Periodicity of Copper Accumulation in the Earth’s ... · 2–3), Poland (Lubin-Sieroszowice), Germany (Mansfeld, P 2), and other regions. Mesozoic–Cenozoic deposits are represented

ISSN 0024-4902, Lithology and Mineral Resources, 2008, Vol. 43, No. 2, pp. 136–153. © Pleiades Publishing, Inc., 2008.Original Russian Text © I.F. Gablina, Yu.M. Malinovskii, 2008, published in Litologiya i Poleznye Iskopaemye, 2008, No. 2, pp. 155–173.

136

Exogenic copper deposits (cupriferous sandstonesand shales) are known in Early Proterozoic–Tertiarysedimentary rocks. Such deposits are found at differentstratigraphic levels in rocks subjected to postsedimen-tary alterations various grades (from diagenesis toamphibolite grade and hypergenesis). They account for32.6% of world Cu reserves mainly confined to largeand giant deposits. The Cu reserve in these deposits isas much as 10 Mt or more.

Regularities in the distribution and structure ofcupriferous sandstone and shale deposits are scruti-nized in (Bogdanov et al., 1973; Gablina, 1983;Gustafson and Williams, 1981; Kirkham, 1989; Lur’e,1988; Lur’e and Gablina, 1972, 1978; Narkelyun et al.,1983; and others). All giant deposits and occurrences ofcupriferous sandstones are characterized by their asso-ciation with terrigenous red rocks. Mineralization islocalized in the organic-rich and pyrite-containing grayrocks that replace the red rocks along the vertical andlateral directions. The genetic model, which most com-pletely explains regularities of the localization andstructure of cupriferous sandstone and shale deposits, isbased on ideas proposed in (Germanov, 1962;Perel’man, 1959; Rose, 1976). According to thismodel, Cu and other metals are transported by ground-waters from the red rocks and concentrated as sulfideson hydrosulfuric geochemical barriers (Ensign et al.,1968; Gablina, 1983; Gustafson and Williams, 1981;Hoyningen-Huene, 1963; Lur’e, 1988; Lur’e andGablina, 1972, 1978; Wodzicki and Piestrzynski, 1986;and others).

In general, ore deposits and occurrences of this typedo not show explicit periodicity across the section. Theoldest objects are represented by the Flake Lake, StagLake, Desbarats, and other ore occurrences associatedwith the Early Proterozoic Lorain red rock formation

(Ontario, Canada), as well as small Mangula andAlaska deposits associated with the Early ProterozoicLomagundi Group confined to red molassic rocks of theDeweras Group in Zimbabwe, South Africa (Narkelyunet al., 1983). In Russia, the Early Proterozoic mineral-ization level is represented by the Udokan deposit con-fined to the Udokan metasedimentary rock group.Small ore occurrences are located in the Kondo–Kareng, East Aldan, and Olekma–Tokka zones of Sibe-ria. Cupriferous rocks of these ore occurrences are usu-ally compared with the Udokan Group. However, someresearchers consider that affiliation of ore-enclosingrocks of the Udokan Group to the Early Proterozoicbased on isotopic datings of rocks is invalid, becausethey contain Typical Riphean stromatolitic species(Amantov, 1978). Medusoid imprints detected in differ-ent suites of the Udokan Group (Vil’mova, 1987) sup-port the Riphean age of these rocks. Thus, if we omitthe Udokan deposit, Early Proterozoic sedimentary andmetasedimentary complexes contain only small oredeposits and occurrences.

Small deposits and occurrences of cupriferous sand-stones and shales are known in Cambrian–Ordoviciansections in the Siberian Platform and Australia. Devo-nian representatives are known at the southern marginof the Russian Platform, the Altai–Sayan cupriferousprovince, and Kazakhstan. Permian and Mesozoic–Cenozoic objects are found in Central Europe, the Rus-sian Platform, Africa, and America (Narkelyun et al.,1983).

Based on the maximal Cu concentration in theEarth’s history, we can recognize the Late Precambrian,Late Paleozoic, and Mesozoic–Cenozoic stages (table).With respect to the scale of Cu accumulation, each sub-sequent stage is significantly inferior to the precedingstage. For example, the distribution of Cu reserve is as

Periodicity of Copper Accumulation in the Earth’s Sedimentary Shell

I. F. Gablina and Yu. M. Malinovskii

Geological Institute, Russian Academy of Sciences, Pyzhevskii per. 7, Moscow, 119017 Russiae-mail: [email protected]

Received January 22, 2007

Abstract

—Physicochemical conditions of the migration and concentration of Cu in sedimentary rock, specificfeatures of the formation of large and unique deposits of cupriferous sandstones and shales, distribution of cop-per deposits in the stratigraphic scale, and causes responsible for the reduction of Cu accumulation from Prot-erozoic to Cenozoic are considered. Genetic link of cupriferous sandstones and shales with arid red molassicrocks is shown. Conditions and periodicity of formation of the ore-generating red rocks are considered. Anexplanation for periodicity of maximum Cu accumulation in the Earth’s history is proposed.

DOI:

10.1134/S0024490208020041

LITHOLOGY AND MINERAL RESOURCES

Vol. 43

No. 2

2008

PERIODICITY OF COPPER ACCUMULATION IN THE EARTH’S SEDIMENTARY SHELL 137

Maj

or e

poch

s of

exo

geni

c co

pper

acc

umul

atio

n in

the

Ear

th’s

his

tory

EpochO

re-g

ener

atin

g re

d ro

ck a

ssoc

iatio

nsO

re-e

nclo

sing

gra

y ro

cks

Dep

osits

Sour

ce

age,

gro

updi

stri

butio

n pa

ttern

form

atio

n,ho

rizo

n, a

ge

faci

es c

ompo

sitio

n,po

sitio

n re

lativ

eto

red

roc

ksno

.na

me

size

Proterozoic

Ear

ly (

?) P

rote

rozo

-ic

, Udo

kan

Gro

upIn

a la

rge

inte

rmon

-ta

ne d

epre

ssio

n up

to 1

000

0 de

ep

Hor

izon

in th

e up

per

Saku

kan

Subf

orm

a-tio

n, U

doka

n G

roup

(P

R

1

?)

Lag

oono

n sh

allo

w-w

ater

m

arin

e py

rite

-bea

ring

sedi

men

ts w

ithin

red

rock

s

1U

doka

nL

arge

(Bog

dano

v et

al.,

196

6,

1973

; Nar

kely

un e

t al.,

19

77, 1

983;

Gab

lina

and

Mik

hailo

va, 1

994;

Vol

odin

et a

l., 1

994)

Low

er S

akuk

an S

ub-

form

atio

n, A

leks

an-

drov

For

mat

ion,

U

doka

n G

roup

(P

R

1

?)

