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MINING GEOLOGY, 41(5), 313•`327, 1991

Hydrothermal Synthesis of Wurtzite and Sphalerite at T=350•‹-250•Ž*

Shoji KOJIMA** and Hiroshi OHMOTO**

Abstract: Wurtzite and sphalerite were synthesized hydrothermally at 350•‹, 300•‹ and 250•Ž using a temperature-gra-

dient transporting method with sphalerite as a starting mineral. Fibrous wurtzite together with sphalerite was formed

only in experiments at 300•‹ and 250•Ž when a Zn-rich solution (1m ZnCl2+1 m NH4CI) was used as the transpor-

ting media; only sphalerite was produced in experiments using a Zn-free solvent (1m NH4CI). Formation of wurtzite

(vs. sphalerite) was not affected by the composition of the starting sphalerite nor by the addition of pyrrhotite and/

or alabandite to the starting materials. These results agree with a thermodynamic prediction that the solubility of

wurtzite is higher than that of sphalerite.

A comprehensive literature survey on the occurrence of wurtzite in hydrothermal ore deposits shows that
wurtzite is not uncommon in shallow subaerial deposits and in submarine hydrothermal deposits of relatively young
ages (mostly Tertiary or younger). For these'deposits, drastic physicochemical changes in the ore-forming solutions,
such as rapid cooling by mixing with local meteoric or sea water, have been postulated during ore mineralizations.
The wurtzite crystals often exhibit fibrous or radial textures, which would be produced by the above changes. Our ex-
perimental data and the occurrence of wurtzite in ore deposits suggest that hydrothermal wurtzite is a metastable
mineral that is formed by rapid crystal growth from highly supersaturated solutions.

20-25 mol% CdS) used in their experimental

Introduction
works are far from those for most natural

The stability relationships of two distinct wurtzites. Even the temperatures around

500•Ž for the minimum temperature of wurt-

phases of zinc sulfide minerals, sphalerite and
zite formation are much higher than those for
wurtzite, is an important subject in ore

mineralogy. Nevertheless, no clear explana- wurtzite in ore deposits, mostly T•¬350•Ž (see

tions for their relationships in natural ores ha- later section). Because natural occurrence of

wurtzite is limited in ore deposits formed at

ve yet been given. Some experimental studies
temperatures below 500•Ž, wurtzite has been
using a dry synthetic method have suggested
considered to be a metastable phase (BARTON
that wurtzite is stable only at temperatures
and TOULMIN, 1966; BARTON and SKINNER,
above 1,020•Ž for pure ZnS (ALLEN and CREN-
1979; RAMDOHR, 1980). Especially, BARTON
SHAW, 1912) and above about 850•Ž for Fe-
and SKINNER (1979) have suggested that high
rich compositions (BARTON and TOULMIN,
concentrations of impurities such as Mn and
1966). High concentrations of impurities, such
Cd may enhance the metastability of wurtzite
as Mn or Cd, contribute to an extension of the
at low temperatures.
wurtzite stability field to lower temperatures,
Based on the experimental results given by
500•Ž (TAUSON et al., 1977; TAUSON and
ALLEN et al. (1914), it was widely believed that
CHERNYSHEV, 1978; JANG, 1985). However, the
the wurtzite precipitation from hydrothermal
compositions of wurtzite (•`25 mol% MnS,
solutions was controlled by acidity and
Received on August 16, 1991, accepted on September temperature of hydrothermal solution. The
21, 1991
effect of acidity, however, has been suspected
* A part of this study was presented at the annual
by experimental studies including COREY
meeting of The Society of Mining Geologists of Japan
(1953), Kiyosu and NAKAI (1971) and SCOTT
held in Tokyo, February 2, 1990.
** Institute of Mineralogy and BARNES (1972). From hydrothermal
, Petrology and Economic
recrystallization experiments at T=300•‹ to
Geology, Faculty of Science, Tohoku University, Sen-
dai 980, Japan. 700•Ž, SCOTT and BARNES (1972) have sug-

Keywords: wurtzite, sphalerite, hydrothermal synthesis, gested that sphalerite and wurtzite are not
solubility, colloform texture, metastable phase polymorphs but independent phases with com-

313
 314 S. KOJIMA and H. OHMOTO MINING GEOLOGY:

Table 1 Equilibrium constants for chemical reactions controlling the solubilities of sphalerite and wurtzite

Abbreviations: sp, sphalerite; wz, wurtzite. *, extrapolated.

