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1. Details of Module

Subject Name Geology

Paper Name ECONOMIC GEOLOGY & MINERAL RESOURCES OF INDIA
Module Name/Title WALL ROCK ALTERATION
Module Id GEL-05-143
Pre-requisites Before learning this module, the users should be aware of
· Origin of orthomagmatic deposits.
· Genesis of igneous iron ore.
· Origin of pegmatites.
Objectives To understand:
· the mode of occurrence or orthomagmatic iron deposits associated
with intermediate to felsic volcanic rocks.
· the mode of occurrence of pegmatites, their mineral wealth, depth-
wise classification of pegmatites and diverse views on their origin.
Keywords Felsic magmatism, orthomagmatic deposits, pegmatites.

2. Structure of the Module-as Outline: Table of Contents only (topics covered with their sub-topics)

1. Introduction
2. Relationship between alteration, gangue and
mineralization
3. Rections between wall rock and fuids
4. Types of wall rock alteration and alteration 4.1 Advanced argillic alteration
assemblages
4.2 Sericilization
4.3 Intermediate argillic alteration
4.4 Propylitic alteration
4.5 Chloritization
4.6 Carbonatization
4.7 Potassic alteration
4.8 Silicification
4.9 Feldspathization
4.10 Toumalinization
4.11 Other alteration types
5. Influence of oter rock types
6. Correlation with type of ore minealization
7. Timinig of wall rock alteration
8. Distribution of alteration assemblages
9. An example of wall rock alteration
10. Summary

3.0 Development Team:

Role Name Affiliation

National Co-ordinator
Subject Co-ordinators
(e-mail:
epggeology640@gmail.com)
Paper Co-ordinator
Prof. M.S. Sethumadhav
Prof. D. Nagaraju
Prof. B. Suresh
Prof. M.S. Sethumadhav
Centre for Advanced Studies
Dept of Earth Science
University of Mysore,
Mysore-6
Centre for Advanced Studies

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Dept of Earth Science

Content Writer/Author(CW)
Content Reviewer (CR)
Prof. B. Krishna Rao
Prof. A. Balasubramaian
University of Mysore,
Mysore-6
Former Professor,
Department of studies in Geology,
University of Mysore,
Mysore-6
Centre for Advanced Studies
Dept of Earth Science
University of Mysore,
Mysore-6

Objectives

To understand

(a) the reactions between the wall rocks and ascending hydrothermal fluids,

(b) types of wall rock alterations associated with hydrothermal deposits

(c) influence of original rock type composition on wall rock alteration

(d) correlation of wall rock alteration with type of ore mineralization and

(e) distribution of wall rock alteration assemblage with different types of

hydrothermal deposits

TITLE: WALL-ROCK ALTERATION

1. INTRODUCTION

The country rocks that enclose ore deposits of hydrothermal origin almost always

show reaction effects that resut from the tendency of hot circulating fluids to equilibrate with

rocks flanking the conduits through which they move. Both the fluids and the rock adjust; the

conduits become lined with what amounts to a layer of insulation between fresh external rock

and the heated, commonly slightly acidic circulating solutions. That layer of “insulation” is

called wall-rock alteration, and the volume it occupies is the alteration zone, halo, envelope,

or selvage. Alteration effects may be visible for as little as a couple of grain widths beyond

vein wall, or they may extend for kilometres around a network of veins. Normally the

envelop around a vein of 1 or 2 m in width is on the order of 10 to 20 m, but many exceptions

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are noted. Some alteration is colourful and texturally and structurally flamboyant; elsewhere

it may be totally inconspicuous.

Many alteration halos show a zonation of mineral assemblages resulting from the

changing nature of the hydrothermal solution as it passed through the wall rocks. the

associated orebodies in certain deposits (e.g., porphyry-type copper deposits) may show a

special spatial relationship to the zoning.

There are two main divisions of wall rock alteration: hypogene and supergene.

Hypogene alteration is caused by ascending hydrothermal solutions and supergene alteration

by descending meteoric water reacting with previously mineralized ground. A third type

mechanism giving rise to the formation of wall rock alteration is the metamorphism of sulfide

orebodies. Studies on hypogene alteration are important because they (a) contribute to our

knowledge of the nature and evolution of ore-forming solutions, (b) are often valuable in

exploration, and (c) produce minerals such as phyllosilicates that can be used to obtain

radiometric dates on the wall rock alteration and, by influence, on the associated ore

mineralization.

The study of hydrothermal fluids has shown that they are commonly weakly acidic,

but may become neutral or slightly alkaline by reaction with wall rocks (or by mixing with

other waters, e.g., ground water). The solutions contain dissolved ions that are important in

ion exchange reactions, and the composition of a particular hydrothermal solution will have

an important bearing on the nature of the wall rock alteration it may give rise to. Since the

chemistry of wall rocks can also vary greatly according to their petrography, it is clear that

predictions as to the course of wall rock alteration reactions are fraught with difficulties.

Nevertheless, there is, despite of variety of controls, a considerable uniformity in the types of

wall rock alteration, which facilitates their study and classification. The controls of wall rock

alteration fall into two groups governed ore-forming fluids. Besides the chemistry of the host

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rocks, other factors of importance are their grain size, physical state (e.g., sheared or

unsheared) and permeability, and for the hydrothermal solution important properties are its

chemistry pH, Eh, pressure and temperature.