Del

taic

and

sha

llow

-wat

erm

arin

e se

dim

ents

at

the

base

of

red

rock

s

2U

nkur

Smal

l

3A

leks

andr

ovSm

all

Lat

e Pr

oter

ozoi

c,or

e gr

oup

In in

term

onta

ne d

e-pr

essi

ons

and

val-

leys

up

to 1

500

m

deep

Low

er R

oan

ore

hori

zon

basa

l lay

ers

of m

arin

ese

dim

ents

at t

he to

p of

red

rock

s

4D

epos

its o

fth

e C

oppe

rB

elt i

n A

fric

a

Lar

ge(

Geo

logy

…, 1

961;

Cai

l-te

ux, 1

973;

Lur

’e, 1

988)

Lat

e Pr

oter

ozoi

c,

Cop

per

Har

bor

Form

atio

n

In a

larg

e fo

rede

epup

to 1

000

m d

eep

Non

esuc

h Sh

ale

(PR

2

)O

rgan

ic-r

ich

basa

l lay

ers

of m

arin

e se

dim

ents

at

the

top

of r

ed r

ocks

5W

hite

Pin

e(L

ake

Supe

rior

, U

nite

d St

ates

)

Lar

ge(W

hite

, 197

1; E

nsig

net

al.,

197

2; L

ur’e

, 198

8)

Ven

dian

–Cam

bria

n,

Loi

khva

r Fo

rmat

ion

In a

larg

e in

term

on-

tane

dep

ress

ion

Loi

khva

r Fo

rmat

ion

Bas

al la

yers

of

mar

ine

sedi

men

ts6

Ain

ak(A

fgha

nist

an)

Lar

ge(Y

urge

nson

et a

l., 1

981;

Y

ashc

hini

n an

d G

iruv

al,

1981

)

Ven

dian

, Izl

uchi

n Fo

rmat

ion

In a

larg

e fo

rede

epup

to 3

00 m

dee

pV

endi

an I

zluc

hin

and

Ven

dian

–Cam

-br

ian

Sukh

arik

ha

form

atio

ns

Ree

foge

nic

carb

onat

e ro

cks,

ba

r sa

ndst

ones

, and

car

bo-

nace

ous

schi

sts

at th

e ba

se

of m

arin

e se

dim

ents

with

-in

and

at t

he to

p of

red

ro

cks

7G

ravi

ika

(Iga

rka

area

)Sm

all

(Rzh

evsk

ii et

al.,

198

8;

Lur

’e, 1

988)

138


Vol. 43

No. 2

2008

GABLINA, MALINOVSKII

(Con

td.)

EpochO

re-g

ener

atin

g re

d ro

ck a

ssoc

iatio

nsO

re-e

nclo

sing

gra

y ro

cks

Dep

osits

Sour

ce

age,

gro

updi

stri

butio

n pa

ttern

form

atio

n,ho

rizo

n, a

ge

faci

es c

ompo

sitio

n,po

sitio

n re

lativ

eto

red

roc

ksno

.na

me

size

Late Paleozoic

Mid

dle–

Lat

eC

arbo

nife

rous

, D

zhez

kazg

anSe

quen

ce

In a

larg

e fo

rede

epup

to 1

500

m d

eep

Dzh

ezka

zgan

Sequ

ence

(C

2–3

)R

eble

ache

d pe

rmea

ble

hori

zons

with

in th

e re

dse

quen

ce

8D

zhez

kazg

an(K

azak

hsta

n)L

arge

(Nar

kely

un, 1

962;

Gab

-lin

a, 1

983;

Lur

’e, 1

988)

Ear

ly P

erm

ian,

Kar

tam

ysh

Form

atio

n

Dep

ress

ions

up

to

1200

m d

eep

Kar

tam

ysh

Form

atio

n (P

1

)Sh

allo

w-w

ater

mar

ine,

ch

anne

l, an

d sa

bkha

with

in th

e re

d se

quen

ce

9B

eres

tyan

dep

osit,

K

arta

mys

h or

eoc

curr

ence

, and

ot

hers

(D

onba

s)

Smal

l(L

ur’e

, 198

8)

Ear

ly P

erm

ian,

Dea

d R

ed B

eds

In la

rge

inte

rmon

t-an

e tr

ough

s, d

epth

up

600

to 1

000

mor

mor

e

Zec

hste

in (

P

2

)B

ar(?

) sa

ndst

ones

and

carb

onac

eous

sch

ists

at

the

base

of

mar

ine

sedi

-m

ents

10M

ansf

eld,

San

ger-

haus

en, R

eich

els-

dorf

, and

oth

ers

(Ger

man

y)

Ord

inar

y(E

isen

hut a

nd K

autz

sch,

19

54; H

oyni

ngen

-Hue

ne,

1963

; Aut

oren

kolle

ktiv

…,

1968

; Lur

’e, 1

974;

Wod

-zi

cki a

nd P

iest

rzyn

ski,

1986

; Lur

’e, 1

988;

Gab

-lin

a, 1

997;

and

oth

ers)

11L

ubin

-Sie

ro-

szow

ice

Uni

que

12D

epos

its o

fth

e N

orth

Sud

ettr

ough

(Po

land

)

ordi

nary

A

nd

Smal

l

Lat

e Pe

rmia

n;U

fim

ian,

Kaz

ania

n,an

d T

atar

ian

stag

es

In th

e U

ral F

ored

eep

Ufi

mia

n an

dK

azan

ian

stag

es(P

2

)

Allu

vial

–lac

ustr

ine

sedi

-m

ents

and

sab

kha

with

in

red

sedi

men

ts; o

rgan

ic-

rich

bas

al la

yers

of

shal

-lo

w-w

ater

mar

ine

sedi

-m

ents

13O

re o

ccur

renc

es o

f th

e w

este

rn U

ral

regi

on (

Kar

galin

G

roup

and

oth

ers)

Smal

l(L

ur’e

and

Gab

lina,

197

2;

Lur

’e, 1

974,

198

8)


Vol. 43

No. 2

2008


(Con

td.)

Epoch

Ore

-gen

erat

ing

red

rock

ass

ocia

tions

Ore

-enc

losi

ng g

ray

rock

sD

epos

its

Sour

ce

age,

gro

updi

stri

butio

n pa

ttern

form

atio

n,ho

rizo

n, a

ge

faci

es c

ompo

sitio

n,po

sitio

n re

lativ

eto

red

roc

ksno

.na

me

size

Mesozoic–Cenozoic

Mid

dle

Jura

ssic

–E

arly

Cre

tace

ous

In d

eep

depr

essi

ons

(up

to 1

000

0 m

)M

iddl

e Ju

rass

ic–

Ear

ly C

reta

ceou

sG

ray

hori

zons

with

in

the

red

sequ

ence

14D

epos

its o

fth

e Y

unna

npr

ovin

ce (

Chi

na)

Lar

ge(N

arke

lyun

et a

l., 1

983)

Ear

ly C

reta

ceou

sIn

mar

gina

l tro

ughs

up

to 1

100

m d

eep

Ear

ly C

reta

ceou

sO

rgan

ic-r

ich

lago

onal

–de

ltaic

, cha

nnel

, and

lacu

s-tr

ine–

oxbo

w s

edim

ents

w

ithin

red

sed

imen

ts

15O

re o

ccur

renc

esof

the

Taj

ik d

ep-

ress

ion

Smal

l(B

ogda

nov

et a

l., 1

973;

N

arke

lyun

et a

l., 1

983)

Pale

ogen

e–N

eo-

gene

, Cor

ocor

o G

roup

In a

n in

trac

rato

nic

trou

gh w

ith a

tota

l de

pth

of 1

000

0–15

000

m

Low

er a

nd u

pper

part

s of t

he C

oroc

oro

Gro

up

Riv

er s

edim

ents

with

in re

d se

dim

ents

16C

oroc

oro

(Bol

ivia

)Sm

all

(Gus

tafs

on a

nd W

illia

ms,

19

81; N

arke

lyun

et a

l.,

1983

)

Neo

gene

In a

n in

term

onta

ne

depr

essi

on u

p to

25

00 m

Plio

cene

Bak

trin

Sequ

ence

Cha

nnel

and

lacu

stri

ne

gray

inte

rlay

ers

with

in th

e re

d se

quen

ce

17N

auka

t(F

erga

na V

alle

y)Sm

all

(Nar

kely

un e

t al.,

198

3)

In a

rif

t zon

eE

arly

Plio

cene

Mar

ine

hori

zons

with

in

the

cont

inen

tal r

ed s

edi-

men

ts

18B

oleo

(M

exic

o)O

rdin

ary

(Gus

tafs

on a

nd W

illia

ms,

19

81; C

ony

et a

l., 2

001)