References: (a), Helgeson (1969); (b), Bourcier and Barnes(1987).

position of Zn1-x,S and Zn1-x, respectively. been substan-tiated experimentally by BOUR-

They have also suggested that the inversion CIER and BARNES (1987), but that of wurtzite
between the two minerals is a univariant func- has not. The primary objectives of this study
tion of sulfur fugacity (fs) and temperature: are therefore to experimentally verify that
wurtzite is stable at lower fs, condition. the solubility of wurtzite is indeed higher
However, it is not certain whether or not this than that of sphalerite in a temperature range
theory applies to natural ores where wurtzite of 350•`250•Ž, and that wurtzite may pre-
contains appreciable amounts of Fe, because cipitate from solutions supersaturated with
the system studied by SCOTTand BARNES (1972) respect to both wurtzite and sphalerite. In
did not contain any Fe. addition, natural occurrences of wurtzite are
Based on detailed descriptions on sulfide reviewed from a literature survey to put con-
minerals from the modern seafloor deposits on straints on the mechanisms of wurtzite forma-

the East Pacific Rise, HAYMONand KASTNER tion and the phase relationships between wurt-

(1981) and GRAHAMet al.(1988) have suggested zite and sphalerite.

that supercooling of hydrothermal fluids with

Mechanisms of Wurtzite Precipitation
high concentrations of Zn and S may cause
Predicted from Thermodynamic Data
rapid precipitation of wurtzite metastably due
to a kinetic effect. For sulfide ores containing Possible mechanisms of wurtzite precipita-
wurtzite at the Toyoha mine in Japan, a tion from hydrothermal solutions, predicted
similar interpretation has been given by by GRAHAM et al. (1988) and SAITOet al. (1989)
DoHMOTOet al.(1986). based on the solubility data of sphalerite and
According to the thermodynamic data sum- wurtzite, are explained here in detail.
marized by HELGESON (1969), the solubility of By combining the thermodynamic data
wurtzite is higher than sphalerite at tempera- reported for minerals and their pertinent ionic
tures from 25•‹ to 300•Ž. This recognition has species, the solubility products for wurtzite
led GRAHAM et al.(1988) and SAITO et al. (1989) and sphalerite have been computed by
to suggest that wurtzite may precipitate when HELGESON (1969). While, the speciation for
a fluid initially saturated (or undersaturated) zinc chloride complexing has been given by
with respect to sphalerite is cooled rapidly to BOURCIER and BARNES (1987) (see Table 1).
become supersturated with respect to wurtzite Assuming that the dominant forms of zinc in.
(and also to sphalerite). The solubility 'of solutions are chloride complexes, the solubil-
sphalerite estimated by HELGESON (1969) has ities of sphalerite and wurtzite can be evalu-
 41(5), 1991 Hydrothermal synthesis of wurtzite and sphalerite at T=350•`250•Ž 315

Fig. 1 Solubility relationships of sphalerite (sp) and wurtzite (wz) for a temperature range of 350•`200•Ž predicted

from thermodynamic data (Table 1). The conditions are: pH=4.5; m•¬=2; and mi.izs=10-1.5 at 350•Ž, 10-2.5 at

300•Ž, 10-3.0 at 250•Ž and 10-4.0 at 200•Ž. Also shown are (a) dissolution-precipitation process according to the

Ostwald's step rule and (b) two possible mechanisms for precipitation of wurtzite: A solution that was initially

saturated with sphalerite may precipitate wurtzite either by mixing with a cooler solution or by simple closed

system cooling. The amount of Zn that may precipitate during the cooling is Xa-Xb. See text for other symbols.

ated from the equilibrium constants summa- by OHMOTOet al. (1983). The activity co-
rized in Table 1. The equilibrium constants efficients for the ionic species were estimated
for the first two reactions in Table 1 indicate using the extended Debye-Hiickel equation pro-
that, under the same T, pH, aHzs and ac1-(a, ac- posed by HELGESON (1969); the Debye-Hiickel
tivity) conditions, the solubility of wurtzite is and the ion size parameters were from HELGE-
always greater than that of sphalerite at SONet al. (1981) and TRUESDELL (1984), re-
temperatures below 350•Ž: by about 1.1 log spectively. The activities of neutral species,
unit at 200•Ž and by about 0.6 log unit at such as H2S (aq) and ZnC12, are assumed to be
350•Ž. The solubilities of wurtzite and the same as that of aqueous CO2 (HELGESON,
sphalerite (both with the ideal composition 1969)
ZnS) are compared in a temperature range of Possible mechanisms for precipitation of
350•Ž to 200•Ž in Fig. 1. The total molality of wurtzite and sphalerite can be discussed using
chloride (mzci) and pH are fixed at 2 and 4.5, the solubility curves in Fig. la. Consider a
respectively. The molality of aqueous H2S (m solution A with the composition X; at the
HZs; mol/kg • H2O) is varied from 10-1.5 at temperature T,. This solution is super-
350•Ž to 10-4.0 at 200•Ž. These pH, mzc, and saturated with respect to both wurtzite and
mH2s values correspond to the average values sphalerite. According to the Ostwald's step
for the Kuroko ore-forming fluids estimated rule of the empirical law of successive trans-
 316 S. KOIIMA and H. OHMOTO MINING GL'OLOGY:

formation (OSTWALD, 1897), wurtzite as a mechanism of wurtzite shown in Fig. lb, us-

metastable phase is predicted to precipitate ing only a thermal-gradient. Powdery crystals

first in preference to sphalerite. Due to pre- of sphalerite as starting materials were placed
cipitation of wurtzite, the solution composition in the end of a closed silica glass capsule
may change to the point B (Xwz). Sphalerite (•`3.5 mm in diameter and •`9 cm in length)
may also nucleate at any point between A and together with a solvent. The capsules were
C. If the dissolution rate of wurtzite is fast, placed vertically in an autoclave, and heated
wurtzite may dissolve in solution and repre- in a vertical type of an electric furnace con-
cipitate as sphalerite until the solution and trolled by upper and lower heaters. The
sphalerite become equilibrated at the point C. temperature gradient of approximately 10•Ž/

