OXIDATION AND SUPERGENE

ENRICHMENT

PROJECT REPORT SUBMITTED FOR THE

PARTIAL FULFILLEMENT OF B.Sc
(HONS.) IN GEOLOGY UNDER
SAMBALPUR UNIVERSITY.

DEPT.OF GEOLOGY
GOVT.COLLEGE,SUNDERGARH

NAME: SWAYAMPRAVA ROUL

ROLL NO: S02416GEL052
CONTENT
1)Introduction
2)Oxidation and supergene enrichment process
Factors affecting the zones
3)Zone of oxidation
a)Gossan
b)Leached zone
c)Oxidised zone
Chemical changes
4)Zone of Supergene enrichment
Chemical changes
5)Hypogene zone
6)Conclusion
7)Questions
8)Reference
 INTRODUCTION
The formation of mineral deposits is complex. There are many
types of deposits, generally containing several ore and gangue minerals.
No two are alike; they differ in mineralogy, texture, content,
shape, size, and other features. They are formed by diverse processes,
and more than one process may enter into the formation of an individual
deposit.
Among the agencies that enter into the formation of mineral deposits,
water plays a dominant role. It may be in the form of water
vapor, hot magmatic water, cold meteoric water, or ocean, lake, or
river water. Temperature, likewise, plays an important part, but
many processes operate at surface temperature and pressure. Other
agencies are magmas, gases, vapors, solids in solution, the atmosphere,
organisms, and country rock. The process of formation of mineral deposits are
grouped into three main types:

 Sedimentary
 Magmatic/igneous
 Metamorphic

The various processes that have given rise to mineral deposits are:
1. Magmatic concentration.
2. Sublimation.
3. Contact metasomatism.
4. Hydrothermal processes.
Cavity filling.
Replacement.
5. Sedimentation .
6. Evaporation.
7. Residual and mechanical concentration.
8. Oxidation and supergene enrichment.
9. Metamorphism.

Two or more of these processes may have combined, either simultaneously or at

different times, to produce many of the mineral deposits. Replacement and cavity
filling commonly operate together;
fissures become filled and the walls are replaced. Deposits formed at the same time
as the rocks that enclose them, such as magmatic or sedimentary iron deposits, are
often referred to as syngenetic; those formed later than the rocks that enclose them
are
referred to as epigenetic. These words are not used here for classifying
mineral deposits but merely as useful descriptive terms.
The various processes of formation of mineral deposits are considered
in detail, starting with original magmatic materials, through those
of lower-temperature conditions of formation, to secondary processes.

SEDIMENTARY PROCESS
The primary minerals are subjected to chemical alternation , of which water is
the principal agents. The products of weathering are transported by sedimentary
process .Three important process are associated with sedimentary mineralisation
which are:
I. Oxidation and supergene enrichment
II. Residual concentration and Mechanical concentration
III. Sedimentation

OXIDISED AND SUPERGENE ENRICHMENT

When ore deposits become exposed by erosion they are weathered
along with the enclosing rocks. The surface waters oxidize many ore
minerals and yield solvents that dissolve other minerals. An ore deposit
thus becomes oxidized and generally leached of many of its
valuable materials down to the ground water table, or to a depth where
oxidation cannot take place. The oxidized part is called the zone of
oxidation. The effects of oxidation ,however, may extend far below the zone of
oxidation. As the cold,dilute, leaching solutions trickle
downward they may lose a part or all of their metallic content within
the zone of oxidation and give rise to oxidized ore deposits. If the down-trickling
solutions penetrate the water table, their metallic content may be preweathered
vein, with oxidized, superprecipitated
in the form of secondary gene enrichment, and primary zones,
sulphides to give rise to a zone of secondary or supergene sulphide enrichment.
The lower, unaffected part of the deposit is called the primary or hypogene zone.
In places the supergene
sulphide zone may be absent, and in rare cases the oxidized zone
is shallow or lacking, as in glaciated areas or regions undergoing rapid
erosion. Special conditions of time, climate, physiographic development,
and amenable ores are necessary to yield the results pictured
above, but they are sufficiently common for oxidized and enriched
supergene ores to occur in most of the non glaciated land areas of the
world. The process of oxidation and supergene enrichment give rise to many large
and rich ore deposits .Both the processes occur together.

