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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.
1987) .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. (Bulletin of the American Association of Petroleum Geologists. M.
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) .
B. . under wet surface conditions: • Primary porosity = 20.9/sorting) • N. roundness. grain size only of secondary importance.Scherer 1987 • Assuming normal random packing in sands.91 + (22. sphericity.
.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.
• Ref: Houseknecht. in clean ssts.S. exported later.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. • Quartz cementation tends to be pre-pressure solution: Silica imported into the rock early in diagenesis. 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. .
g. evaporites) Percolating groundwater Expulsion from shales Mineral and organic reactions .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.
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. .
•quartz precipitates (low solubility) and slowly forms monocrystalline overgrowths •Other common cements: •Carbonates •Sulphates •Haematite •Clay minerals . silica: High levels of supersaturation. soluble forms precipitate • opal.e.g. chalcedony form thin crusts and mosaics on grains Low levels.
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. .
• quartz dust abraded during transportation – Later • Mainly pressure solution . • glass shards.Sources of cement • Silica – During early diagenesis: • skeletal remains of diatoms and radiolaria (amorphous silica).
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….
K-feldspar Albite .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.
Replacement of quartz • High depths of burial • Calcite replaces quartz in alkaline conditions of precipitation (quartz is more soluble in these conditions) .
g.Shallow burial replacement • Replacement can occur at shallow depths • E. surface weathering • Feldspar kaolinite (oxygen required) .
there is a regular sequence of cementation near surface: – Precipitation of silica cements. • In many cases. clay minerals and feldspars – Quartz continues to precipitate for a long period – Carbonates and sulphates precipitate .The Diagenetic Sequence • Succession of diagenetic events with increasing depth determined by the primary components available.
. water • Generally migrate through the most permeable units and fractures. • Hydrocarbons. • Sandstones = most permeable units. the evolve FLUIDS. gases.Remember this! • As rocks are buried.
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 .
+ Ca2+ • Assuming the dominant aqueous species is HCO3- . shrinkage.The development of Secondary Porosity • Secondary φ critical in oilfields • Fracturing. dissolution • Dissolution of carbonates very important • CaCO3 + H+ = HCO3.
• HCO3. Both are likely contributors .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.increases and the reaction favours precipitation – If pH not fixed • H2CO3 dissociates releasing H+ which decreases the pH. favouring dissolution of carbonate.
Section 2: Diagenetic Regimes .
Near surface sandstone diagenesis .
amphiboles etc) .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.
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.
• If grain had a clay rim. the hollow rim often remains visible in thin section.Intrastratal mineral dissolution • Partial or complete dissolution of instable minerals • Shows as solution pits on the grain surface • Occasionally. . whole grain is removed.
twin planes and ultimately the whole grain – Tend to be Mixed Layer Clays (see later)_ .Replacement • Minerals with a dominant cleavage: – Clays replace along the cleavage planes.
Al3+. Fe3+. Mg2+. Ca2+ • May migrate from system OR precipitate as new minerals • Commonest are: – – – – – – K-feldspar Zeolites Quartz Calcite M.C’s Iron minerals • Form growths in pore spaces and dissolution voids .Authigenic mineral growth • Dissolution of unstable minerals releases ions: • K+. Si4+.L.
Amphibole Pyroxene olivine .Special Case: Red Beds • A product of a more restricted form of near surface diagenesis • In this case. the unstables dissolved are Ferich silicates such as: – – – – biotite.
• Near surface: these release Fe3+
•reprecipitated on grain surfaces as haematite: hence the red colour
•Fe3+ reduces near surface to Fe2+
•Fe2+ can be incorporated into carbonates
•Ferroan calcite, ferroan dolomite, siderite (FeCO3)
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 • VLF’s illite ) smectite kaolinite (releases K+. e.g. authigenic illite . Si2+ for cements.
– Clays flatten to form a matrix: reduces permeability of the sedimentary rock.Result • Thus: – Any sand rich in feldspars and VLF’s generates a lot of clay generated in diagenesis. – Micas and mudstone clasts also flatten and deform to reduce permeability (bend around grains) .
Brief review of cements • Silica • Clays • Carbonates .
poor for reprecipitation. • Formation of quartz overgrowths inhibits pressure solution and help to preserve remnant porosity .Silica • Dissolution of quartz • Dissolution of feldspars • Clay transformation (Smectite Illite) • Reprecipitates as quartz overgrowths as long as the detrital quartz has NO CLAY COATINGS (nucleation problem) • NB Clays good for silica dissolution.