However, if the wurtzite is isolated from the cm was imposed outside the vessel. Under

solution or the dissolution rate of wurtzite is such a configuration, the actual temperature

slow, it may remain as a metastable phase. differences between the hotter and cooler ends

Furthermore, sphalerite would be formed if were found to be approximately 10•‹-15•Ž.

the solution with the composition XW, is The thermal-gradient must be enough to

heated from T, to T2. generate metastabilities induced by super-

There may be a variety of processes that saturation (SCOTT and BARNES, 1972; SCOTT,

cause a fluid to become supersaturated with 1974). The powdery crystals were dissolved at

respect to wurtzite, including rapid cooling, the , lower (hotter) end of the capsule,

rapid pressure-drop, and rapid boiling. Two transported upward by the convecting fluid,
examples of rapid cooling, one with a closed and reprecipitated at the upper (cooler) end of

system cooling (e.g., conductive cooling) and the capsules. The experiments were conducted
the other caused by mixing with a cooler and by using two modes of capsules, which are

dilute solution (e.g., seawater, meteoric water) similar to those used in KoJIMA (1990); namely

are shown in Fig. lb. If a fluid that was the mode A with a straight shape and the

saturated with sphalerite at 350•Ž was cooled mode B with a necked path as a role of baffle

rapidly by heat conduction, precipitation of (see Fig. 1; KOJIMA, 1990). The aqueous solu-
wurtzite may first occur at lower temperatures. tion used in Series I experiments was 1 m NH4
In such a case, the amount of supersaturation Cl solution with pH=4.8 at 25•Ž.

corresponding to the value of Xa-Xb may be In the second series of experiments (Series
regarded as a driving force for the growth of II), attempts were made to produce wurtzite
wurtzite. In submarine conditions, seawater by using a solution with an excess zinc concen-

mixing with an ore-forming solution may tration. The experimental solutions were a mix-

cause precipitation of wurtzite (see an arrow ture of 1 m ZnC12+1 m NH4C1 (pH=5.6 at

in Fig. lb). According to recent studies, 25•Ž). The starting materials and other ex-

seawater mixing combined with heat conduc- perimental conditions were similar to Series I
tion is considered a major cooling mechanism experiments.
for the ore-forming fluids responsible for The nutrient materials as powdery minerals
mineralization in modern seafloor deposits were synthesized at 800•‹ to 850•Ž by an
(e.g., TIVEY and DELANEY, 1986; HANNINGTON evacuated silica glass tube method using
and Sco-r-r, 1988). 99.9+ percent metals and sulfur. Sphalerite

solid solutions with various Fe contents (ZnS,

Experimentals
Zn0 .95Fe0.05S, Zn0.85Fe0.15S and Zn0.7Fe0.3S) are
Experimental method the main nutrient materials, and used by com-
All hydrothermal experiments were perform- bining with pyrrhotite (IC, NFes=0.97), ala-
ed by a conventional transport method using a bandite and crystalline sulfur. The experi-
temperature gradient in an autoclave (SCOTT, ments were carried out at temperatures between
1974). In the first series of experiments (Series 350•‹ and 250•Ž. The temperatures at the cooler
1), we attempted to substantiate the formation .end were controlled within •}3•Ž during the
 41(5), 1991 Hydrothermal synthesis of wurtzite and sphalerite at T=350•‹-250•Ž 317

Table 2 Summary of the conditions and results of hydrothermal experiments

1: Values in parentheses indicate the FeS mol % of sphalerite.

2 : Run period (days). 3 : Quench pH.
Abbreviations: wz-sp, wurtzite-sphalerite aggregate; sp, sphalerite; py,
pyrite; po, pyrrhotite; alb, alabandite; S, sulfur(solid); S, spherulitic
(pisolitic); C, colloform; P, polyhedral; *, sector-zoned. See text for
modes A and B.

run, and were measured directly by a chromel atures, the reaction vessel was quenched using
-alumel thermocouple inserted into the inner an electric fan and the capsules were taken out
vessel near the top of the reaction capsule. In from the furnace. Precipitated products in
all runs, the confining pressure was maintained the upper (cooler) part of capsule were investi-
at approximately 250 kgf/cm2, and monitored gated using a transmitting microscope, a
via a Bourdon-type pressure gauge. Guinier-Hagg camera and an electron micro-
After 6 to 17 days at experimental temper- probe analyzer. Particularly in the microscop-
 318 S. Koii,si,, and H. OHylolo MINIM. Gioi oov:

Fig. 2 Microscopic textures of wurtzite and sphalcrite synthesized in the hydrothermal experiments. A and B, col-

loform wurtzite (Run No. 11-21, 250•Ž); C, zoned wurtzite (Run No. 11-9, 300•Ž); D, pisolitic wurtzite (Run No.