Factors affecting these two zones are:

i. Topography
ii. Water table at great depth
iii. Porosity and permeability of rocks
iv. Presence of economic minerals
v. Time of exposure is high
vi. Low rate of erosion
vii. Climate

The oxidation zone divided into following:

A. GOSSAN OR IRON CAP

Gossans are signboards that point to what lies beneath the surface.
They arrest attention and incite interest as to what they may mask.
Most ore deposits, save in glaciated regions, are capped by gossans;
hence the finding of one may herald the discovery of buried wealth.
Noncommercial mineral bodies, however, also yield gossans. To distinguish
between them is of vital importance; but it requires experience, knowledge, and
careful observation. The distinctions involve delicate differences of color and form
that are difficult to transmit by written word; they must be seen.
Gossan is a Cornish word used to designate the oxidized outcropping
cellular mass of limonite and gangue overlying aggregated sulphide
deposits. The present tendency is to use also the term capping or cap
rock to designate the oxidized outcrops of disseminated deposits.
FORMATION OF GOSSAN:
 Limonite[Fe(OH)3 ] universally formed during oxidation of iron bearing
sulphide (pyrite) in the oxidised zone and imparts diagnostic colors. Other
persistent oxidised minerals in the gossans are former sulphides, carbonate
of lead , native silver . Gold generally persists in the croppings as native
gold .The limonite so formed may be indigenous and transported .

INDIGENOUS LIMONITE:

 They become fixed as oxide by occupying the voids left by former sulphides
.

 The indigenous are present as insoluble ferric state .

 It is generally compact and hard and has subdued colors .

TRANSPORTED LIMONITE:
  Sulphide derivation may either be dissolved , transported , precipitated
elsewhere forming transported zone .The transported is in soluble ferrous
state .
 They may form haloes around the empty voids , or it may permeate the
gangue or enclosing rocks .
 The structure assumed by limonite is called boxwork .
.
False Gossans : Transported iron, precipitated by reacting rocks,
may form an iron-stained area that resembles a true gossan, and the
resemblance is closer if the limonitic area is reworked by weathering.
The false gossan is distinguished from the true by the lack of
indigenous limonite, the lack of sulphide voids, and the nature of the
transported limonite. Such false gossans do not overlie ore deposits,
but their presence may indicate former sulphides not far distant.
Copper, like iron, may yield false croppings beneath which there is
no ore body. Transported copper may move outward from the original
deposit and be precipitated in the country rock as copper carbonates.
A disseminated copper ore body 140 feet wide observed by
the writer in Kenya Colony proved to be a false cropping— a deposit
without roots. The copper had migrated laterally and presumably
down structure from the eroded upward projections of narrow copperbearing
fissures. The carbonate ore became exposed on a surface
lowered by erosion. It was recognized as transported copper because
of
(1) the lack of original sulphide voids;
(2) no associated indigenous
limonite;
(3) no indigenous copper carbonate;
(4) the occurrence of the copper carbonate in the form of paint, impregnations,
carbonate
soaked clay, veinlets, and as open-space fillings with banding and
gel structure;
(5) the lack of hypogene rock alteration.
An apparent large disseminated copper deposit actually turned out to be of little
value. A similar occurrence of transported copper was observed in Lower
California. Copper is rather inclined to form false croppings. Some false croppings
have no tie with any known ore bodies;
they presumably have come from deposits above that have been completely
eroded.
BOXWORK LIMONITE COLOUR C

None Transported Brick red

 B. LEACHED ZONE
An ore body thus become oxidised and generally leached of many of its
valuable materials down to the water table ,or to depth where oxidation
cannot takes place.The leached solution loses a part of their mineral content
within the zone of oxidation as oxidised ore to form sulfuric acid and other
solutions that continue moving downward.