2. RELATIONSHIP BETWEEN ALTERATION, GANGUE AND MINERALIZATION

Alteration mechanisms normally are completely continuous with and a part of the

hydrothermal ore-forming process. Alteration is defined by any change in the mineralogical

composition of a rock brought about by physical or chemical means, especially by the action

of hydrothermal fluids. Alteration minerals can be considered as much the result of

mineralization processes as are the ore minerals themselves.

The nature of the alteration products depends upon (1) the character of the wall rock,

(2) the character of the invading fluid, which defines such factors as Eh, pH, vapour pressure

of various volatile species, anion – cation composition, the degree of hydrolysis, and (3) the

temperature and pressures at which the reaction take place. The alteration halos around many

deposits are more widespread and much easier to locate than the ore bodies within them. For

example, the copper ore body at Morenci, Arizona, is only 2 km2 in outcrop, but the readily

mappable alteration zones cover an area of 6 by 12 km, or 72 km2.

Alteration effects may reach old or present surfaces, or they may be “blind” and found

only in underground workings or in drill holes. Since 1970s, a great deal of work has been

done in attempting to determine the exact relationship between various types of ore deposits

and the alteration minerals that surround them. These studies focus on answering the

following aspects: what types of alteration products are associated with particular types of

ores? What changes are to be expected in the country rocks at various distances from the

orebodies? Where in the alteration halos are the ores most likely to be found? What

directional aspects can be discerned? What can be learned about mass transfer and the

geochemistry of the systems?

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Alteration may result from (1) diagenesis in sediments, (2) regional processes, such as

metamorphism, (3) post magmatic or post volcanic processes associated with cooling, and (4)

direct hydrothermal mineralization processes. For example, propylitization is the result of

low-temperature-pressure peripheral alteration around many orebodies, e.g., porphyry-type

Cu deposits. The propylite assemblage consists of epidote, chlorite, Mg-Fe-Ca carbonates,

and sometimes albite-orthoclase, all involved in partial replacement of wall-rock minerals.

The same assemblage can be produced by saussuritization of mafic to intermediate volcanic

rocks as a consequence of regional metamorphism of green schist facies. It can also be

produced during cooling history of basalt-andesite-dacite pile. Hence hydrothermal alteration

(surrounding ore deposits) can be confused with other phenomena, and vice versa. In such

cases, geochemistry can be extremely useful; for example, wherever bona fide hydrothermal

propylitization exists, anomalous values of 100 to 400 ppm Cu or Zn are common.

3. REACTIONS BETWEEN WALL ROCKS AND FLUIDS

During wall rock alteration process chemical gradients are most important whereas

temperature gradients are probably normally of secondary importance and pressure gradients

are only rarely significant. If it is accepted that chemical and thermal gradients are the

principal determinants of the type and extent of wall-rock alteration, and that hydrothermal

fluids are at least fundamentally similar, then the particular altered wall-rock mineral

assemblage (i.e., reaction products) must be largely governed by (1) the types of alteration

reactions that actually proceed, (2) wall-rock composition, (3) the pressure and temperature

of the environment.

Reactions that are important to alteration are of many types: (1) hydrolysis, (2)

hydration-dehydration, (3) alkali or alkali earth metasomatism, (4) decarbonation (5)

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silication, (6) desilication, (7) oxidation-reduction, and finally, a number of addition-removal

interactions such as carbonatization, desulfidation, sulfidation, and fluoritization.

Hydrolysis refers specifically to the involvement of H+. It is profoundly important

because hydrolysis of wall-rock minerals serves both to convert anhydrous silicates like the

feldspars to hydrolized silicates like the mica and clay minerals and to buffer the pH of the

fluid in turn affecting solubility and association – dissociation relationship in it. In reactions

of the following type

3KAlSi3O8 + 2H+(aq) ↔ KAl3Si3O10(OH)2 + 6SiO2 + 2K+(aq) --- 1

K-feldspar Muscovite Quartz

(Sericite) (Crystalline or

aqueous)

3NaAlSi3O8 + 2H+(aq) ↔ NaAl3Si3O10(OH)2 + 6SiO2 + 2Na+(aq) --- 2

Albite Paragonite Quartz

It is crucial to realize that the consumption of H+, to alter feldspar to muscovite,

affects the pH of the fluid and the degree of dissociation of hydrogen containing complexes

including molecular HCl. That in turn, by the common ion effect, affects the degree of

association of NaCl, KCl, and metal-chlorine complexes, and the solubility of metals in the

solution, so hydrolysis of feldspars is bound symbiotically to the transportation-deposition

characteristics of the fluid. This reaction shows how alteration and mineralization are so

interdependent. Reaction of metals with (HS)- to produce sulfides releases H+ such that

mineralization may actually cause alteration. Further, hydrolysis controls the progressive

alkali stripping of muscovite to kaolin by

2KAl3Si3O10(OH)2 + 2H+ ↔ 3Al2Si2O5(OH)4 + 2K+ ----------- 3

Sericite Kaolinite

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So it can be seen that the stability of feldspars, micas, and clays and the transfer from

rock-silicate into solution to K+, Na+, Ca2+, Mg2+ and other ions is controlled in large part by

hydrolysis. These reactions and the minerals involved are obviously an important key to the

interaction and mutual buffering of fluids and alumino-silicate wall rocks. The potassium,

sodium and calcium analogs function at the same time in the same system.