140


Vol. 43

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2008


follows: 21% in Precambrian rocks, approximately10% in Paleozoic rocks, and 1.6% in Mesozoic–Ceno-zoic rocks (Yanshin, 1972). The maximum Cu concen-tration is related to Late Proterozoic (Late Riphean–Vendian) rocks. Deposits of this level are known at vir-tually all continents. Large deposits occur in the CopperBelt of Africa (Roan Antelope, Musoshi, Mufulira, andothers), United States (White Pine), Afghanistan(Ainak), India, and China (Inming and Lusue). The sec-ond (smaller) Cu peak is observed in the Carbonifer-ous–Permian. Deposits of this period are known inKazakhstan (Dzhezkazgan, C

2–3

), Poland (Lubin-Sieroszowice), Germany (Mansfeld, P

2

), and otherregions. Mesozoic–Cenozoic deposits are representedby Corocoro in Bolivia (Paleogene–Neogene) andBoleo in Mexico (Neogene). Small ore deposits andoccurrences are found in Jurassic, Cretaceous, andPaleogene red rocks in the Yunnan and Hunan prov-inces of China (Narkelyun et al., 1983). Cupriferousrocks are also developed in the Lower Cretaceous sec-tion of the Tajik depression and the Neogene section ofthe Fergana Valley (Naukat).

CONDITIONS OF COPPER MIGRATION

Red Rocks and the Nature of Their Coloration

Irrespective of the age and metamorphism grade ofhost rocks, mineralization of cupriferous sandstonesand shales is confined either to red sequences or tobasal horizons of the overlying marine sequences(Fig. 1). Mineralization is less common in the underly-ing marine sediments at their contact with the red rocks(Northern group of deposits in the Dzhezkazgan districtand Horizon A in the Igarka district). Beginning fromthe Proterozoic, arid red rocks are found in almost allsystems, but they are most developed in the Late Prot-erozoic, Devonian, Permian, Triassic, Cretaceous, andNeogene (Fig. 2).

The spatial association of cupriferous sandstonesand shales with the red rocks is related to specific fea-tures of the geochemical behavior of Cu in the exogenicenvironment. According to (Perel’man, 1959, 1968;Lur’e, 1988; and others), arid red rocks serve as sourceand migration medium of Cu.

In addition to color, the red rocks have the sandy–clayey composition. In some places, their matrix con-tains carbonates as independent lenses and interlayerssometimes associated with evaporites. In general, theserocks represent orogenic molasses accumulated in foot-hills and intermontane depressions (table). The redcolor is related to the dissemination of iron oxides andhydroxides, which can be preserved under conditionsof long-term domination of oxidizing environment.Therefore, continental conditions, as well as with dryand hot climate, are most favorable for the accumula-tion of red rocks. The FeO/Fe

2

O

3

ratio (correspond-ingly, the mineral form of Fe in sediments) is the majorindicator of redox potential of sedimentation medium.

In the red rocks, the ratio is <1; i.e., oxide forms of ironcompounds prevail. In the gray rocks, the ratio is >1;i.e., bivalent iron minerals (sulfides, silicates, and car-bonates) dominate (Gablina, 1990).

Chukhrov et al. demonstrated in (

Gipergennye …

,1975) that nature of the pigmenting material of redrocks can be dualistic: either introduction as goethite(FeOOH) suspension or precipitation as ferrihydrite(2.5Fe

2

O

3

· 4.5H

2

O) from solution. The first migrationform is typical of tropical zones with a high oxidationrate. The second form is commonly developed in tem-perate zones, where the oxidation rate is less intenseand Fe transferred as bicarbonate into the solution isremoved by groundwaters. When such waters flow outto the surface, Fe is oxidized and ferrihydrite is formed.Rocks acquire the yellowish brown color in the courseof its transport to sedimentation sites as flakes and coat-ings on clayey particles. At ordinary temperatures, theferrihydrite is instantly transformed into hematite dueto the release of water (

Gipergennye…

, 1975). Thetransitional phase can be present as hydrohematite(fine-crystalline hematite) that contains as much as 8%of the weakly bonded water, which is released at 100–150

°

C. Investigation of red rocks of the Middle–UpperCarboniferous Dzhezkazgan Sequence in Kazakhstan(Gablina, 1983) showed that the ferruginous pigment inthese rocks is primarily represented by the fine-dis-persed hematite. The less altered Ufimian (Upper Per-mian) red rocks of the western Ural region mainly con-tain hydrogoethite (Kossovskaya and Sokolova, 1972).In Late Precambrian rocks of the Diaoyutai Formation(China), hematite is supplemented with goethite in thecement of clastic rocks (

Gipergennye…

, 1975). Thecement also contains goethite and hematite in LowerRoan red rocks of the Shaba province (Zaire) character-ized by minimal metamorphism (Cailteux, 1973).

Domination of the oxidizing environment duringsedimentation and subsequent stages of lithogenesis isessential for the appearance and preservation of redcolor of rocks. This condition is provided by a low orvery low content of buried organic matter. According toStrakhov (1964), red rocks are formed at the C

org

con-tent of <0.3%. Greenish gray and gray rocks are formedat higher C

org

contents. According to Tazhibaeva et al.(1964), the C

org

content is 0–0.07% in red rocks of theDzhezkazgan Sequence. Gray rocks of the underlyingLower Carboniferous Taskuduk Formation of the tran-sitional type (relative to marine sediments) are enrichedin C

org

up to 0.74% (Arustamov et al., 1963). In theIgarka district, the average content of residual C

org

is<0.1% in red rocks of the Late Proterozoic IzluchinFormation and varies from 0.12 to 0.38% in the grayvariety from the overlying Vendian–CambrianSukharikha Formation (Gablina, 1990). The total Fecontent in the red rocks is often higher than that in sed-imentary rocks with other colors. At the same time, theFe content is inversely correlated with the grain size ofrocks. Favorable conditions for the formation and pres-ervation of red rocks are typical of continental rocks


Vol. 43

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2008


Fig. 1.

Relationship of cupriferous sandstones and shales with red rocks. (1) Dolomites; (2) stromatolitic dolomites; (3) limestones;(4) marls; (5) mudstones and shales; (6) siltstones; (7) sandstones; (8) breccia and conglobreccia; (9) conglomerates; (10) albitites;(11) authigenic indicator-mineral of the redox potential of rocks in the metamorphosed Udokan Group: (

a

) pyrite and pyrrhotite,(

b

) hematite and magnetite; (12, 13) rock color: (12) red: (

a

) observed, (

b

) reconstructed; (13) gray; (14) copper mineralization. (I–XI) deposits and ore occurrences: (I) Mansfeld, Sanderhausen, Lubin-Sieroszowice, and others; (II) Dzhezkazgan; (III) Northerngroup deposits; (IV) Horizon A; (V) Horizon B; (VI) Graviika; (VII) White Pine; (VIII) Udokan; (IX) Unkur; (X) Krasnoe;(XI) Pravyi Ingamakit.