11-26, 250•Ž); E, sector-zoned sphalerite (Run No. 1-8, 300•Ž); F, fibrous sphalerite (Run No. 1-9, 300•Ž). B is

taken under crossed polars; the others are under planepolarized light. The white bar is the scale of 150pm and the

black bar 300 um.

is analyses, both internal texture and anisotro- Chemical analyses of precipitated sphalerite
py of the run products were carefully observed and wurtzite were performed by the energy
using doubly polished thin sections. For dispersive method using a Shimadzu-ARL,
a precise identification of the products, X-ray EMX-2 type electron microprobe analyzer
powder diffraction analysis was carried out equipped with an EDAX detecting unit.
under the operating conditions of 30 to 35 kV Results and remarks
and 10 to 14 mA, using the CuKƒ¿1 radiation Approximately 50 runs for Series I and II ex-
monochromatized by a curved quartz crystal periments were carried out. Most runs produc-
and reagent CaF2 as an internal standard. ed appreciable amounts of sphalerite and/or
 41(5), 1991 Hydrothermal synthesis of wurtzite and sphalerite at T=350•‹-250•Ž 319

wurtzite (Table 2). Table 2 shows several im-

portant aspects on wurtzite formation. First,

the appearence of wurtzite is limited to Series

II experiments in which the ZnClz-bearing

solution was used as a solvent, and wurtzite

was not formed in Series I experiments. These

results suggest that the excess zinc dissolved in

hydrothermal solutions (i.e., solutions highly

supersaturated with respect to sphalerite)

plays an important role in nucleation and

growth of wurtzite. It further suggests that the

solubility of wurtzite is indeed higher than Fig. 3 Scanning electron micrograph of wurtzite

that of sphalerite. There is a distinct temper- synthesized at 250•Ž (Run No. 11-26).

ature effect for wurtzite precipitation from the

experimental solutions: no wurtzite formed in strongest (100) reflection near -3.309•ð, in-

the runs at 350•Ž, but wurtzite formed in some dicating that these wurtzites belong to the 2H-

Series II runs at 300•Ž and all Series II runs Me wurtzite (SMITH, 1955).

at 250•Ž. The significance of this observation will Some examples of the internal textures of

be discussed in the next section. Table 2 the precipitated zinc sulfides are shown in

also shows that both wurtzite and sphalerite Fig. 2. Most wurtzites formed at 300•Ž and

were formed under nearly identical pH condi- 250•Ž show colloform textures with radial or

tions, suggesting that the formation of wurt- fibrous structures (Fig. 2A), and distinct

zite is not dependent on pH. anisotropy under crossed polars (Fig. 2B).

In Series 11 experiments at 300•Ž, wurtzite Usually, wurtzite appears to be intergrown

tends to form when pyrrhotite was added as a closely with sphalerite. Wurtzite sometimes ex-

nutrient material (see Table 2). This feature hibits a growth-banded zonation from

may indicate that a lowsulfur fugacity (fs2) con- brownish core to yellowish rim (Fig. 2C), sug-

dition is favorable for the formation of wurt- gesting a variation of the FeS content. Wurt-
zite, as suggested by SCOTT and BARNES (1972). zite with similar color banding has been

In nature, an intimate association of wurtzite reported in wurtzite-rich ores from some

and pyrrhotite is found in some base-metal modern seafloor deposits (OUDIN, 1983; KOSKI

and polymetallic ore deposits (e.g., SuGAKI et et al., 1984). All the wurtzites formed at 250•Ž

al., 1984; ZIERENBERG et al., 1984; PETER and are submicron-sized aggregates, showing

SCOTT, 1988; KANBARA et al., 1989). However, spheroidal and pisolitic textures (Fig. 2D).

the fact that wurtzite was formed in the ex- Such textures of wurtzite suggest the precipita-

tion from highly supersaturated solutions

perimental runs without pyrrhotite at 250•Ž
suggests that a low fs, is not necessarily an (e.g., SUNAGAWA, 1984). Figure 3 shows a scan-
essential condition for wurtzite formation. ning electron photomicrograph of wurtzite

Similarly, the presence or absence of alaban- produced at 250•Ž, displaying characteristic

dite in the starting materials, i.e. the presence morphologies of pumpkin- and bugle-like

or absence of Mn in the system, does not ap- shapes. Sphalerite crystals formed in Series I

experiments show a wide variety of textures

pear to be a determining factor in the forma-
tion of wurtzite (see Table 2). The FeS content (see Figs. 2E and 2F). Polyhedral sphalerite
of the starting sphalerite or the mode of the (< 1 mm) showing a sector-zoned structure,
reaction capsule have no significant effect on which is also found in natural ores (e.g., BAR-

the formation of sphalerite or wurtzite. TON, 1970), was frequently produced in the