C. OXIDISED ZONE
 Solution travelling downward from the leached zone react with other
primary minerals in the oxidised zone to form secondary minerals such as
sulfates , carbonates and limonite ,which is a characteristics product in all
oxidised zones.

Chemical Changes Involved

There are two main chemical changes within the zone of oxidation:
(1) the oxidation, solution, and removal of the valuable minerals, and
(2) the transformation in situ of metallic minerals into oxidized compounds.
Most metallic mineral deposits contain pyrite. This mineral under
attack readily yields sulphur to form iron sulphate and sulphuric acid
pyrrhotite does the same. The following reactions indicate, without
intermediate steps, their general trend:
a)Formation of sulphuric acid and iron sulphate from pyrite:
FeS2 +7O +H2O =FeSO4 +H2SO4

The ferrous sulphate readily oxidises to ferric sulphate and ferric hydroxide:

6FeSO4 +3O+3H2O =2Fe(SO4)3 +2Fe(OH)3

b)In case of chalcopyrite:

CuFeS2 +2Fe2(SO4)3 =CuSO4 +5FeSO4 +2S

The chief ore minerals which occur as minerals are native gold
,carbonates , silicates, and oxides of copper ,zinc ,lead and silver

Examples are :

Chalcopyrite CuFeS2,Covellite CuS, Calcocite Cu2S ,

Malachite[CuCO3(OH)2] , Azurite [Cu(CO3)(OH)2] ,Zincite ZnO,
 Smithsonite ZnCO3 ,Sphalerite ZnS, Cerrusite PbCO3, Galena PbS
,Argentite Ag2S,Pyrite FeS2 ,Siderite FeCO3 .

Similarly other minerals are dissolved yielding, except for lead, soluble
sulphates of the metals. The sulphuric acid also attacks various
sulphides, yielding sulphates of their metals. Chlorides, bromides, and
iodides, chiefly of silver, are also formed. Most of the sulphates formed are readily
soluble, and these cold, dilute solutions slowly trickle downward through the
deposit until the proper conditions are met to cause deposition of their metallic
content .If pyrite is absent from deposits undergoing oxidation, only minor
amounts of the solvents are formed; little solution occurs, and the sulphides tend to
be converted in situ into oxidized compounds, and the hypogene sulphides are not
enriched. This is illustrated in the New Cornelia mine at Ajo, Ariz., where a
deficiency of pyrite has resulted in chalcopyrite being converted to copper
carbonate and supergene sulphides are negligible. This also happens where a
supergene chalcocite zone lacking pyrite is oxidized; the chalcocite is not dissolved
but is converted into copper carbonates, cuprite, or native copper. A country rock
of limestone tends to inhibit migration of some sulphate solutions; it immediately
reacts with copper sulphate, for example,to form copper carbonates, thus
precluding any supergene sulphide enrichment. The general tendency of the
chemical changes in the zone of oxidation is to break down complex minerals and
form simple ones. In general, among the metallic minerals, those lacking in oxygen
(sulphides, etc.) are most susceptible to oxidation, and most metallic oxides are
little affected. Native metals may be attacked; quartz is resistant, but silica set free
during oxidation is generally dissolved.