ÏÏ

Ï Ï

Ï ÏÏ ÏÏ Ï

Ï

Ï ÏÏ

Ï

ÏÏ

ÏÏ

Ï ÏÏ ÏÏ Ï

m5

4

3

2

1

0

P

2

P

1

Rot

liege

nde

Zec

hste

in

CentralEurope

30

20

10

0

P

2

Stag

eK

azan

ian

Ufi

mia

n

600

400

200

0

P

1

ë

2–3

ë

1

II

III

Dzh

ezka

zgan

Sequ

ence

R

3

600

400

200

0

V

V–C

1

~

Sukh

a-Fo

rmat

ions

Izlu

chin

Che

rnay

aR

echk

a

V,VI

IV

40

30

20

10

0

Non

esuc

h Sh

ale

Cop

per

Har

bor

Con

glom

erat

e

VII

5000

4000

3000

2000

1000

Udo

kan

Gro

up

PR

1

Chi

t-A

lek-

But

inSa

kuka

n

Nam

i-

Form

a-at

ions

VIII

IX

X, XI

1

2

3

4

5

6

7

8

9

10

11

12

13

14

‡·

‡·

Western Uralregion

Dzhezkazgandistrict

Igarkadistrict

MichiganState

Kodar–Udokanzone

I

m

rikh

a

nga

drov

san-

kand

a

142


Vol. 43

No. 2

2008


formed in arid climate. Such rocks are abundant in thePhanerozoic. Precambrian red rocks are mainly devel-oped in the Riphean and Vendian, e.g., Ushakov Forma-tion and Oselkov Group (southern framing of the Sibe-rian Platform), Izluchin Formation (Igarka district),Lower Roan (Africa), and others. Older red rocks arerepresented by the Early Proterozoic Lorain Formation(Canada), Jatulian Group (Karelia), and others.

Phanerozoic and Precambrian red rocks formed indifferent settings. The Phanerozoic red rocks are mark-ers of arid climate. Climate did not play any significantrole in the Precambrian because of the absence of landvegetation. According to (Cloud, 1973; Melezhik,1987; and others), formation of the Precambrian redrocks is related to the vital activity of cyanobacteria thatpromote the photosynthesis of oxygen. Based on reli-able findings of stromatolites and microfossils begin-ning from 3.5–3.3 Ga (Notre Pol, Australia; Onvervaxt,South Africa), Krylov (1983) suggested that the atmo-spheric oxygen content was close to the present-dayone by the initial Proterozoic owing to the vital activityof organisms.

Thus, researchers do not doubt the presence offavorable conditions for the formation of red rocks andtheir existence in the Precambrian. However, it is ratherdifficult to identify them in the Precambrian metamor-phosed sequences. We proposed mineral–geochemicalcriteria for the identification of primary red rocks in thePrecambrian metasediments, which lost the red color inthe course of metamorphism (Gablina, 1990).

As was mentioned, red and gray rocks in theunmetamorphosed sediments are distinguished by theFeO/Fe

2

O

3

ratio, the mineral form of Fe, and the C

org

content. Based on these criteria, we reconstructed theprimary color of rocks of the Udokan Group, the meta-morphism of which varies from the greenschist to theepidote–amphibolite facies. Thus, we deciphered rockcomplexes (with the primary gray color) formed in thereducing environment and primary red rocks formed inthe oxidizing environment. The first type is character-ized by the prevalence of Fe

2+

(FeO/Fe

2

O

3

> 1), abun-

dance of authigenic pyrite (or pyrrhotite) dissemina-tion, and high content of the residual C

org

(up to 1.11%,average 0.4%). The primary red rocks are marked bylow values of C

org

(<0.1%, on average) and FeO/Fe

2

O

3

(average 0.5), as well as the presence of newly formedhematite and magnetite. Validity of this reconstructionis supported by positions of cupriferous levels in thesection. Like in unmetamorphosed sequences, high Cuconcentrations in the metamorphosed sequences arecontrolled by geochemical barrier zones: boundaries ofthe replacement of primary red rocks by gray rocks orsectors of primary gray rocks within the red complexes(Fig. 1). The present-day gray color of metasedimen-tary primary red continental rocks is related to theselective recrystallization of fine-dispersed hematiteand its transformation into magnetite under the influ-ence of high temperatures and reduction of oxidativepotential during metamorphism.

Such reconstruction can also be accomplished forother continental molassic rocks. For example, rocks ofthe Katanga system in the Copper Belt of Africa aremetamorphosed to different degrees. According toF. Mendelsohn, the metamorphism grade increasesfrom the north to south and southwest (

Geology…,

1961). At the northernmost margin (Shaba province,Zaire), where the Katanga rocks are not metamor-phosed, sandstones and conglomerates beneath the orehorizon have preserved the red color. Pigment in themis represented by goethite and hematite. In the southernpart of the Copper Belt, increasing grade of metamor-phism leads to replacement of the red coarse-clasticrocks beneath the ore horizon by the gray variety withcrystalline hematite and magnetite in the cement (RoanMuliashi syncline).

Geochemical Setting of the Formation of Red Rocks

From the point of view of physical chemistry, redrocks represent the stability region of Fe

3+

. The Eh–pHdiagram (Fig. 3) shows that this region includes all(bivalent, monovalent, metallic, and sulfide) species of

Fig. 2.

Red rocks and large copper deposits in sandstones and shales. Length of horizontal lines corresponds to the age range of redrocks. Bold lines show the thickest red sequences. Data on the red rocks are adopted from (Anatol’eva, 1978) and modified.(1–18) Deposit numbers as in the table; (19–28) numbers of deposits and districts omitted in the table due to the lack of infor-mation: (19) Mount Lyell cupriferous shale deposit (Australia), (20) Altai–Sayan cupriferous province, (21) Weiniya and Milichanore districts (China), (22) Happy Jack deposit (United States), (23) Seboruco deposit (Venezuela), (24) Kashueiras deposit(SW Africa), (25) Merja deposit (North African province), (26) Heili ore district (China), (27) Beni Mellal cupriferous district(North African province), (28) Timna deposit (Israel). Box size corresponds to the reserve of deposits.

34

12

728

65

Cu

19 208

9

1311

1221

102214

25

26

2427

23

1618

17

R V C

~

O S D C P T J K P N

?

15


Vol. 43

No. 2

2008


Cu known in nature. At the same time, their stabilityfields replace each other sequentially during the drop ofredox potential. The Fe

3+

/Fe

2+

boundary is located inthe stability field of copper sulfides.

Enrichment of rocks with Cu is atypical of redrocks. The Cu content in rocks is close or slightly lowerthan the clarke value (Borisenko, 1980; Perel’man andBorisenko, 1962). Depending on the Eh and pH valuesof solutions, the Cu content in ground (interstitial andformation) waters of red rocks can exceed 50 mg/l(Pushkina, 1965; Shcherbakov, 1968). It is now com-monly accepted that Cu and other nonferrous metals aremainly transported in water solutions as complex com-pounds. Sedimentation waters of continental red rocksare characterized by high oxidizing potential and nearlyneutral medium (Fig. 3, field I) during sedimentation.Subsidence and consumption of oxygen for oxidizingreactions lead to decrease in the Eh value of pore solu-tions and development of an oxidation-to-reductiontransitional medium (Fig. 3, field II). Under such con-ditions, the bivalent Cu is reduced to the monovalentstate (Lur’e, 1988). Formation waters of continental redrocks usually contain Cl ion, which makes up water-soluble complexes with Cu

+

. Compounds of Cu

2+

areless mobile. In nearly neutral natural waters typical of

the formation waters of red rocks, the Cu

2+

content isvery low and varies from

n

×

10

–3

to

n

×

10

–4

(Golevaet al., 1968; Perel’man, 1968; Shcherbakov, 1968; andothers).