As is well known, there are many polytypes mode A experiments at both 350•‹ and 300•Ž

of wurtzite. The X-ray powder diffraction pat- (Fig. 2E). In the mode B experiments, fibrous
terns of all the synthesized wurtzites show the sphalerite with a growth-banded zonation was
 320 S. KOJIMA and H. OHMOTO MINING GEOLOGY;

Table 3 Compositional ranges for wurtzite and

Discussion
sphalerite synthesized in the hydrothermal ex-
periments Degree of supersaturation
As stated in the previous section, excess zinc
in the experimental solutions appears to have
played the most important role in the forma-
tion of wurtzite. In crystal growth theory, the
degree of supersaturation (saturation index)
has often been related' to the stability of
mineral and the variation of crystal mor-
phology (e.g., SUNAGAWA, 1984). The degree
of supersaturation with respect to wurtzite is
Values in parentheses are numbers of analyses .
defined as the ratio of the activity product of
pertinent aqueous species in a solution to the
formed (Fig. 2F). Such differences in the tex- equilibrium constant for the following reac-
tural features suggest that a higher degree of tions involving wurtzite (wz):
supersaturation with respect to sphalerite was ZnS(wz)+2H++nCl-
generated in the mode B runs compared to the =ZnCl2-nn+H2S(aq) .
mode A runs. Therefore, saturation index can be evaluated

Table 3 summarizes the ranges of Fe and Mn quantitatively by estimating pH and activities

contents of the wurtzite and the sphalerite of ZnCl2-nn and H2S(aq). In the calculations, it

shown in Fig. 2. The wurt-zite crystals formed was assumed that NH4C1 is completely

in Series II experiments shows a limited range dissociated into NH: and Cl-. Judging from

of Fe content, from 0.2 to 4.5 at.%, regardless the quench pHvalues in Table 2 and stability

of the presence or absence of pyrrhotite of NH:, the pH range was estimated as

in the nutrient. The Mn contents of wurtzite 5.0•}0.5 at the experimental temperatures. As

formed in the presence of alabandite are ex- mentioned earlier, the temperatures of the hot

tremely low (>0.1 at.%), suggesting that the ends were regarded as •`360•Ž for the 350•Ž

concentrations of impurities such as Mn do runs, •`310•Ž for the 300•Ž runs, and •` 265•Ž

not play an important role in the wurtzite for- for the 250•Ž runs. All the equilibrium con-

mation. In contrast to the wurtzite, the sphale- stants at these temperatures were interpolated

rite exhibits a wider range of Fe content from or extrapolated using a least-squares method.

1.9 to 16.0 at.%. The sphalerite shown in Fig. For the experimental solutions of Series I,

2E contains •`5.0 at.% Fe in the Fe-poor saturation index corresponds to the ratio of ac-

sector, •`8.0 at. YO Fe in the Fe-rich sector, tivity products of ZnC12-n and H2S(aq) at the

and •`16.0 at. %O Fe in an extremely Fe-rich temperatures of sphalerite dissolution (360•‹,

sector. The fibrous sphalerite in Fig. 2F shows 310•‹ and 265•Ž) to those of wurtzite at

a marked compositional heterogeneity: its cen- precipitation temperatures (350•‹, 300•‹ and
tral part is Fe-rich (•`10.0 at.% Fe) and the 250•Ž). For the experimental solutions of

Series II, dissolved zinc contents (mZncl2-nn) at

periphery is Fe-poor (•`1.9 at.% Fe). In the
literature (e.g., PANKRATZ and KING, 1965; the temperatures of sphalerite dissolution

Scorr and BARNES, 1972), nonstoichiometries were firstly calculated using the speciation for .

of zinc sulfide minerals have been discussed: the zinc chloride complexes given by BOURCIER

sphalerite is zinc-deficient and wurtzite is and BARNES (1987) and the following charge

sulfur-deficient. However, such deviations in and mass balance eauations:

the Zn/S stoichiometry were not observed mCI- + mZnCl3+2mZnC12-4-•¬mNH+mZnCl+

within a range of 0.5 at.% (see Table 3). mcl-+mzncl++2mzncl2+3mznCl3+4mzncl2-4•¬3

Next, aH2s(aq) in the solutions at pH=5 was in-

ferred from the mzncl2-nnand equilibrium con-
 41(5), 1991 Hydrothermal synthesis of wurtzite and sphalerite at T=350•‹-250•Ž 321

created a situation where the solubilities of

sphalerite (and wurtzite) are much higher than
in other experimental solutions. It is therefore
considered that supersaturation with respect
to wurtzite was not produced in Series II ex-
perimental solutions with liquid sulfur.
However, KiYosu and NAKAI(1971) have suc-
ceeded in hydrothermal synthesis of wurtzite
in a similar system ZnCl2-S-Na2CO3-H2O.
Generally, the addition of dissolved carbonate
(Na2CO3) causes an increase of fluid pH (and
also a decrease of fs,) at the starting condi-
tions, so that supersaturation with respect to
wurtzite may have been produced in their
Fig. 4 The calculated saturation indices (SI) of ex- study.
perimental solutions with respect to wurtzite. See A similar effect of excess zinc in the forma-
text for detailed explanations.
tion of wurtzite has been previously observed