Hydration refers to removal of molecular water from a fluid into a mineral, and

dehydration to its addition to the fluid. Equation 1 to 3 (above) involves both hydrolysis and

hydration. A similar reaction important in seafloor alteration is

2Mg2SiO4 + 2H2O + 2H+ ↔ Mg3Si2O5(OH)4 + Mg+2 ----- 4

Olivine Serpentine

A more direct hydration seen in low-temperature alteration of hematite is

Fe2O3 + 3H2O ↔ 2Fe(OH)3 ----- 5

Hematite Goethite

Dehydration normally occurs as pressure or temperature increases around

alteration assemblages. An excellent example is as follows

Al2Si2O5(OH)4 + 2SiO2 ↔ Al2Si4O10(OH)2 + H2O ----- 6

Kaolinite Quartz Pyrophyllite

Alkali and alkali-earth metasomatism are also significant Magnesium

metasomatism, for example, may produce dolomite from limestone by

2CaCO3 + Mg+2 (aq) ↔ CaMg(CO3)2 + Ca+2 (aq) ------ 7

Calcite Dolomite

Or chlorite from k-feldspar in a rhyolite or arkose by

KAlSi3O8 + 6.5 Mg+2 + 10H2O ↔ Mg6.5(Si3Al)O10(OH)8 + K+ + 12H+ ----- 8

K-feldspar Chlorite

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Alkali metasomatism can either cause readjustment of feldspar compositions

by

KAlSi3O8 + Na+ ↔ NaAlSi3O8 + K+ ----- 9

K-feldspar albite

or result in overall increase in k-feldspar with or without sericite, albite with or

without paragonite or a halo of high Rb/K+ ratios, for example,

Decarbonation reactions are at the center of skarn formation, whereby silicates and

oxides are produced by the removal of CO2 from limestone-dolomite sections and the

recombination of components. They can be represented by

CaMg(CO3)2 + 2SiO2 ↔ (CaMg)Si2O6 + 2CO2 (gas) ----- 10

Dolomite Diopside

Or more simply by

MgCO3 ↔ MgO + CO2 (gas) ----- 11

Magnesite Periclase

Silicification and silication are also common reactions. Silicification refers to the

addition of silica as quartz or one of its polymorphs such as chalcedony, opal, or jasper, while

silication refers to the process of conversion to, or replacement by, silicate minerals:

silicification is addition or production of a quartz-family mineral, as in the silicification of

limestones

2CaCO3 (c) + SiO2 (aq) + 4H+ ↔ 2Ca+2 (aq) + 2CO2 + SiO2 (c) + 2H2O ----- 12

Calcite Quartz

Or as in the simple precipitation of silica in any pore space

SiO2 (aq) ↔ SiO2 ----- 13

Or as in the breakdown of the orthopyroxinebrozite

MgSiO3 + CO2 (aq) ↔ SiO2 + MgCO3 ----- 14

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bronzite quartz Magnesite

Silication occurs in contact metamorphism by such reactions as

CaCO3 + SiO2 ↔ CaSiO3 + CO2 (gas) ----- 15

Calcite Silica Wollastonite

and as equations 10 which describes silication to produce diopside from (dolomite +

quartz). Desilication-silicification occurs in many skarns according to

Ca3Fe2(SiO4)3 ↔ 3CaCO3 + Fe2O3 + 3SiO2 ----- 16

Garnet Calcite Hematite Quartz

Oxidation – reduction reactions most importantly affect ferrous-ferric iron and sulfur

mineralogies and complexes, but they also impinge upon systems containing Mn, V, U and

other redox pairs Two representative reactions are:

4Fe3O4 + O2 ↔ 6Fe2O3 ----- 17

Magnetite Hematite

and

2KFeAlSi3O10(OH)2 + O2 ↔ 2KAlSi3O8 + 2Fe3O4 + 2H2O ----- 18

Ferrous iron biotite k-feldspar Magnetite

(annite)

Sulfur ranges in valance from S+6 in sulfate radicals through zero in native sulfur (S0)

to S-2 in bisulfide ions (HS-), hydrogen sulfide (H2S) and many sulfide minerals. Traces of

native sulfur are found where sulfide minerals are oxidized to sulfates in the weathered

portions of ore deposits

Cu2S + 4Fe+3 + 6SO4= à 2Cu+2 + 4Fe+2 + 6SO4= + S0 ----- 19

Chalcocite native sulfur

The final reaction type involves sulfidation, fluoridation, and a host of additions and

substractions, such as

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2KFe3AlSi3O10 (OH)2 + 6S2 ↔ 2KAlSi3O8 + 6FeS2 + 2H2O + 3O2 (gas) ----- 20

Ferrous iron biotite (annite) K-feldspar pyrite

OH-mica + HF ↔ F-mica + H2O ----- 21

Hydroxy sericite Fluorosericite

During wall rock alteration, although most rock-forming minerals are susceptible to

attack by acid solution, carbonates, zeolites, feldspathoids and calcic plagioclase are least

resistant; pyroxenes, amphiboles and biotite are moderately resistant, and sodic plagioclase,

potash feldspar and muscovite are strongly resistant. Quartz is often entirely unaffected. As

wall rock alteration is in many cases a relatively rapid and incomplete geological process,

compared say with regional and contact metamorphism, some of these more resistant

minerals may persist as unstable relics in new assemblages more commonly than in the case

during metamorphism.