ZONE OF SUPERGENE ENRICHMENT

The metals in solution that escape capture in the oxidized zone
trickle down to where there is no available oxygen, generally the water
table, and there undergo deposition as secondary sulphides. The
metals removed from above are thus added to those existing below,
thereby enriching the upper part of the sulphide zone. This forms the
zone of secondary enrichment or, as it is now more generally referred
to, the supergene sulphide zone. It in turn is underlain by the primary
or hypogene zone . Progressive erosion permits deeper
oxidation, and after a time the supergene sulphides themselves become
oxidized, and their metal content is then transferred to the downward progressing
enrichment zone. The primary ore may thus be enriched
to as much as ten times its original metal content. Rich ores are made
richer, lean ores are made valuable, and noncommercial primary material
or protore is built up to commercial grade.
Favorable conditions must exist for supergene sulphide enrichment
to take place, but they are sufficiently common that sulphide-enriched
deposits are widely scattered over the nonglaciated areas of the earth.
The process is of greatest importance with copper and silver deposits,
and the following pages deal mainly with them.This is the richest part of an ore
deposits , lying below the water table.This is a zone of chemical changes and
molecular arrangement.This zone contains sulphide ores only.
EXAMPLES ARE :Galena PbS ,Argentite Ag2S ,Pyrite FeS2,
chalcopyrite CuFeS2,Covellite CuS, Tetrahedrite Cu8Sb2S7 .

The primary requisites for supergene enrichment are:

 Oxidation,
 Presence of primary minerals to yield necessary solvents,
 Permeability of rock to enable the solutions to penetrate
 Absence of precipitates in the oxidised zone ,
 Zone of no available oxygen where the secondary sulphides may
be deposited ,
 Presence of hypogene minerals below the water table to cause
precipitation of secondary minerals.
In the zone of supergene enrichment the precipitation of the metallic
sulphides is affected following Schurmann’s law in the following order:

Mercury ,Silver , Copper ,Bismuth ,Lead ,Zinc ,Nickel ,Cobalt

,Iron ,Manganese .. according to increasing solubility.

CHEMICAL CHANGES
The reducing environment favours the precipitation of ore minerals as
sulphide .This deposition takes place by the process of replacement where
the pre existing metallic sulphides are replaced. The chemical changes are:

In case of copper sulphide:

CuSO4+ PbS = CuS+ PbSO4

5FeS2 +14CuSO4 +12H2O =7Cu2S +5FeSO4+ 12 H2SO4

 In case of silver sulphide:

ZnS +Ag2SO4=Ag2S+ZnSO4

The secondary enrichment may be partial or complete depending upon

the degree of replacement of hypogene minerals . It may be selective in case
of veinlets of hypogene minerals replaced or only certain minerals.

The enrichment ceases to take place in case of:

1)complete enrichment

2)non availability of primary ores

3)burial of secondary enrichment under thick cover of sediments, or

lavas from volcanos

4)submergence of oxidised and enriched zone

PRIMARY OR HYPOGENE ZONE

This zone occurs deep below the earth’s surface , which tend to form
deposits of primary minerals.This is usually the reducing zone , containing
unaffected part of ore body ,disseminated sulfide minerals (pyrite
,chalcopyrite , sphalerite.
CONCLUSION
Supergene , oxidation and reduction environment go hand in hand . Without
oxidation there can be no supply of solvents from which minerals may later be
precipitated in the two zones .In some places the supergene zone is absent and
in rare cases the oxidised zone may be shallow or lacking( as in some glaciated
areas undergoing rapid erosion).Special conditions of time , climate,
physiographic development and amenable ores are necessary for the process of
oxidation and supergene enrichment to be effective.When pyrite is absent from
deposits undergoing oxidation ,minor amount of solvents are formed ,little
oxidation occurs , the sulphides tend to be converted in situ into oxidised
compounds , and hypogene deposits are not enriched.
reference

 A textbook of geology – G.B. Mahapatra(2016),CBS PUBLICATION,

process of formation of ore deposits ,(page 253-255)

 Economic geology second edition - Umeshwar Prasad ,CBS

PUBLICATION process of formation of minerals(page 22-27)

 Economic mineral deposits (third edition)-Mead L. Jensen &Alan M .

Bateman ,BOOK SELECTION CENTRE ,oxidation and supergene
enrichment ( page 239-250)

 https://en.m.Wikipedia.org./wiki/oxidationandsupergeneenrichment

 Principle of engineering geology –K M Banger(second edition) Ore

deposits(page 328 ,329)