Clays • • • • • • • SiO2 tetrahaedra in sheet form Layers bound by OH-. Ca.s. Na. / Large surface area Surface charges cause coagulation/ dispersion Charge proportional to grain size Generally +ve at end points. Mg Base Exchange responsible for variations Small g. K. -ve on flat surfaces .
montmorillonite. when pore water becomes more alkaline kaolinite transforms to illite (K+ from waters required) . mixed layer clays (smectite-illite. chlorite) – Deeper levels • Illite and some chlorite – Acid conditions: Kaolinite predominates.Clays in sandstones • Common (90% ssts contain authigenic clays) • The commonest clays are: – Shallow depth: • Smectite.
g.What are mixed layer clays? • Interlayered clays • E. smectite-illite (S/I) clays • There is a sequence of development: • Progresses through increasing burial • Transformation begins at 70-100°C .
No K+ migration and no illite. Hydrocarbon emplacement has prevented illitization .The North Sea • Oil migration into ssts predates illite formation To convert Kaolinite to Illite : need K+ Pore space plugged with hydrocarbons Thus.
. solid at all other times.This imparts a Thixotropic property to clays: liquid when disturbed.
• Stage 2: To remove structural H2O – need 100°C+ (3km) – At this point H2O is removed and clay structure and chemistry is changed. only 30%vol H2O left: – Not free water: either crystal lattice water or adsorbed onto crystal surface. .Clay Diagenesis • Compaction: expulsion of fluids: mudrock is reduced to 10% original thickness. • Stage 1: by 1km burial.
.B. Temperature is the primary cause of clay mineral transformation.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.
Water loss from compacting mudrocks .
pyrophyllite replace clays •Illite & chlorite can survive .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.
Change in clay mineralogy of fine grained sediments through time • Lower Palaeozoics/ Pre-Cambrian dominated by illite & chlorite (more stable). surface weathering: reflected in a change of clay formation . • Upper Palaeozoic – present : wider mix of clays • Temporal variation also enhanced by: – Land plants: changed the soil forming process.
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 .
Note significant φ between layers .Poroperm • Kaolinite – Forms booklets – Greatly reduces porosity but spaces between layers allow flow: do not reduce permeability Kaolinite booklets in pore spaces of sandstone.
1. North Sea: c.9km .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.
Smooth fusing of edges distinguishes from chlorite .Poroperm • Smectite (montmorillonite) – Forms honeycombe structures – Some reduction of both porosity and permeability Typical authigenic smectite showing honeycombe structure.
. roseatte… – Some reduction of both porosity and permeability Commonest morphology for authigenic chlorite. Individual idiomorphic plate-like crystals. honeycombe.Poroperm • Chlorite – Many forms: platy.
Carbonate Diagenesis .
e clean quartzites) • Main cement responsible for φ and K reduction (fluid flow barriers) • Remember: Fine grained sediments release ionrich fluids (Ca2+.): reprecipitate as cement. • THUS: carbonate cements particularly common near sst/mst contacts.Carbonates • Very common cement in sandstones • Uncommon in quartzose sandstones (i.. Mg2+. HCO3. .
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. – Siderite: rare in a carbonate rock • Marine calcite: “high” Mg content (Ca90Mg10)CO3 . High Mg and Low Mg.
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 Corraline algae Halimeda Foraminifera Gastropods Corals Echinoidea Composition High Mg calcite Aragonite High Mg calcite Aragonite + Low Mg calcite Aragonite High Mg calcite ← Increasing micritization .
Ease of micritization probably related to size (echinoids: large plates) .
– Layering occurs – Beer bottles etc in cemented crust (probably mapping students) . Bermuda.Subsea cementation • Thought impossible until Ginsbruck & Shim found cemented material in coral reef a few hundred years old. 1970 • Persian Gulf: large areas of sea floor cemented 1-60m deep.
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 SOIL HUMIC ACID 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. Dissolution of fossils and cavities .e.
• 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 .
any atmospheric calcite δ C/δ O 13 18 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
W.L. show 30% thickness reduction due to stylolitization • This releases a lot of calcite for cementation .Measurements in the local U.
• 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 .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.
(c) a and c terminate (a) (b) .
– 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° .Triple Junctions • Boundary of 3 crystal faces.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 Fluvial sst Fluvio-deltaic Deep marine Shallow marine Generally high % quartz cement More clays More carbonate + quartz Quartz cement + zeolite cement 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 .
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. low birefringence. Birefringence. open matrix . colourless. mod. low reief • Illite KAl3Si3O10(OH)2 • Low relief.Main cements in sandstones • Pore-filling – Clays • Kaolinite Al2Si2O5(OH)4 • Colourless. pore filling.