4. TYPES OF WALL ROCK ALTERATION AND ALTERATION ASSEMBLAGES

The common wall rock assemblages are displayed in Fig.1 (Fig. 3.7 Page 46, Evans)

using ACF and AKF diagrams, whose use is described in Best (1982), Winkler (1979) and

other text books on metamorphic petrology. Types of wall rock alteration have been

described by Meyer and Hemley (1967) and the Rose and Burt (1979) from whose work

much of the following is drawn.

4.1 Advanced argillic alteration

This alteration is characterized by Dickite, Kaolinite [both Al2Si2O5(OH)4]

Pyrophyllite [Al2Si4O10(OH)2] and quartz. Sericite is usually present and frequently alunite,

pyrite, tourmaline, topaz and zynyite. At high temperatures andalusite may be present. This is

one of the more intense forms of alteration, often present as an inner zone adjoining many

base metal vein or pipe deposits associated with acid plutonic rocks, as at Butte, Montana and

Cerro de Pasco in Peru. It is also found in hot spring environments and in telescoped shallow

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precious metal deposits. The associated sulfides of the orebodies are generally sulfur-rich;

covellite, digenite, pyrite and enargite are most common.

This alteration involves extreme leaching of bases (alkalis) from all aluminous phases

such as feldspars and micas, but is present only if aluminium is not appreciably mobilized.

When aluminium is also removed it grades into silicification and with increasing sericite, it

grades outwards into sericitization. The generation of advanced argillic alteration can be very

important in developing the high permeability necessary for the circulation of enormous

quantities of hydrothermal fluids and vein growth (Brimhall and Ghiorso 1983).

4.2 Sericitization

In orefields the world over this is one of the commonest types of alteration in

aluminium-rocks such as slates, granites etc. The dominant minerals are sericite and quartz,

pyrite often accompanying them. Here sericite is represented by muscovite. Muscovite is

stable over a wide pressure-temperature field and these accounts for its common occurrence

as an alteration mineral. If potassium is introduced into the wall rocks then rocks low in this

element, such as diorites, can be sericitized in significant amounts. During the sericitization

of granite, the feldspars and micas may be transformed to sericite, with secondary quartz as a

reaction by-product (see eq.1), but the primary quartz may be largely unaffected except for

the development of secondary fluid inclusions. Wall rock alteration is progressive, with some

minerals reacting ad being altered more rapidly than others. If shearing accompanies this, or

any of the other types of alteration carrying phyllosilicates, then a schistose rock may result,

otherwise hornfelsic-like textures develop.

With the appearance of secondary potash feldspar and/or secondary biotite,

sericitization grades into potassic alteration, which is very common in the central deeper

portions of porphyry copper deposits as at Bingham Canyon, Utah. In fluorine-rich

environments, topaz together with zunite and quartz may accompany the sericite to form

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greisen. Outside the sericitization zone lower grade intermediate argillic alteration may occur.

Thus sericitization may grade into three types of higher grade alteration and one of lower

grade.

4.3 Intermediate argillic alteration

Formerly known as argillic alteration and given its present name by Hemley and

Jones (1964) to avoid any confusion with advanced argillic alteration. The principal minerals

are Kaolinite-and Montmorillonite-group minerals occurring mainly as alteration products of

plagioclase. These may be accompanied by “amorphous clays (clays sensibly amorphous to

x-rays and commonly called allophone). The intermediate argillic zone may itself be zoned

with montmorillonite minerals dominant near the outer fringe of alteration and kaolin

minerals nearer the sericite zone. Sulfides are generally unimportant. Outwards from the

intermediate argillic alteration zone propylitic alteration may be present before fresh rock is

reached.

4.4 Propylitic alteration

This is a complex alteration generally characterized by chlorite, epidote, albite and

carbonate (calcite, dolomite or ankerite). Minor sericite, pyrite and magnetite may be present,

less commonly zeolites and montmorillonites. The propylitic alteration zone is often very

wide and therefore, when present, is a useful guide in mineral exploration. For example, at

Telluride, Colorado, narrow sericite zones along the veins are succeeded outwards by a wide

zone of propylilization.

4.5 Chloritization

Chlorite may be present alone or with quartz or tourmaline in very simple

assemblages; however, other porpylitic minerals are usually present, and anhydrite may also

be present. Hydrothermal chlorites often show a change in their Fe: Mg ratio with distance

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from the orebody, usually richer in iron adjacent to the sulfide veins, although the reverse has

been reported.

