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(MINING

GEOLOGY),39(6),393401,1989

2,3

Fe-Mn

**

Chemical composition of chlorite with special reference to the iron vs. manganese variation,
from some hydrothermal vein deposits, Japan.
By Tetsuro YONEDA
Abstract:
Chlorite, which occurs commonly as a gangue mineral in four hydrothermal vein deposits, that is, Chitose,
Yatani, Sado and Ohe, was quantitatively analyzed by X-ray microanalyser. Chlorite from Yatani, Sado, and Ohe, is
Fe-rich, while chlorite from Chitose is Mg-rich. The chlorite geothermometer (WALSHE,1986) applied to these vein
chlorites gives temperatures equivalent to or slighly lower values than those obtained by fluid inclusion thermometry.
They contain a large or small amount of manganese (maximum MnO content 17.5 wt. % at Sado deposit), and show
Fe-Mn compositional variation at more or less constant MgO content in each vein. This is probably owing to their
difference of time and space of chlorite formation. For example, the activity of Fe2+ ion relative to that of Mn2+ ion in
hydrothermal solution decreases with temperature lowering at Chitose and Yatani deposits. While, the activity ratio increases with decreasing temperature at Sado and Ohe deposits.

The exchangeof Fe2+ and Mn2+ betweenchlorite and hydrothermal solutionis a function of physicochemical
parameters (e.g. temperature, oxygen fugacity, pH, total dissolvedsulfur, and activity of Mn2+ and Fe2+ ions in
aqueous solution). It is inferred that the compositionalvariationof chloritein a vein might be influencedby the localor
temporal changesof hydrothermalenvironments, such as oxidation-reductionstate and/or temperature.

NIEVA,

1.

).

, .
,

1985;

SHIKAZONO

WALSHE,

and

1986;

KAWAHATA,

BRINDZIA
1987;

and

OHTA

and

Fe-Mg

SCOTT,

1987;

YAJIMA,

1988

Fe-Mg

Fe/

Mg

Fe/

, ,

, ,

Mg

. ,

, Fe-Mn

( ,1960;

. ,

1976 ).

, ,

Fe-Mn

2.

3 , 2 ,

and SOLOMON,

1981; STOESELL, 1984; SVERJENSKY, 1984; CATHELINEAU

( WALSHE

and

,
.

198933

,1989118

*1989131
**

39

(Department
sources

Development

Sapporo 060,

Keywords:
variation,

Engineering,

Hokkaido


of

Re-

University,

Japan)

Chlorite,

Chemical

Hydrothermal

vein,

composition,
Physicochemical

, , ,

Compositional

. ,

parameter.
393

394
Table

Mineral

A brieaf

description

of ore samples

which

:
contain

chlorites.

abbreviation
chl:chlorite,
ser:sericite,
sm:smectite
, c/s:chlorite/smectite
interstratified
mineral.
ad:adularia, qz:quartz,
rhc:rhodochrosite,
carb:carbonate
mineral,
ht:hematite
, sp:sphalerite.
py:pyrite,
gl:galena,
cp:chalcopyrite,
th:tetrahedritetennantite.
Ag:Ag-mineral.
el:electrum.
Ginguro
is
a fine-grained
mixture
of
several
sulfides
including
quartz,
silver
mineral
and
electrum.
The
literal
meaning
of
ginguro
is
silver-black
ore .


( ,1970;
SHIMAZAKI,1986),

YAJIMA,

1979;

SHIKAZONO

and


Table 1 . ,

, ,

(YT-A,

B)

(Fig.1),
YT-B

YT-A

( )
,YT-BYT-A
.


,SATO

et al,(1980)

2,3

39(6),1989

Fe-Mn

III .

(1989)

001

B),

trioctahedral

B),

3.
3.l

EPMA

EPMA
50A

JXA-

JXA-733

(1989)
Table
FeO

.
Mn

MnO,

Fe

(CT-2),
(SD-1,SD-2)

(CT-1,2)trioctahedral

(Fig.2).