Proterozoic continental red rocks do not containreducers (Yanshin, 1972). In contrast, their Phanero-zoic counterparts represent more complex compoundsowing to the appearance of higher plants on continents.They often contain relicts of organic remains testifyingto the incomplete process of oxidation. Therefore,Lur’e (1988) distinguishes two basically different (ore-generating and barren) types of red rocks. In the ore-generating rocks, Cu occurs as the mobile Cu

+

ion withEh value corresponding to field II in Fig. 3. In the bar-ren red rocks, the Eh value can be higher (field I in theCu

2+

stability field) or lower (field III in the sulfide Custability field). In the latter case, new insoluble (sulfideand native) forms of Cu are formed. With respect to theCu occurrence mode, these red rocks do not differ fromthe gray variety (Cu in them is inert). Therefore, theirrole as a source of Cu is negligible. The barren typeincludes Devonian red rocks in the northwestern Rus-sian Platform, Permian and Triassic rocks in middlePechora, Neogene rocks in Karakum, and others(Borisenko, 1980). In fact, only two (Late Precambrian

Eh

0.5

0.4

0.3

0.2

0.1

0

–0.1

–0.2

–0.3

–0.43 4 5 6 7 8 9 10 11 pH

1

2

3

CuOCuO + Fe

2

O

3

Cu

2+

+CuCl

2–3

++CuCl

–2

64 mg/l

Cu

2+

+ Fe

2+

I

II

Cu

2

O + Fe

2

O

3

Cu

2

O

Cu

Fe2O

3Fe 2+

III

H2O

H2

CuFeS2

Cu5 FeS

4 + FeS2

Cu2S + FeS

2

Cu2 S + Fe

2 O3

Cu2++ Fe2O3

6mg/l

Cu + Fe2 O

3

Fig. 3. Diagram showing the stability of copper compounds and geochemical settings of Cu migration and concentration. Basedafter (Lur’e, 1988). (1) Cu–Fe–S–O–H system at T = 25°C, total P = 1 atm, and ΣS = 10–4 mol; (2) Cu–S–O–H–Cl system at T =25°C, ΣS = 10–4 mol, and Cl– = 0.5 mol (as NaCl); (3) isolines of the Cu content in the NaCl solution. (I–II) Geochemical settings:(I) in sedimentary waters during the accumulation of continental red sediments in the course of active water exchange, (II) in for-mation waters during peneplanation and retarded water exchange (formation of ore-bearing solutions during catagenesis), (III) inthe reducing geochemical barrier zone (sulfide formation period).

144

LITHOLOGY AND MINERAL RESOURCES Vol. 43 No. 2 2008


and Permian–Carboniferous) epochs of the wide devel-opment of arid red rocks coincide with the maximumCu accumulation in sedimentary rocks (Fig. 2). TheDevonian period can serve as example of reverse rela-tionships: intense development of red rocks in theDevonian is not accompanied by the formation of anysignificant deposits of cupriferous sandstones andshales. The absence of reducers in the Proterozoic con-tinental red rocks could foster their maximal Cu pro-ductivity.

Middle–Upper Carboniferous red rocks of the Chu-Sarysui Depression contain abundant remains of landvegetation as molds of red ocherous clays that aredevoid of any signs of bleaching. Reducing environ-ment was not developed here because of the completeoxidation of plant tissues. Hence, these sediments wereunfavorable for the local precipitation of Cu and thewhole reactive Cu could migrate. Such sediments arethe most probable source of Cu for the Dzhezkazgandeposit. In contrast, their Permian counterparts in thewestern Ural region and Donbas contain abundantremains of coalified plant tissues and shales with a

green rim, suggesting the reduction of Fe. Theseregions incorporate only small deposits, because theenvironment was unfavorable for the transport of largemasses of Cu. Thus, mobility of Cu in Paleozoic conti-nental red rocks also varied depending upon conditionsof the burial of organic matter.

As was mentioned, the third (Mesozoic–Cenozoic)stage of Cu accumulation in the Earth’s history wasleast productive. Decrease in the Cu accumulation dur-ing this stage could be related to variation in the forma-tion condition of red rocks. Mesozoic–Cenozoic redrocks formed in the course of postsedimentary oxida-tion of primary gray rocks. Therefore, the red rocksretained the relatively low Eh values corresponding tothe boundary between stability fields of bivalent andtrivalent Fe species (Fig. 3). Under such conditions,mainly insoluble (sulfide and metallic) forms of Cucould be developed in the red rocks.

Deposits of the cupriferous sandstone and shale typehave not been found so far in Quaternary sediments.This can be explained by the absence of Quaternaryarid red rocks. According to (Rukhin, 1969), the forma-tion of cupriferous sandstones and shales in the Quater-nary period is hampered by the abundance of grasscover that was not developed in dry regions in the pre-vious period. However, based on the study of present-day and Tertiary (alluvial, deltaic, coastal-marine,evaporitic, and eolian) sediments in the maritime desertregion of northern Baja California, Walker (1967) dem-onstrated that several millions of years are needed forthe formation of red rocks. Although such sedimentswere accumulated under constant facies and climaticconditions, one can see gradual change of color fromgray to red during the transition from Quaternary sedi-ments to Tertiary ones. This is related to the decompo-sition of Fe-bearing clastic minerals, which produce theauthigenic ferruginous pigment. Migration and disper-sion of Fe are caused by fluctuations of Eh and pH inpore solutions.

According to data presented in (Ronov, 1983), theFe content in the Earth’s sedimentary shell graduallydecreases due to the reduction of areas with exposuresof basic effusive rocks. Decrease in the Fe content isaccompanied by decrease in the background Cu content(Fig. 4). Since intensity of the formation of ore solu-tions in red rocks allegedly influences the average Cucontent therein, the gradual decrease in the Cu contentshould be reflected as decrease in the ore-generatingpotential of the red rocks.

CONDITIONS OF COPPER CONCENTRATION

Investigation of cupriferous sandstones and shalesof different ages revealed that Cu was precipitated inthe sulfide form. Isotope data indicate the biogenic ori-gin of sulfide sulfur in ores. Sulfate-reducing bacterialplayed a crucial role in the generation of hydrogen sul-fide during the formation of sulfide ores. Hence, the

300

200

0

100

Cu, ppm

Fe

Fe, %

Cu

6

4

0

2

MZPZ10 2

A PR1 – 221

PR3

Share of cupriferous sandstones and shales, %

Fig. 4. Variation in the average content of Fe and Cu inshales along the stratigraphic scale. Modified after (Ronov,1983).



presence of fossil organic and sulfate-reducing bacteriais essential for Cu concentration.

Carbonaceous matter and problematic organicremains are known in sedimentary rocks since 3.8 Gaago (Isua, Greenland), whereas undoubted stromato-lites and siliceous microfossils are known since 3.5–3.3 Ga ago (Krylov, 1983). Anaerobic sulfate-reducingbacteria are likely among the oldest living organisms.Like the stromatolite builders (cyanobacteria), theanaerobic bacteria appeared more than 2 Ga ago.Results of their vital activity (iron sulfides in carbon-aceous sediments) are known at the oldest levels of Pre-cambrian sedimentation. Thus, conditions needed forthe Cu concentration in sedimentary rocks appeared noless than 3 Ga ago.

Cupriferous sandstones and shales formed at synge-netic and epigenetic geochemical barriers. The synge-netic barriers are particularly interesting for investiga-tion of the periodicity of Cu accumulation in the Earth’shistory. Their formation is related to the simultaneousaccumulation of organic matter and sediments. Suchbarriers are known in the shallow-water marine,lagoonal, boggy, channel, and deltaic facies settings.The shallow-water marine and lagoonal barriers, whichwere typical of the entire history of cupriferous sand-stones and shales, are most widespread. Sediments ofthe shallow-water marine facies host several Precam-brian deposits, such as the majority of deposits in theCopper Belt of Africa, White Pine deposit (Fig. 5a), oreoccurrences in the framing of the Siberian Platform.This facies also includes many Phanerozoic deposits(Mansfeld, Lubin-Sieroszowice, and cupriferous sand-stones in the Kazanian Stage of the western Cis-Uralregion). Maximal Cu accumulation in the Precambriansedimentary sequences corresponds in time to the Mid-dle Riphean period of blooming and rapid spreading ofstromatolite builders (cyanobacteria) in the Earth(Fedonkin et al., 1987; Semikhatov, 1987). Their vitalactivity produced organic-rich sediments over vastareas of previous seas.