The development of secondary chlorite may result from the alteration of mafic

minerals already present in the country rocks or from the introduction of magnesium and

iron, though of course both processes can occur together, as at Ajo, Arizona. Chloritization is

common in alteration zones alongside tin veins in Cornwall (England).

4.6 Carbonatization

Dolamitization is common accompaniment of low to medium temperature ore

deposition in limestones, and dolomite is probably the commest of carbonates formed by

hydrothermal activity. Dolomitization is associated most commonly with low temperature,

lead-zinc deposits of “Mississippi Valley-type”. These can have wall rocks of pure dolomite;

usually this rock is coarser and lighter in colour than the surrounding limestone.

Dolomitization genererally appears to have preceded sulfide deposition, but the relationship

and timing have been much debated in the various ore districts where dolomitization occurs.

Nevertheless, dolomitization often appears to have preceded mineralization, to have increased

the permeability of the host limestones and thus to have prepared them (ground preparation)

for mineralization.

Other carbonates may be developed in silicate rocks, especially where iron is

available and ankerite may then be common, particularly in the calcium-iron environment of

carbonatized basic igneous rocks and volcanoclastics. This is particularly the case with many

Precambrian and Phanerozoic vein gold deposits, for example, Mother Lode in California,

where ankerite, sericite, albite, quartz, pyrite and arsenopyrite are well developed in the

altered wall rocks. At Larder Lake in Ontario, dolomite and ankerite have replaced large

masses of greenstone. As with the chlorites, there may be a chemical variation in the Fe:Mg

ratio with proximity to orebody.

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The chemical significance of carbonatization may take two different forms.

Dolomitization of limestone involves very extensive magnesium metasomatism, but only as a

base (K+, Na+, Ca+) exchange process. This is called cation metasomatism and in this case the

mineralizing (or premineralization) solutions must have carried abundant magnesium,

Carbonatization of silicate rocks involve inter alia anion metasomatism with the introduction

of CO32- rather than phases.

4.7 Potassic alteration

Secondary potash feldspar and/or biotite are the essential minerals of this alteration.

Clay minerals are absent but minor chlorite may be present. Anhydrite is often important

especially in porphyry copper deposits, e.g., El Salvador, Chile, and it can form up to 15% of

the altered rock. It is, however, easily hydrated and removed in solution, even at depths of up

to 1000m, so that it has probably been removed from many deposits by ground water

solution. Magnetite and hematite may be present and the common sulfides are pyrite,

molybdenite and chalcopyrite, i.e., there is intermediate sulfur: metal ratio.

4.8 Silicification

This involves an increase in the proportion of quartz or crypto-crystalline silica (i.e.,

cherty or opaline silica) in the altered rock. This silica may be introduced from the

hydrothermal solutions, as in the case of chertified limestones associated with lead-zinc-

flourite-baryte deposits, or it may be the by product of the alteraion of feldspars and other

minerals during the leaching of bases. Silicification is often a good guide to ore, e.g., the

Black Hills, Dakota. At the climax porphyry molybdenum deposits in Colorado, intensive

and widespread silicification accompanied the mineralization.

4.9 Feldspathisation

This is the term often applied when potassium or sodium metasomatism has produced

new potash feldspar or albite unaccompanied by the other alteration products characteristic of

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potassic alteration. Albilization is found adjacent to some gold deposits, often replacing

potash feldspar, e.g., Tread Well, Alaska.

4.10 Tourmalinization

This is associated with medium to high temperature deposits, e.g., many tin and some

gold veins have a strong development of tourmaline in the wall rocks and often in the veins

as well. The Sigma Gold Mine in Quebec has veins that in places are massive tourmaline and

this mineral is well developed in the adjacent wall rock. This is also the case in the

granodiorite wall rock of the Siscoe Mine, Quebec. At Llallagua, Bolivia, the world’s largest

primary tin mine, the porphyry host is altered to quartz-sericite-tourmaline rock.

If the altered country rocks are lime-rich then axinite rather than tourmaline may be

formed.

4.11 Other alteration types

There are many other types of alteration; among these may be mentioned

alunitization, which may be of either hypogene or supergene origin; pyritization, due to the

introduction of sulfur which may attack both iron oxides and mafic minerals; hematitization,

an alteration type often associated with uranium (particularly pitchblende deposits);

bleaching, due in many cases to the reduction of hematite; greisenization, a frequent form of

alteration along side tin-tungsten and beryllium deposits in granitic rocks or gneisses;

fenitization, which is associated with carbonatite hosted deposits and is characterized by the

development of nepheline, aegirine, sodic amphiboles and alkali feldspars in the aureoles of

the carbonatite masses; serpentinization, and the allied development of talc, can occur in both

ultrabasic rocks and limestones; it is associated with some gold and nickel deposits but where

serpentine and talc are developed in limestones there is generally an introduction of SiO2 and

H2O and frequently some Mg; finally zeolitization is marked by the development of stilbite,

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natrolite, heulandite, etc., and often accompanies native copper mineralization in

amygdaloidal basalts.