in some experiments under dry conditions. In

stants in Table 1. Consequently, the ratio of synthetic experiments by a vapor depositing

the product of this aH2s and aznCl2-nn (for the in- method, SHALIMOVA and MOROZOVA (1965)

itial solutions of mZnCl2=1m) to that of wurt- have demonstrated that the addition of ZnC12

zite at the precipitation temperatures is regard- to ZnS leads to a high abundance of wurtzite

ed as the saturation index. The effect of Fe in the deposited film at temperatures between

dissolved in the solutions were not taken into 600•‹ and 400•Ž. This phenomenon is very

account in the calculations. similar to our experimental results in the

The results of the calculations, showing the respect that the excess zinc is likely to cause

changes in the saturation indices of the ex- the formation of wurtzite.

perimental solutions with respect to wurtzite, Natural occurrence of wurtzite

are illustrated in Fig. 4. It shows that hydro- In order to obtain information on condi-
thermal fluids in Series I experiments are highly tions favorable for formation of wurtzite, a
undersaturated with respect to wurtzite, and literature survey on natural occurrence of
that those in Series II experiments are apparent- wurtzite was carried out. Major ore deposit
ly supersaturated with respect to wurtzite at types and mining districts where wurtzite was
300•‹ and 250•Ž, but slightly undersaturated reported are summarized in Table 4. The
at 350•Ž. These features are in excellent deposits in the table, including low-temper-
agreement with the observation that wurtzite ature deposits such as the Mississippi Valley-
formed in some Series II experiments of 300•‹ type and the Alpine-type, are all regarded as
and 250•Ž. hydrothermal deposits formed under shallow-
In the systems containing liquid sulfur at subaerial or submarine conditions. In partic-
300•Ž, only sphalerite (+pyrite) was formed ular, wurtzite appears to occur frequently in
(see Table 2). The hydrolysis reaction of base-metal (polymetallic) ore deposits of
sulfur is the likely cause for an extremely low relatively young geologic ages; most abun-
pH (0.4-1.6), as seen in the following reac- dantly in those formed during Neogene Terti-
tion: ary or Quaternary ages (see Table 4).
4S•‹+4H2O=3H2S+HSO-4+H+. The transformation of wurtzite to sphalerite
As inferred from the dissolution reactions in without solution/dissolution reactions is a
Table 1, pH is the most effective parameter kinetic process, and probably a function of
controlling the solubilities of wurtzite and temperature, pressure and time. Some old
sphalerite. The above experimental condition deposits (e.g., Mississippi Valley-type) may
322 S. KOJIMA and H. OHMOTO MINING GEOLOGY:

Table 4 Reported occurrences of wurtzite in ore deposits

< >: total number of deposits. * : deposits of Tertiary or Quaternary ages .

(References)
(1) Imai (1941,
.1978), (2) Anderson (1947), (3) Umpleby (1917), (4) Morris (1968) ,
(5) Myer (1962), (6) Thompson(1950), (7) Ramdohr(1980), (8) Ahlfeld and Schneider-
Scherbina (1964), (9) Fleet (1977), (10) Ianovici and Borcos (1982)
, (11) Bogdanov
(1982), (12) Maeda and Ito (1989), (13) Yoshikawa (1975), (14) Williams(1968) , (15)
Bussell et al.(1990), (16) Sakurai(1973) , (17) Watanabe (1941a), (18) Watanabe
(1941b), (19) Huang (1955, 1965), (20) Tolman and Ambrose (1937), (21) Haraguchi
and Tajima (1969), Dohmoto et al.(1986), Kanbara et al .(1989), (22) Weed (1912),
Meyer et al.(1968), (23) Butler (1913), (24) Loucks et al .(1988), (25) Imai et
al.(1985), Fukahori and Sakogaichi (1990) , (26) Smith et al.(1957), (27) Sugaki et
al.(1983), (28) Sugaki et al.(1984), (29) Morvai (1982) , (30) Dill (1979), (31) Ito
and Sakurai(1947), (32) Henmi(1941) , (33) Urabe (1974), (34) Takahashi and Nambu
(1951), (35) Watanabe and Nakano (1936), (36) Frenzel and Ottemann (1967) , (37)
Behre et al.(1937), (38) Evans and McKnight(1959)
, (39) Olson(1984); (40) Roedder
(1968), (41) Lindgren (1928), (42) Schulz (1968), (43) Playford (1975)
, (44) Brown (
1971), (45) Hannington et al . (1986) , (46) Tivey and Delaney (1985
, 1986), (47)
Hannington and Scott (1988), (48) Koski et al .(1984), Paradis et al.(1988), (49)
Peter and Scott (1988), (50) Graham et al.(1988) , (51) Haymon and Kastner (1981.),
Oudin (1983), Zierenberg et al.(1984), (52) Marchig et al .(1988), (53) Herzig et
al.(1988), (54) Urabe and Kanazawa (1989), (55) Motomura et al .(1989), (56) Urabe
et al.(1990), (57) Missack et al.(1989), (58) Blum and Puchelt (1991) .
 41(5), 1991 Hydrothermal synthesis of wurtzite and sphalerite at T=350•‹-250•Ž 323