It is evident that the possibility of cupriferous solu-tions running against the potential geochemical barriersdepends on the scale of barriers. Hence, the develop-ment of carbonaceous sediments in the terminal Pre-cambrian over large areas provided maximal facilitiesfor Cu concentration. The boggy and channel faciesappeared only since the Devonian owing to the devel-opment of land plants. These geochemical barriersbecame particularly widespread since the Permian.However, fragmentary character of the burial of planttissues in continental sediments resulted in the disper-sion of Cu as numerous small ore occurrences (e.g.,cupriferous sandstones in Upper Permian sequences ofthe western Cis-Ural region). Large Cu deposits of thistype are unknown.

Epigenetic geochemical barriers appear at catage-netic stages in the course of the percolation of reducers(oil waters, bitumens, oil, and gases) in collector-rocks

of red-bed associations (Fig. 5b). Such barriers arecommonly represented by the clastic and coarse-clastic(deltaic, alluvial, proluvial, fan, and others) facies ofred rocks with signs of local catagenetic alterations,such as bleaching, pyritization, and calcitization(Gablina, 1983), as well as bituminization in someplaces (Rzhevskii et al., 1988). Their formation in theEarth’s history was provided by two essential condi-tions: the presence of organic matter and the develop-ment of carbonaceous formations near the red molassicsequences. Hence, availability of corresponding combi-nations of geological factors could provide the forma-tion of epigenetic barriers and associated copper depos-its without any variations over the whole time intervalunder consideration. The largest copper deposits of thistype (and associated syngenetic barriers) are found attwo stratigraphic levels coinciding with peaks of theaccumulation of carbonaceous sediments, on the onehand, and the abundance of red rocks, on the otherhand. The first (Riphean–Vendian) level incorporatessome deposits in Zambia and separate orebodies con-fined to the Izluchin Formation at the Graviika deposit.The second (Permian–Carboniferous) level includesthe Dzhezkazgan deposit.

Thus, conditions essential for the formation ofcupriferous sandstones and shales appeared simulta-neously with the origination of the first arid red rocks,which served as ore-generating formations for Cu,more than 2 Ga ago. Variation in the setting of exogenicCu accumulation in the Earth’s history is related to theevolution of living matter in our planet. Maximum Cuconcentration in the Riphean–Vendian corresponds intime to the blooming period of cyanobacteria. Appear-ance of land plants in the Phanerozoic promoted theformation of barren red rocks and the facies diversity ofsediments that served as geochemical barriers.

SPECIFIC FEATURES OF THE FORMATIONOF LARGE AND UNIQUE COPPER DEPOSITS

IN SEDIMENTARY SEQUENCES

Irrespective of dimension, cupriferous sandstoneand shale deposits are characterized by common regu-larities of structure and localization. However, they canform only under the following conditions: (1) the pres-ence of large sedimentary basins with red rocks; (2) thepresence of large geochemical barriers; and (3) thelong-term and unilateral development of sulfide-form-ing process (Gablina, 1997). In the case of depositsassociated with syngenetic barriers, the first and secondconditions are provided by marine transgression intoforedeeps and intermontane depressions filled with redsediments (Fig. 5a).

The table shows that large and giant deposits of thistype are related to large marine barriers. Local(intraformation) syngenetic barriers of the channel,boggy, and other facies formed in the continental set-ting incorporate small separate ore deposits and occur-rences scattered over a large area (e.g., deposits of the

146



Kargalin group in the Ufimian red rocks of the westernUral region and ore occurrences in the Kartamysh For-mation of the Donbas region).

However, some areas with large marine geochemi-cal barriers incorporate only small ore deposits (e.g.,ore occurrences in the Belebeev and other zones of theKazanian Stage in the western Ural region). Althoughore occurrences discussed above and cupriferousdeposits in Europe (Zechstein type) formed in similarspatiotemporal settings, one can see certain differencesbetween them. Marine Zechstein sediments overlielarge troughs (depth up to 600–1000 m or more) filledwith the Rotliegende. In the western Ural region, such

large depressions with red coarse-clastic rocks areabsent at the Kazanian seafloor and the coarse-clastic(permeable) rocks fill up only fragments of channel (upto 10-m-deep) downcuttings in the Ufimian red clayeyrocks beneath the Kazanian marine sediments (Fig. 6).This feature is clearly reflected in the scale of mineral-ization. Low productivity is also typical of syngeneticbarriers at the base of red rocks (Horizon A of theIgarka district, Northern group of copper deposits in theDzhezkazgan district, as well as Unkur and other cop-per ore occurrences at the base of the Middle SakukanSubformation and Aleksandrov Formation of theKodar–Udokan zone), because processes of diffusion

(a)White Pine

ore zoneNonesuch sea level

Nonesuch sediments

Copper HarborCopper Harbor

RhyoliteRange

Portage Lake lave series

1

Fig. 5. Models of the formation of copper deposits in sedimentary sequences at (a) syngenetic and (b) epigenetic geochemical bar-riers. (a) Formation model of the White Pine deposit in H2S-bearing bottom sediments of the marine basin (White, 1971).(1, 2) Inferred direction of groundwater motion in the underlying Copper Harbor red rocks: (1) infiltration, (2) elision. (b) For-mation model of the Dzhezkazgan deposit in the rebleached collector-rocks (Gablina, 1983). (1) Red mudstones and siltstones;(2) red sandstones and conglomerates; (3) gray sandstones and conglomerates; (4) dissemination of copper sulfides; (5) pyrite dis-semination; (6) gray mudstones and siltstones; (7) limestones; (8) ore lodes; (9) direction of the percolation of Cu-bearing solutions:(10) migration paths of reducers (hydrocarbons and H2S). (P1gd) Lower Permian rocks (Gidelisai Formation); (C2–3dg) productive Mid-dle–Upper Carboniferous Dzhezkazgan (red rock) Sequence; (C1n) marine Lower Carboniferous gray sediments (Namurian Stage).

(b)

2

SW

NE

Oxidizing settingzone

Zone of interaction between oxidizing and reducing settings

Hydrosulfuric

setting zone

Kingirpaleoridge

Modern erosionlevel

Cu

Cu

Cu

Cu

C1n

P1gd

Red rocks

ë2–3dg

Transitionalmember

Gray marinesediments

12345

678910

Cu



responsible for mineralization of this type can only pro-duce low-grade sulfide dissemination in gray rocks atthe contact with red rocks.

Large deposits can only be formed at epigenetic bar-riers in the case of the presence of large sedimentarybasins with the elisional regime of groundwaters andsynsedimentary uplifts, near which the groundwaterscould discharge (Fig. 5b). Epigenetic barriers can onlyform under conditions of the existence of conjugated

bituminous rocks (sources of reducers) and faults (orlithological windows), which could promote thehydraulic connection between geochemically contrast-ing solutions (fluids). These conditions were availablein Dzhezkazgan located on the slope of the synsedi-mentary Kingir Uplift in the northern sector of the largeDzhezkazgan–Sarysui Depression filled with continen-tal red sediments of the Dzhezkazgan Sequence. Thered Dzhezkazgan Sequence is underlain by a thickLower Carboniferous carbonate (oil- and gas-generat-

1

2

3

4

5

6

7

8

9

10

11

12

13

ÄB

CE

F

G

(a)

D

Fig. 6. (a) Paleogeographic scheme of the Belebeev sector at the end of the Ufimian Age and (b) lithofacies profiles (Lur’e andGablina, 1972). (1, 2) Continental sedimentation settings: (1) coastal plain (primarily, red shales and siltstones), (2) channels andfans (primarily, red sandstones); (3–5) basinal sedimentation settings: (3) bars and shoals (gray sandstones), (4) sectors with ele-vated salinity (dolomites, gypsum, siltstones, and shales with gypsum), (5) freshened lagoons (intercalation of red shales, siltstones,and less common sandstones); (6) areas characterized by the complete erosion of Kazanian rocks; (7) abandoned deposits; (8) min-eralized zones in sections (Cu > 0.1%); (9–13) Cu content at the base of Kazanian marine sediments (Linguba Member, kg/m2):(9) <2.5, (10) > 2.5, (11) >5, (12) >10, (13) >20. Ratio of horizontal and vertical scales in the sections is 1: 10.