5. INFLUENCE OF ORIGINAL ROCK TYPES

A survey of world literature on the subject shows that wall rock alteration exhibits

certain regularity with respect to the nature of the host rock (Boyle 1970). There are of course

exceptions, but certain generalizations can be made. Thus, for example, the most prevalent

types of alteration in acidic rocks are sericitization, argillization, silicification and

pyritization. Intermediate and basic rocks generally show chloritization, carbonatization,

sericitization, pyritization and propylitization. In carbonate rocks the principal high

temperature alteration is skarnification, whereas normal shales; slates and schists are

frequently characterized by tourmalinization, especially when hosting tin the tungsten

deposits.

6. CORRELATION WITH TYPE OF MINERALIZATION

Boyle (1970) has shown that certain types of mineralization tend to be accompanied

by characteristic types of alteration. For example, Red bed uranium, vanadium, copper, lead

and silver deposits are generally accompanied by bleaching. Vein deposits of native silver are

usually characterized by carbonatization and chloritization and molybdenum bearing veins by

silicification and sericitization.

7. TIMING OF WALL ROCK ALTERATION

The problem of disentangling age relationships between different assemblages of wall

rock alteration minerals in a given deposit can be extremely difficult. Their presence, together

with evidence such as crustiform banding, has suggested by many workers that the

mineralizing solutions came in pulses of different compositions (polyascendant solutions). In

some deposits however, such as Butte, Montana, there is a considerable body of data

suggesting a single long-lasting phase of mineralization and accompanying alteration during

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the formation of the main stage veins. Both mechanisms have probably taken place and some

deposits may have been formed from monoascendant solutions whilst others are the result of

polyascendant mineralization (Meyer and Hemley 1967).

8. DISTRIBUTIONS OF ALTERATION ASSEMBLAGES

Alteration associated with magmatic deposits: Wall-rock alteration around magmatic

segregation and magmatic injection deposits generally inconspicuous and non-diagnostic.

Contacts between ore and wall rocks at most magmatic deposit areas are sharply defined

especially in injection-type deposits in which the magma was differentiated at depth prior to

emplacement in cold wall rocks. Wall-rock alteration around injection-type deposits is likely

to be very thin or absent; only rarely has the injection been accompanied by or followed by

hydrothermal activity. Minor hydration is described around the “offset” orebodies of the

Sudbury Complex in Ontario (Canada), but alteration effects around most magmatic deposits

are more aptly described as “regional metamorphism” than wall-rock alteration.

A special case is an assemblage called fenite, the result of a process called

fenitization, which occurs around most carbonatite intrusions. Fenitization is characterized by

the development of nephelene, aegirine, sodic amphiboles and alkali feldspars in the aureoles

of the carbonatite masses. These halos represent sodium metasomatism, hydrolysis, and

oxidation, with increased sodium, hydrous silicates, and hematite. They suggest that

hydrothermal activity may be important in generating some ores in carbonatiites.

Alteration associated with porphyry base metal deposits: Broadly the spatial arrangement of

alteration zones that is the fabric of porphyry base metal deposits is one of domal or coaxial

arrangement outward and upward from a deep core of potassic alteration, a shell of phyllic

merging outward to phyllic-argillic or argillic, and an outer zone of propylitic material.

Phyllic alteration in many districts is generally later and has “overprinted” an earlier lateral

continuum of potassic outward to propylitic. Early alteration is thus characterized more as

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alkali metasomatism with minor hydrolysis, with profound hydrolysis-hydration developed

later as part of the same sequence, amounting as it does to a retrograde collapse of thermal

gradients and invasion of meteoric waters.

Alteration associated with skarn deposits: Wall-rock alteration products associated with

skarn deposits around intrusive masses are extensive in many places and contain conspicuous

diagnostic minerals-grossularite and andradite granite, wollastonite, epidote, and pyroxenes

such as hedenbergite, salite and salites, amphiboles principally tremolite and actinolite ilvaite,

idocrase, minerals of humite group, serpentine, spinels, scapolite and many others. Both

silication and silicification are common. The character of the alteration products depends in

large part upon the invaded materials and to a lesser extent upon solution composition. For

example, the introduction of siliceous fluids into limestone oridinarily results in such

calcium-rich minerals as wollastonite and idocrase where as the invasion of the same fluid

into dolomites forms magnesium rich minerals, such as serpentine and diopside. The

following reactions illustrate possible reactions.

CaCO3 + SiO2 (aq) ↔ CaSiO3 + CO2 (gas)

Dolomite Wollastonite

CaMg(CO3)2 + SiO2 (aq) ↔ (CaMg)Si2O6

Diopside

Shales in igneous metamorphic zones tend to develop the characteristic fine-grained

sugary textures of hornfels. Locally, knots of chlorite, andalusite, garnet, or cordierite form,

and epidote may be abundant. Volcanic rocks undergo comparable alteration. For example,

the abundant andesites and andesitic tuffs of central and northern Chile contain conspicuous

epidote near intrusive masses. Carbonate rocks near intrusions are often thoroughly

metasomatized to skarn that consists of various silicate and oxide minerals.

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Alteration effects around contacts between igneous and sedimentary rocks range in

width from less than 1cm to several kilometres. In general, the more extensive the

metamorphic-metasomatic zone in a mineralized district, the more favourable the area is for

ore because heat and hydrothermal fluids have obviously penetrated the rocks. Contact zones

that are simply recrystallized and show no other metamorphic effects are said to be “dry” and

they seldom contain ore deposits.