preserve wurtzite if they were not buried to rapid cooling of highly supersaturated fluids.
greater depths and/or subjected to higher Precipitation of wurtzite from highly super-
temperatures. Even in young deposits, some saturated conditions explains why wurtzite
primarily precipitated wurtzites have changed formed usually exhibits radial and fibrous tex-
to the stable cubic phase (sphalerite) over a tures.
geologic period. In fact, pseudomorphic tex- In nature, the occurrence of fibrous wurtzite
ture suggesting the transformation of primary appears to be limited to geologically recent
wurtzite to sphalerite has been observed fre- deposits formed under either shallow-
quently in zinc-rich ores from both ancient subaerial or submarine conditions. This
(Tertiary age) and modern deposits (e.g., phenomenon may lead to an interpretation
BEHREet al., 1937; IMAI, 1941, 1978; PARADIS that wurtzite from hydrothermal ore deposits
et al., 1988). This instability of wurtzite ex- is a metastable product formed by drastic
plains why wurtzite is found only in relatively physicochemical changes in the fluids.
young deposits. Acknowledgments: We would like to thank
Natural wurtzite occurs commonly as radial Prof. M. AKIZUKI, Dr. A. KITAKAZE and Dr. K.
or fibrous aggregate forms, and exhibits HAYASHI for their useful discussions, and Mr.
heterogeneous compositions. As it is stated in T. NAGASE for his assistance in scanning elec-
the earlier section, such features probably in- tron microscopy. Also we thank Dr. S.
dicate that the wurtzite precipitated from solu- POULSON for critical reading of this
tions of very high degrees of supersaturation manuscript. This study was supported by a
(e.g., SUNAGAWA, 1984). Because the supercool- Grant-in-Aid from the Ministry of Education,
ing of fluid caused by rapid mixing of Science and Culture of Japan.
hydrothermal fluid with cold seawater should
References
cause a high degree of supersaturation with
respect to sphalerite and wurtzite, radial and AHFELD, F. and SCHNEIDER-SCHERRINA,
A. (1964): Los yaci-
fibrous minerals such as wurtzite are likely to mientos minerals y de hidrocarburos de Bolivia.
form in submarine-type deposits. A similar Dept. Nacional de Geologia, Boletin 5, La Paz, 388p.

process of supercooling has been postulated ALLEN, E. T. and CRENSHAW, J. L. (1912): The sulphides

for some shallow subaerial deposits, such as of zinc, cadmium and mercury. Am. Jour. Sci. 4, 34,

341•`396.
the Bolivian-type polymetallic ore deposits
ALLEN, E. T., CRENSHAW, J. L. and MERWIN, H. E. (1914):
(GRANTet al., 1980), where meteoric water ap- Effect of temperature and acidity in the formation of
pears to have mixed with hotter hypersaline marcasite (FeS2) and wurtzite (ZnS); a contribution
fluid during ore mineralizations. All of the to the genesis of unstable forms. Am. Jour. Sci. 4,
above features suggest that wurtzite is a 38, 393•`431.
metastable phase precipitated from solutions ANDERSON, A. L. (1947): Epithermal mineralization at the
that attained supersaturation with respect to Last Chance and Hornsilver mines, Lava Creek

wurtzite due to drastic changes in the physico- district, Butte Country, Idaho. Geol. Soc. Amer.

chemical parameters. This suggestion is com- Bull., 58, 451•`482.

patible with the results obtained for our ex- BARTON, P. B., Jr. (1970): Sulfide petrology. Mineral,

Soc. Amer. Spec. Pap. 3, 187•`198.

perimental study.
BARTON, P. B., Jr. and TouLMIN, P. III. (1966): Phase rela-
Conclusions tions involving sphalerite in the Fe-Zn-S system.

Econ. Geol., 61, 815•`849.

Wurtzite was produced at 300•‹ and 250•Ž in
BARTON, P. B., Jr. and SKINNER, B. J. (1979): Sulfide
the hydrothermal transporting experiments
mineral stabilities, In Geochemistry of Hydrothermal
using a zinc-rich solution and synthetic
Ore Deposits, 2nd ed. (BARNES, H. L., ed.), New
sphalerite crystals as starting materials. Our ex- York, Wiley-Interscience, 278•`403.

perimental results suggest that the solubility of BEHRE, C. H., Jr., SCOTT, E. R. and BANFIELO, A. F.
wurtzite is higher than that of sphalerite, and (1937): The Wisconsin lead-zinc district. Preliminary

that wurtzite precipitation is favored by the paper. Econ. Geol., 32, 783•`809.
 324 S. KOJIMA and H. OHMOTO MINING GEOLOGY:

BLUM, N. and PUCHELT, H. (1991): Sedimentary-hosted W. (1980): Evolution of the porphyry tin deposits of

polymetallic sulfide deposits of the Kebrit and Bolivia, In Granitic Magmatism and Related
Shaban Deeps, Red Sea. Mineral. Depoista, 26, Mineralization (ISHIHARA, S. and TAKENOUCHI, S.,
217•`227. eds.), Mining Geol., Spec. Issue 8, 151•`173.
BOGDANOV,B. (1982): Bulgaria, In Mineral Deposits of HANNINGTON, M. D., PETER, J. M. and SCOTT, S. D. (1986):
Europe Vol. 2: Southeast Europe. (DUNNING, F. W., Gold in sea-floor polymetallic sulfide deposits. Econ.