148



ing) sequence, which could serve as the source ofreducing fluids (Fig. 5b).

Duration of mineralization plays a significant role inthe formation of giant deposits. Ores of the Dzhezka-zgan deposit formed in the course of catagenesis andmetagenesis of enclosing sediments. The long-termevolution of these processes was provided by stabilityof hydrodynamic regime in the Dzhezkazgan–SarysuiDepression. An elisional groundwater regime wasdeveloped in the basin due to its long-term (Devonian–Permian) synsedimentary subsidence. Waters squeezedout from clayey sediments percolated along aquifersfrom the depression center to flanks and local uplifts.Ores were deposited near the synsedimentary KingirUplift crosscut by long-lived deep faults. Waters withcontrast geochemical characteristics were dischargedand mixed in this zone for a long time (Gablina, 1983,1997).

Formation of the giant Lubin-Sieroszowice depositwas related the activity of a syngenetic barrier at theboundary between the organic-rich basal Zechstein lay-ers and the underlying Rotliegende. This process con-tinued during syngenesis, diagenesis, and catagenesisof enclosing rocks. At initial stages, Cu was deliveredto nonlithified Zechstein sediments during the dis-charge of slightly oxidizing elision waters from theunderlying red rocks located at the Zechstein seafloor.Oxygen-bearing waters were delivered to lithifiedZechstein rocks along the same conduits (permeablelayers of the Rotliegende) in a different hydrodynamicsetting of the later stage. Their long-term influence fos-tered the oxidation, redeposition, and considerableenrichment of primary copper ores, as well as the inputof new ore elements (Gablina, 1997; Ermolaev et al.,1996; Wodzicki and Piestrzynski, 1986). Rocks of theUdokan Sequence were initially mineralized duringdiagenesis and catagenesis of enclosing rocks at the

A B(b)

B a s a l b e dUfimian Stage5700 m

L i n g u l a m e m b e r

B a s a l b e d

Ufimian Stage

C D

E FB a s a l b e d L i n g u l a m e m b e r

Ufimian Stage

1325 m

Lingula member

Ufimian Stage

F G

L i n g u l a m e m b e r

Fig. 6. Contd.



syngenetic barrier (members of primary gray pyrite-bearing rocks in a thick red sequence). The present-dayappearance of the Udokan deposit was developed in thecourse of the whole (Proterozoic–Recent) history ofore-enclosing rocks. In this process, the Cu concentra-tion was significantly controlled by superimposed pro-cesses related to the regional and contact metamor-phism and hypergenesis (Gablina, 1997; Gablina andMikhailova, 1994).

PERIODICITY IN THE FORMATION OF CUPRIFEROUS SANDSTONES AND SHALES

The stratigraphic distribution of cupriferous sand-stones and shales lack any explicit periodicity (table).One can only see an irregular distribution of ore depos-its in the stratigraphic scale.

However, periodicity in global changes is wellknown, e.g. the formation and breakup of superconti-nents (Wilson Cycle); Bertrand Cycle (~180 Ma); peri-odic fluctuations of the World Ocean level; periodicityof glacioeras, biospheric rhythms, and so on. The for-mation of ore deposits should also be associated withthese processes. We should investigate cupriferoussandstones and shales against the background of globalchanges in order to unravel the hidden periodicity intheir accumulation. This approach reveals a clear linkof unique and large deposits with the Panotia and Pan-gea supercontinents (Fig. 7). Large deposits of the Cop-per Belt of Africa, White Pine (Lake Superior, UnitedStates), and Ainak (Afghanistan), and, probably, theunique Udokan deposit were formed in the Panotiasupercontinent. Existence of Pangea fostered the for-mation of very large deposits of the Dzhezkazgan group(Kazakhstan), copper deposits confined to the Rotlieg-ende and Zechstein rocks of Europe (Mansfeld, Sanger-hausen, Reichelsdorf, and others in Germany), and thegiant Lubin-Sieroszowice deposit (Poland).

This pattern of the formation of cupriferous sand-stones and shales is natural from the point of view ofthe model described above. The existence of thicksequences of ore-generating red rocks and carbon-aceous geochemical barriers is essential for the forma-tion of large deposits. The formation of thick continen-tal red sequences is related to climatic features of super-

continents. Their environment was most favorable forthe formation of giant ice sheets and specific climaticconditions characterized by virtual absence of thehumid tropical belt (Zharkov, 2004). Onset of thebreakup of the supercontinents was dominated by thecontinental arid climate at their lower and middle lati-tudes, as suggested by the Permian and Triassic paleo-geography of Pangea (Zharkov, 2004).

Lowstand of the World Ocean during the onset ofextension of the Earth’s continental crust promoted theaccumulation of huge masses of red rocks in the newlyforming grabens. The specific type of atmospheric andoceanic circulation related to glaciation was retainedafter the degradation of glaciers. For example, a humidtropical belt appeared only in the Albian (Chumakov,2004) almost 100 Ma after the degradation of glaciers.Therefore, accumulation of red rocks coupled withsandstones and shales is not drastically terminated butgradually decreased. For example, the Middle–UpperCambrian level incorporates only one moderate-sizedeposit (Timna, Israel) and some small ore occurrencesin the West Arabian cupriferous zone, southern framingof the Siberian Platform, and others (Narkelyun et al.,1983). The maximum Cu accumulation in the UpperJurassic–Lower Cretaceous related to deposits in theNorth African province and China (Yunnan and Heiliore districts) is much smaller than the Permian peak.

Thus, large exogenic copper deposits were formedduring glacioeras and the subsequent arid epochs.However, the prolonged (Middle Ordovician–Silurian)glacial period, which was not accompanied by strongdecrease in the World Ocean level and large-scale con-tinental glaciation, did not promote the formation oflarge copper deposits. In addition to small ore occur-rences at the framing of the Siberian Platform, only onemedium-size cupriferous clay deposit (Mount Lyell,Australia) is known in Late Ordovician rocks (Narke-lyun et al., 1983). Thus, the scale of glaciation showsinverse correlation with the size of copper deposits.This regularity is also typical of all other Phanerozoicore-bearing and petroliferous rocks (Malinovskii.1982).

Maximums of cupriferous sandstones and shaleslack any periodicity, but their minimums correspond toEarly Ordovician, Early Carboniferous, and Late Creta-

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Fig. 7. Copper deposit in shales against the background of very intense global alterations. Dots show red rocks according to (Ana-tol’eva, 1978). Deposit numbers are as in Fig. 2.

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ceous. Interval between the minimums is approxi-mately 180 Ma (Bertrand period). These epochs arecharacterized by the minimal accumulation of red andcarbonaceous rocks, the maximal World Ocean level,and the maximal expansion of humid tropical zones.The latter process also continued at the beginning ofglacioeras.

Transition from warm eras to glacial epochs isapparently paradoxical, because the maximal warmingis abruptly replaced by the glacial process against thebackground of highstand of the World Ocean and themaximal reduction of arid zones. As is known, suchperiods are characterized by reduction of the Earth’sreflectance (albedo) and increase of the solar energyinput. Transition from glacioeras to warm epochs is noless surprising: drastic cooling is suddenly replaced bywarming in the course of the maximal development ofcontinental glaciation and climate aridization when theEarth’s surface can only consume a minimal portion ofsolar energy. Degradation, for example of the Permianice sheet, took place without any change in the positionof Pangea (Zharkov, 2004). Such paradoxical scenariocan testify to self-oscillating nature of the phenomenon(Malinovskii, 2007). Such self-oscillations took placein the biosphere, that according to V.I. Vernadsky, theprocess of natural oscillation includes living matter,hydrosphere, troposphere, and upper part of the lithos-phere. What is their possible mechanism?