(YT-A,

Table

,
2

, 61wt.%

,
,

(YT-A,

(OE-1,2)

7A

,
Mg


,OINUMA

(SD-13),

.X

(14A,7A,4.7A)

et al.(1972)

Fe

395

Fig. 2 I(14A)-I(7A)-I(4.7A)
plots for chlorite on a
diagram after OINUMAet al. (1972). Chitose (CT 1,
CT-2), Sado (SD-1, SD-2, SD 3), Yatani (YT-A,
YT-B), Ohe (OE-1, OE-2). See text for discussion.

Fig. 1
Photomicrographs
of chlorite,
showing two
different occurrences
in a ore sample (Yatani,
86050603). See Table 1 for explanation of A and B, and
for abbreviations.

II

. ,

,
(CT-1)

(YT-A/B)

, EPMA

. ,
(SD-1,SD-2)

, (ATEM)

396
Table

The results

co-existing

of EPMA

sericite.

PT:

analysis

analytical

of chlorite.

number

The values

in the brackets

are the corrected

ones

for the contamination

, , (

) ,

. SiO2,

( Fig.3

).

FeO,

EPMA

.
3.2

MgO

,O10(OH)8(

28)

(Table 3) ,

, Mg

(MnO=1.117.5wt.%)

MnO,

Al2O3,

. ,

Fe

of

of the sample.


,EPMA

Table

Si

0.81.2

A1
,

Mg

39(6),1989

2,3

.
1.221.87

A1

Mg

5.875.59
.
Si-total

Fe

Fe-Mn


(Table3).

397

Fe-Mn-Mg

(Fig.5).

A1-R2+(Fe+Mn+Mg)

(Fig.4),

Table

Structural

in Table

formula

of chlorite.

PT:

the same

as

2.

Fe,Mn,Mg

Fe

Fig.

FeK)

Comparison
between

tron

microscope

Sado

deposits.

Fig. 4

Si-Al-R2+

triangle:

Ohe.

of
EPMA

X-ray
and

(ATEM)

atomic

Mn

intensity
analytical
analyses

ratios

ratio

(MnK-

transmission

elec-

for

from

chlorite

for chlorite.

Small

solid circle:

Chitose,

large

solid circle:

Yatani,

solid square:

Sado,

solid

398

and NIEVA(1985)

, Los

Azufres

A1
6
,

Vacancy

. , (1985) ,

, A1

.
,Salton

,WALSHE(1986)

Sea

,

.
,
,WALSHE

, ,
Fig. 5

Mg2+-Fe2+-Mn2+

Marks

correspond

dicate

trends

part or earlier
vein.

atomic

to the same

ratios

for

chlorite .
in-

2C2 (Mg5Al2Si3O10
(OH)8) + 14/3SiO2+8/3H2O=

as in Fig. 4. Arrows

for compositional
stage to upper

variations,
part or later

from

lower

C5 (Al4Si4O10
(OH)8) +10/6C1(Mg6Si4O10 (OH) 8)

stage in each

,C1,
)

. C1,

C2(

, , ,

C3(

)(Mn25+Al2Si3O10(OH)8)

Mn

,Fe/

. , , ,

,Fe/Mn

,C1,C2,C5

and

HELGESON
HELGESON

Fe/Mn

( ,

. , , ,
Mg

, 2:1

Table

and KIRKHAM(1974),

et al.(1978)WALSHE(1986)

500bar

C5
C7(

WALSHE(1986)

, Fe/Mn

SOLOMON(1981)

( , ),

(WALSHE

),

.
WALSHE

C5

)(Fe25+Al2Si3O10(OH)8),

C2,

Fig.6

(Fig.6

( ,1981,1986),

, .

.
,
Fe-Mn

Mg

150200C,

50 ,
(CT-1)

(CT-2)

, ,

,

(YAJIMA,1979)

, (SD-2,

4.

3),

(SD-1)

.
(240260C)

(200250)

. , ,
CATHELINEAU

39(6),1989

2,3

Fe-Mn

399

Fig. 7 Relation between temperature of chlorite formation and the the number of Al ion in the tetrahedral
sheets of chlorite.