Silication is abundant around skarn deposits. Shales, which are less permeable and

thus not as receptive to ore-bearing fluids, may be rendered hard and brittle by silication, and

more permeable upon subsequent fracturing. Silication of sedimentary sections is thus one

form of ground preparation, whereby soft, impermeable, and unfavourable rocks are made

more competent and more receptive to the ore fluids and to the deposition of ores.

Alteration associated with hydrothermal vein-type deposits: Cordilleran vein deposits refers

to fault-fissure-controlled lead-zinc-copper-mineralined vein deposits; such as Casapalca,

Peru; Superior, Arizona; the May flower mine in the Park city, Utah; and many others

thought to be related to nearby intrusive activity. Sericite is the most persistant and abundant

alteration mineral flanking Cordilleran vein deposits; carbonate minerals are also common,

especially calcite and dolomite. Siderite, rhodochrosite, and ankerite are conspicuous in

places. Chlorite, most characteristic of epithermal deposits, may also form around these

veins; it commonly develops outside the sericite envelops away from the ore. Silica is

generally present.

At Butte, Montana, it is considered that the alteration products were an integral part of

the ore mineralization, i.e., the alteration minerals were deposited at essentially the same time

and by the same fluids as the ore. Successive zones of sericitized, argillized, and porpylitized

quartz monzonite lie adjacent to every Main-stage ore-bearing fissure, regardless of its size,

attitude, ore mineralogy, or relative age. Sericite is found adjacent to the vein, and clay

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minerals are between the sericitized rock and fresh quartz monzonite. Nowhere does the

sericite zone grade directly into fresh wall rock. The sequence of alteration is even more

striking in detail. The argillic zone is invariably made up of a kaolinitic phase close to vein

and a montmorillonite-rich phase close to the unaltered wall rock. Further, the relative

proportions of chemical components change systematically from the vein outward, presenting

a graphic picture of the hydrothermal alteration process. The sodium, calcium, and silica

contents increases; a similar but less striking decrease is also shown by iron and magnesium.

These changes reflect the fact that outermost plagioclase was readily hydrolyzed, releasing

silica, calcium, and sodium, and that the ferromagnesian minerals were altered to chlorite.

Continued alteration leached iron, calcium and magnesium from the montmorillonite to form

kaolinite. Further hydrolysis finally broke down the orthoclase, supplying potassium for the

production of sericite. Sulfur content shows a marked increase near the vein; iron liberated by

the early destruction of ferromagnesian minerals combined with hydrothermally delivered

sulfur to form pyrite, and both iron and sulfur were added. Silica released from feldspars was

deposited as quartz near the vein. Thus there was a two-way transfer of ions by diffusion,

some ions moving into the wall rock and others moving toward the vein. As long as active

fluid circulation continued along the vein, each zone migrated away from the fissure, that is,

it grew at its outer edge and simultaneously was encroached upon by the next inner zone at its

veinward edge.

In alteration assemblage of limestone replacement ores jasperoid is commonly

encountered near veins. It may contain enough trace elements near ore occurrences to be a

useful exploration guide, but its mere presence is explorationally significant. Preore

dolomilization of limestone followed by the generation of granular “sandy dolomite is

common around dolomite-replacement Ag-Pb-Zn deposits at Gilman and Leadville,

Colorado.

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Lowering (1949) recognized 5 stages of sequential hydrothermal alteration in Pb-Zn-

Ag replacement deposits at Tintic, Utach. The stages are (1) an early barren stage, during

which limestones were dolomitized and volcanics were chloritized, (2) a midbarren stage,

characterized by argillization, (3) a late barren stage closely associated with the ore shoots

and characterized by jasperoid, baryte, pyrite and minor chlorite in the carbonate, quartzite

and shales, with allophone quartz, baryte, pyrite, calcite, and minor iron-rich chlorite in the

volcanics, (4) an early productive stage closely associated with ore bodies but consisting of

only an in conspicuous zone of sericite-quartz and pyrite, and (5) the productive stage, during

which ore was deposited with quartz, sericite and pyrite as products of wall rock alteration

Alteration associated with epithermal deposits: Epithermal precious metal “bonanza”

ore deposits are characterized by enormously high and extensive induced permeability along

fault and fracture zones. Alteration is commensurately broad, and complicated by the fact that

retrograde boiling zone can be identified in many ore districts. In general, a feldspar-stable

zone (adularia-albite assemblage) occurs at depth. In some ore districts it extends almost to

the surface. Alteration gradually flares upward and outward the surface, as structural opening

proliferates. Chlorite is one of the most abundant minerals in the wall rocks around

epithermal deposits in andesites, and in deposits such as the Comstock Lode, Nevada, the

enclosing rocks are extensively and pervasively chloritized to a propylitic assemblage.

Sericite is more abundant in latite and rhyolite wall rocks, but even here a thin propylite zone

may occur at the margins. In general, the more felsic the host rocks, the higher the overall

sericite-to-chlorite ratio. Other alteration minerals are quartz, alunite, zeolites, chalcedony,

opal, calcite and other carbonates along the veins. Argillization may be especially widespread

in the wall rocks. Among the numerous layer silicate minerals, nacrite, dickite, kaolinite,

pyrophyllite, elite, and montmorillonite may be present. Probably the most diagnostic

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minerals are the clays, pyrophyllite, sericite, and chlorite in the altered rocks, and quartz,

locally amethystine, opaline, or chalcedonic in the veins.