The water column of the present-day World Oceanis mainly stratified by temperature. Temperatures ofdeep and intermediate waters are approximately 2.5°C,on average. According to (Huber et al., 2000), the tem-perature of deep waters of the Late Cretaceous oceanvaried from 7–11 to 20%C before the onset of glacioeraand the waters were stratified by salinity. They flowedfrom equators to poles (Kuznetsova and Korchagin,2004). In contrast, the present-day water current isdirected from poles to equator. Following (Lisitsyn,1989), we can accept that all glacioeras were character-ized by T-circulations, whereas warm eras were charac-terized by S-circulations. The T-circulation is formedby “natural refrigerators” near poles, whereas the S-cir-culation is related to the sink of warm saline waters inarid zones. The T-circulation creates the “cold ocean,”while the S-circulation creates the “warm ocean.” How-ever, Lisitsyn believes that the climate of continent onlydepends on the type of its new climatic zone. The S-cir-culation is much weaker than the T-circulation, as sug-gested by the absence of contourites at the bottom ofthe Cretaceous ocean. The point is that water circula-tion should be weak in the Cretaceous (particularly,Late Cretaceous) when the water was almost com-pletely stratified by salinity.

The T-circulation comes to a standstill when theentire ocean becomes cold. Consequently, surficialwarm currents of the Golf Stream type do not operateand heat is not transferred to poles. Thus, the environ-ment becomes favorable for the maximal glaciation and

aridization of climate. This process leads to the forma-tion of heavy (high-salinity) warm waters at low lati-tudes of the ocean. After the accumulation to a certainlimit, the waters sink to deep zones and flow to poles.Thus, the currents drive the interoceanic conveyer anddestroy the glaciation. This scenario is typical of thefirst (carbonaceous) phase of biospheric rhythms (Mali-novskii, 2007) that can be compared with the globalupwelling. The atmosphere is concentrated with CO2owing to the upwelling and the input of biogenic ele-ments into the oceanic photosynthesis zone. Ultimately,this process is accompanied by the augmentation ofbioproductivity and the emission of carbon in bothmarine and continental ecosystems (Malinovskii, 1982,2007). Thawing of glaciers fosters the rise of the WorldOcean level. Carbonaceous sediments of the firstphases of biospheric rhythms overlie the ore-generatingred rocks formed during the “calcic” phases of previousrhythms, resulting in the formation of syngeneticgeochemical barriers.

Consumption of the high-salinity warm waters isaccompanied by the retardation of oceanic currents,resulting in the gradual onset of the second (“calcic”)phase of biospheric rhythms. This phase goes on for amore prolonged period (relative to the carbonaceousphase) until the accumulation of the next critical massof waters at low latitudes. The process can be initiatednear critical states by external forces (fall of space bod-ies, earthquakes, and so on). Thus, the S-circulationresponsible for the warm ocean also represents a rhyth-mic process (biospheric rhythms). Heating of all watersof the ocean is followed by the gradual attenuation ofthe S-circulation, resulting in expansion of zones withthe humid tropical climate, termination of the processof accumulation of high-salinity waters in the interoce-anic conveyer, and cessation of the delivery of heat topoles (Malinovskii, 2007).

Such conditions existed in the Early Ordovician,Early Carboniferous, and Late Cretaceous. Theseepochs were characterized by the low amount of car-bonaceous sequences, minimal accumulations of sedi-mentary deposits, and maximal deposits of carbonates.Stratification of waters of the “warm climate” and theconsequent weak functioning of the interoceanic con-veyer against the background of warm humid climateprovoked continental glaciation in the Middle Ordovi-cian, Middle Carboniferous, and Paleogene. Portions ofcold and denser waters accumulated near the polar“refrigerators” were transported to the equator in deepzones of the ocean, resulting in the T-circulation andbiospheric rhythms. Biospheric rhythms of both T- andS-circulations have a similar structure: the first phasehas the carbonaceous composition, whereas the secondphase has the calcic composition. The first phase pro-motes a short-period humidification of climate,whereas the second phase is often terminated by theformation of salts. The well-known triad (carbonaceoussediments–carbonates–salts) represents biosphericrhythms (Malinovskii, 2003).



Cupriferous sandstones and shales occupy a certainposition in the biospheric rhythms at the boundarybetween the “calcic” phase and the “carbonaceous”phase of the next rhythm. The “carbonaceous” phase ofbiospheric rhythm begins drastically and graduallygives way to the “calcic” phase. During glacial epochs,the carbonaceous phase is accompanied by the oceanlevel rise due to the periodic melting of ice. Therefore,carbonaceous sediments can more often overlie thecontinental red sequences formed during the calcicphase of the preceding biospheric rhythm. The “calcic”phase of biospheric rhythms is characterized by theintensification of climate aridization, which reaches themaximum degree at the end of the “calcic” phase. Con-sequently, the most contrasting transitions of sedimen-tation environment coincide with the barriers of bio-spheric rhythms, resulting in the development ofgeochemical barriers that are involved in the formationof exogenic copper deposits.

Thus, the formation of cupriferous sandstones andshales is governed by the general law of periodicity inthe accumulation of petroliferous and ore-bearing sed-iments in accordance with the Bertrand and Wilsoncycles. However, the Wilson cycle (~400–450 Ma),which is related to the maximal development of redrocks at supercontinents, plays the major role in thisscenario.

CONCLUSIONS

1. Relationship of cupriferous sandstone and shaledeposits with red molassic sequences is explained bythe mobility of Cu (Cu+) in a weakly oxidizingmedium, which is typical of formation waters in the redsequences. Cu is precipitated as sulfides at the H2S-richbarriers of two (syngenetic and epigenetic) types.

2. Decrease in the Cu concentration in the Earth’ssedimentary shell from the Precambrian to Cenozoiccan be related to the influence of the following pro-cesses: evolution of living matter in the Earth’s history;decrease in the background Cu content in sedimentaryrocks; and variation in the formation condition of redrocks.

3. Maximal Cu concentrations in the sedimentaryshell is mainly related to the presence of large andunique deposits (reserve more than 10 Mt) that can onlyform under the following conditions: the presence oflarge depressions filled with ore-generating red rocks;the presence of large areas of reducing barriers; and thelong-term process of ore formation. Therefore, the old-est copper deposits, the formation of which is stillgoing on due to secondary enrichment in the hypergen-esis zone, also often represent the largest Cu concentra-tors in sedimentary rocks.

4. The periodic formation of cupriferous sandstonesand shales is related to global biospheric rhythms. Themajor epochs of copper accumulation coincide withinitial stages of the rearrangement of gyres and corre-

spond to the replacement of the calcic phase of largebiospheric rhythms by the “carbonaceous” phase of thenext rhythm.

5. Periodicity of the maximal Cu accumulation inthe Earth’s history described in our work coincides withperiods of the maximal development of red rocks atsupercontinents (Panotia and Pangea), the originationperiod of which corresponds to the Wilson cycle (400–450 Ma).

ACKNOWLEDGMENTS

This work was supported by the Earth SciencesDivision of the Russian Academy of Sciences (programno. 2) and the Russian Foundation for Basic Research(project no. 05-05-64952).

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Documents

Periodicity of Copper Accumulation in the Earth’s ... · 2–3), Poland (Lubin-Sieroszowice), Germany (Mansfeld, P 2), and other regions. Mesozoic–Cenozoic deposits are represented