,Los

Azufres

Al
(CATHELINEAU

and

NIEVA ,1985)

5.

Fe-Mn

Fe-Mn

(C7)

Fe2+

(C3)

Mn2+

Fig. 6

Temperature

of chlorite formation calculated fr

Mn2+

the chlorite geothermometer


(WALSHE,1986). Bars indicate temperature ranges of ore formation es
timated from the fluid inclusion study.

200240(YT-A),260280(OE-1)

B),230280(OE-2)

aMn2+) .
HELGESON

SVERJENSKY(1984),WALSHE(1986)
.

S,V

, (Fig.6).

10 ,

.
, WALSHE

et al.(1981),
,

25C,1

MAIER-KELLEY

C7+FeO=C3+MnO
V=0,Cp=0

(aFe2+/

et al.(1978),HELGESON

. ,

,500bar

Fe2+Mn2+

, 170190(YT-

Fe2+

,S=0,
.

, ,

Fe2+Mn2+


Fig.8

, ,

Fe2+-Mn2+

, . , ,

, A1
Fig.7

WALSHE(1986)

400

Log(aFe2+/aMn2+)aqueous

Fig. 8 Temperature-Log (aFe2+/aMn2+)


aq diagram. Based
on the multisite mixing model for chlorite shown by
WALSHE
and SOLOMON
(1981), and WALSHE
(1986). The
Fe-Mn compositional variation of chlorite corresponds
to the variation of temperature and aFe2+/aMn2+
of
hydrothermal solution, and they appear to show two
different trends, i.e. I for Chitose and Yatani, and II for
Sado and Ohe. Marks are the same as in Fig. 4.

Fig. 9 Temperature-Log fo2 diagram. Equi-compositional curves of chlorite (log (ac7/ac3)=0.0, -5.0) are
shown. Arrows I and II indicate possible trends for the
variations shown in Fig. 8.

fo2
Fe2+-Mn2+

, Fe2+-Mn2+

, ,
fo2 ,

.
Fe2+-Mn2+
Fee+-Mn2+

Mg

Fig.5

, Fe-Mn

.
Fe-Mg

Fe2+-Mg2+

SHIKAZONO and
,

KAWAHATA(1987)
Fe2+

(fo2),

Fe2+-Mn2+

Mn2+

, pH,

.
Fe2+-Mn2+

fo2
. ,
-fo2

.

, Fe2+-Mn2+

pH

, ,

pH

Fe2+-Mn2+

.
, Fe2+-Mn2+

,

.

Mn2+
Fe2+-Mn2+
Fig.9
,

fo2
,

6.

HENLEY et al.(1984)

Fe-Mn
,

, pH

Mg2+-Fey+-Mn2+

(Fig.8)

, , ,
Fe2+-Mn2+

, fo2

. ,

Fe2+-Mn2+

Mn2+

Fe2+

39(6),1989

2,3

.
pH,

Fe-Mn

OHTA,

,
(

4,

E.

(5),

and

YAJIMA, J.

(1988)

indicator

of type

as

Mining

Geol.

K.,

J.

Spec.

for

Toyo

Univ.,

MAEDA,

Geol.,

from

and

H.,

temperatures

H.

deposits

and

differences

in

KAWAHATA,
chlorite

hydrothermal

from

ore

259`267.

function

CATHELINEAU,

M.

and

Sci.,

NIEVA,

D.

(1985)

system.

The

Contri.

H.

of the

trolytes
the

and

at high

: A

thermodynamic
pressures

Am. J.

Sci.,
H.

K.

274,

C.,

(1978)

J.

of

of aqueous

of the

of

NESBITT,

and

critique

H.
of

minerals.

KIRKHAM,
prediction

electrolytes

281,
HENLEY,

W.

the

and

BIRD,

WALSHE,

D.

Am.

and

J.

Sci.,

FLOWERS, G.

thermodynamic
pressures

activity

apparent

molal

properties

R.

W.,

to

TRUESDELL,

reactions

equilibria

in
1,

99`113.

in

A.

80,

Compositional

(1986)

altered

Min.,

25,

: Sulfur

vein-type

rocks

465`474.

isotope

study

deposits

solution

of

in Japan.

