18O)
• Plots of such data are now more refined
– Allow distinction between marine/ non-marine
environments
– Depth of water
δ C/δ O any atmospheric calcite
18
13

deep sea carbonates

13
C
(c) Subsurface cementation and
diagenesis
• Absolute mechanisms not fully understood
• Cementation occurs continuously: new term
applied – Lithification: production of a solid
limestone with no porosity
• However:
– Modern lst muds have 40 – 70% φ whilst lsts
never have >5%
– Cannot be blamed on compaction (delicate
fossils preserved)
– Where does the CaCO3 come from to close the
space?
Pressure Solution and
Stylolitization
• P.S. is a popular choice for pore closure
– Any strained part of a crystal becomes highly soluble:
– CaCO3 migrates to areas of lower energy
• Stylolites: impurities in the lsts along a layer
become stress razors (pressure points)
– Interpenetration occurs (see graphic next)
– Definitely a solution phenomenon since stylolites can
cut fossils
– Material dissolved is a calcite source
Measurements in the local U.W.L. show 30%
thickness reduction due to stylolitization

• This releases a lot of calcite for cementation


Recrystallization/ Neomorphism
• Change in crystal shape/ orientation without
compositional change
• The orientation of the first (seed) crystal govern
the direction in which further crystals grow.
• The calcite scalenohaedral phase is the fastest
growing
• Upright axes survive in most cases so most pore
filling calcite crystals have c-axis normal to
surface
(c)

a and c terminate

(b)
(a)
Triple Junctions
• Boundary of 3 crystal faces.

– Most common angle of contact is 180° in


cements

– Commonly, one crystal terminates by growing


into another stops

– Most common angle in recrystallized crystals is


120° - more stable due to reduced surface angles
Patterns in Clastic Diagenesis
Quartz cements
• Timing is temperature controlled
• Can be as low as 80°C – thus the presence
of qtz cement infers temps in excess of this
Common environment cement
characteristics
Aeolian sst Generally high % quartz cement

Fluvial sst More clays

Fluvio-deltaic More carbonate + quartz

Deep marine Quartz cement + zeolite cement

Shallow marine Quartz dominated


Main cements in sandstones
• Pore coating
– Quartz
• low birefringence
• No cleavage
• Clear/ colourless
• Optically continuous with substrate
• euhedral
Main cements in sandstones
• Pore-filling
– Carbonate
• Calcite
– Usually early
– Usually fills porosity completely
– Calcrete: terrestrial cementation – fills porosity and
corrodes silicates
• Dolomite
– Fe dolomite: typically forms rhombs
– Fe calcite
– Siderite: typically smaller brown rhombs
Main cements in sandstones
• Pore-filling
– Clays
• Kaolinite Al2Si2O5(OH)4
• Colourless, low birefringence, low reief
• Illite KAl3Si3O10(OH)2
• Low relief, mod. Birefringence, colourless,
fringe-structure
• Chlorite-smectite: solid solution series
• (MgFeAl)(AlSi)O10(OH)4 –(NaKCa)(MgFeAl)(SiAl)O10(OH)8
• Chlorite: greenish fringe
• Smectite: colourless to greenish, pore filling,
open matrix