9. AN EXAMPLE OF WALL ROCK ALTERATION

Piroshco and Hodgson (1988) investigated the alteration beside auriferous quartz

veins of the Coniaurum Mine in the Porcupine Camp of eastern Ontario (Canada) (Fig.2)

(Fig. 3.8, Page 50 Evans). The authors recognised in the mafic metavolcanics that form the

wall rocks: (a) a least altered facies consisting of the regional greenschist metamorphic

mineral assemblage which, on approaching a vein gave way to (b) a chlorite facies, in which

the actinolite is replaced by chlorite; albite is progressively replaced by

calcite+quartz+chlorite; and clinozoisite disappears as sericite develops; (c) an ankerite facies

zone, in which the fresh rock takes on a bleached appearance, in contrast to the green colour

of the chlorite facies rocks; this colour change correlates with the appearance of ankerite as

the carbonate mineral and its considerable volumetric increase; there are concomitant

increases in quartz and sericite as the vein is approached and chlorite decreases; and (d) a

narrow zone occupied by the vein envelope facies. In the last named, chlorite is virtually

absent, sericite and quartz are prominent, ankerite appears to have a higher Mg:Fe ratio and

pyrite is significantly developed.

The mineral assemblages of the various zones can be considered as metamorphic

greenschist facies assemblages, which grew under the influence of different CO2

concentrations in the interstitial fluid. The mineral assemblage of the least altered facies had

the lowest CO2 concentration and the other assemblages grew in environments having

successively higher CO2 concentrations. Piroshco and Hodgson therefore concluded that the

zonation is the result of lateral gradients in XCO2, rather than temperature gradient.

10 SUMMARY

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à There are two categories of wall rock alteration: hypogene and supergene.

Hypogene alteration is caused by ascending hydrothermal fluids, and supergene alteration, by

descending meteoric water reacting with previously mineralized ground. A third type of

mechanism giving rise to the formation of wall rock alteration is the metamorphism of sulfide

deposits.

à Reactions that are important to wall rock alteration are of many types which

include (1) hydrolysis, (2) hydration – dehydration, (3) alkali or alkali earth metasomatism

(4) carbonatization – decarbonation, (5) silication – desilication (6) oxidation – reduction, and

a number of addition - removal interactions such as (7) sulfidation – desulfidation, (8)

fluoritization and (9) tourmalinization

à The following equations are typical examples of a few reactions involved during

wall rock alteration:

(a) Hydrolysis: 3KAlSi3O8 + 2H+(aq) ↔ KAl3Si3O10(OH)2 + 6SiO2 + 2K+(aq)

K-feldspar Muscovite Quartz

(b) Hydration: 2Mg2SiO4 + 2H2O + 2H+ ↔ Mg3Si2O5(OH)4 + Mg+2 (aq)

Olivine Serpentine

(c) Dehydration: Al2Si2O5(OH)4 + 2SiO2 ↔ Al2Si4O10(OH)2 + H2O

Kaolinite Pyrophyllite

(d) Silication: CaCO3 + SiO2 ↔ CaSiO3 + CO2 (gas)

Calcite Wollastonite

(e) Megnesium metasomatism: 2CaCO3 + Mg+2 (aq) ↔ (CaMg)(CO3)2 + Ca+2 (aq)

Calcite Dolomite

(f) Alkali metasomatism: KAlSi3O8 + Na+ ↔ NaAlSi3O8 + K+

k-feldspar albite

(g) Decarbonation: (CaMg)(CO3)2 + 2SiO2 ↔ (CaMg)Si2O6 + 2CO2 (gas)

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Dolomite Diopside

(10) Silication: CaCO3 + SiO2 (aq) ↔ CaSiO3 + CO2 (gas)

Calcite Wollastonite

(11) Oxidation: 4Fe3O4 + O2 ↔ 6Fe2O3

Magnetite Hematite

à Types of wall rock alteration include (1) advanced argillic alteration, (2)

sericitization, (3) intermediate argillic alteration, (4) propylitic alteration, (5) chloritization,

(6) Carbonatization, (7) Potassic alteration, (8) silicification, (9) feldspathisation, (10)

tourmalinization, (11) alunitization (12) pyritization, (13) bleaching, (14) serpentinization,

(15) zeolitization, (16) fenitization, (17) greisinization and (18) skarnification.

--- carbonatites often show imprints of fenitization

--- Porphyry type Cu deposits are characterized by significant presence of zones of

altertered wall rock which include zones of (a) potassic alteration, (b) phyllic alteration, (c)

argillic alteration and (d) propylitic alteration.

--- Dolomitization is a common accompaniment of low to medium temperature ore

deposition in limestones (e.g., lead-zinc deposits of “Mississippy Valley” type)

--- Wall rock alteration associated with vein-type hydrothermal deposits include

sericitization, carbonatization, chloritization and argillization.

----- O ----- O -----

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