32,

: The

distribution

and

for

of divalent

oxides,

silicates

trace

and

basis.

hydro-

Geochim.

853`864.

: A six-component

the

model

205`212.

Thermodynamic

49,

site-mixing

Min.,

I.

L.

and

chlorite

conditions

of

geothermal

systems.

C.

(1981)

behavior

and

and

600

of

copper

and
Am.

H.

and

BARTON,
fluids.

system.

J.

P.

In

Fluid-mineral

Reviews

B.

Sci.,

(1984)

in

Econ.

and

(1979)
west

solid

chlorite

solution

formation
Econ.

in

Geol.,

81,

M.

(1981)

formation

of

using

six-component

Geol.,

76,

: Neogene

: An
the

geology,

mineralogy,

into

chlorite

solid

Mt.
stable
solution

246`284.

mineralization

Hokkaido,

investigation

volcanic-hosted

Japan.

of the
Bull.

Geol.

Teine-Chitose
Surv.

Japan,

645`674.

relative
J.

of
deposits,

Econ.

YAJIMA, J.

30,

osmotic

5 Kb.

model.

district,

temperatures:

standard

and

SOLOMON,

environment

Lyell

278-A,

coefficients,

hydrothermal

hydrothermal

(1987)

Can.

sulfides,

(1986)

and

J.

the

thermodynamic

1249`1516.

Redox

Geol.,

high

of

and

molal

H.

of the
at

Calculation

coefficients,

D.

epithermal
Geol.,

681`703.

M.,

rock-forming

C.,

aqueous

partial

L.

model

hydrothermal

solvent.

(1985)

Acta,

isotopes,

H.

Theoretical

IV.

A.

solutions:

WALSHE, J.

elec-

Summary

H.

Zn-Pb

: Regular
Clay

between

Cosmochim.

1`229.

HELGESON,

from
Econ.

15, 2331.

(1984)

D.

elements

1089`1198.

DELANY,

19,

Clays

SVERJENSKY,

solution

: Theoretical

I.

estimated

hydrothermally

SHIMAZAKI, H.

K.

therml

(1974)

properties

: Summary

properties

STOESELL, R.

ex-

geothermal

temperatures:

thermodynamic/electrostatic

HELGESON,

solid

behavior

and

An

235`244.

H.

Ohe

Mining

assemblage

(1986):
,
. , , 19, 8387.

chlorites.

chlorite

91,

D.

fugacity:

(Mexico)

Petrol.,

KIRKHAM,

of

50`76.

Azufres

Mineral.

C.

prediction

Los

composition

oxygen

287,

the

and

J.

geothermometer.

HELGESON,

sulfur

Am.

and

(1981):

of

study.

: Mineral

of
Japan.

Japan.

deposits.

J.,

as

(1980)

inclusions

in

Geochem.

. .

perimental

chlorites.

of temperatures

of fluid

vein-type

and

chlorite

S.
data

Hokkaido,

: A comparison

Au-Ag

: The

Triangular
of

electrum-sphalerite-pyrite-argentite

the Yatani

(1987)

1`33.

ONO,

deposits,

SHIRAZONO, H.

D.

and
inclusion

S.

(1972)

compositions
No.15,

Y.

fluid

. ,

SCOTT,

of

277`288.

filling

and

and

deposit.

KINRYD,

(1985)

the

SHIKAZONO,

T.

ratio

ore

1415`1424.

: ,

L.

iron

17`22.

T.

Education,

vein-type

Au-Ag

BRINDZIA,

12,

Suno,

chemical

and

30,

SHIKAZONO, H.

to

of hydrothermal
No.

(1970):

paragenesis

: Magnesium

and

Gen.

polymetallic

20, 149165.

SATO, J.,

. ,

S.

surveying

Issue,

SHIMODA,

diagrams

7, 7584.

383397.

chlorite

OINUMA,

Fe2+Mn2+

(1960):
,

401

(1976):

(1989):

/ .
.39,
181190.

(1985):
,
. , 25, 107112.