MYKURA, W. and SLATER, D., eds.), London, Inst. Geol., 81, 1867•`1883.
Mining Metall. Mineral. Soc., 215-232. HANNINGTON, M. D. and SCOTT, S. D. (1988): Mineralogy
BOURCIER, W. L. and BARNES, H. L. (1987): Ore solution
and geochemistry of a hydrothermal silica-sulfide-
chemistry-VIl. Stabilities of chloride and bisulfide
sulfate spire in the caldera of Axial Seamount, Juan
complexes of zinc to 350•Ž. Econ. Geol., 82, de Fuca Ridge. Can. Mineral., 26, 603•`625.
1839•`1863.
HARAGUCHI, M. and TAJIMA, Y. (1969): Lead-zinc
BROWN, A. C. (1971): Zoning in the White Pine copper mineralization of the Toyoha mine, with special
deposit, Ontonagon Country, Michigan. Econ. reference to the nature and occurrence of sphalerite
Geol., 66, 543•`573. and the behaviour of silver. Mining Geol., 19, 9•`18
BUSSEL.L, M. A., ALPERS, C. N., PETERSEN, U., SHEPHERD,
(in Japanese with English abstract).
T. J., BERMUDES, C. and BAXTER, A. N. (1990): The HAYMON, R. M. and KASTNER, M. (1981): Hot spring
Ag-Mn-Pb-Zn vein, replacement, and skarn
deposits on the East Pacific Rise at 21•‹N: Preliminary
deposits of Uchucchacua, Peru: Studies of structure, description of mineralogy and genesis. Earth Planet.
mineralogy, metal zoning, Sr isotopes, and fluid inclu-
Sci. Lett., 53, 363•`381.
sions. Econ. Geol., 85, 1348•`1383. HELGESON, H. C. (1969): Thermodynamics of hydrother-
BUTLER, B. S. (1913): Geology and ore deposits of the San mal systems at elevated temperatures and pressures.
Francisco and adjacent district, Utah. U. S. Geol. Am. Jour. Sci., 267, 729•`804.
Surv., Prof. Pap. 80, 212p. HELGESON, H. C., KIRKHAM, D. H. and FLOWERS, G. C.
COREY, A. S. (1953): Note on sphalerite and wurtzite.
(1981): Theoretical prediction of the behavior of
Amer. Mineral., 38, 141•`143.
aqueous electrolytes at high pressures and
DILL, H. (1979): Lagerstattenkundliche Untersuchungen
temperatures: Calculation of activity coefficients,
zur Entstehung der Pyrit-fuhrenden Blei-Kupfer-
osmotic coefficients, and apparent molal and stan-
Zink-Lagerstatte Accesa (SW-Toskana). Mineral.
dard and relative partial molal properties to 600•Ž
Deposita, 14, 57•`80.
and 5 kb. Am. Jour. Sci., 281, 1249•`1516.
DOHMOTo,A., MATSUEDA, H. and ISHIKAWA, Y. (1986): HENMI, K. (1941): Wurtzite from the Okkoppe mine,
Characteristics of the mineralization at the Ishikari Aomori Pref. Jour. Geol. Soc. Japan, 48, 527•`528
vein of the Toyoha mine, Hokkaido, Japan. Sci. (in Japanese).
Tech. Repts. Mining College, Akita Univ., no. 7, HERZIG,P. M., HANNINGTON, M. D., SCOTT,S. D., THOMP-
13-21 (in Japanese with English abstract). SON, G. and RONA, P. A. (1988): Comparison of
EVANS, H. T., Jr. and McKNIGHT, E. T. (1959): New wurt-
sulfides from the TAG and Snakepit hydrothermal
zite polytypes from Joplin, Missouri. Amer.
fields (Mid-Atlantic Ridge) and the Troodos ophiolite
Mineral., 44, 1210•`1218.
(Cyprus) (abst.). EOS Trans. Am. Geophys. Union,
FLEET, M. E. (1977): The birefringence-structural state
69, 1488.
relation in natural zinc sulfides and its application to HUANG, C. K. (1955): Gold-copper deposits of the
a schalenblende from Pribram. Can. Mineral., 15, Chinkuashih mine, Taiwan, with special reference to
303•`308. the mineralogy. Acta Geol. Taiwanica, no. 7, 1•`20.
FRENZEL., G. and OTTEMANN, J. (1967): Eine HUANG, C. K. (1965): Further notes on the mineralogy of
Sulfidparagenese mit kupferhaltigem Zonarpyrit von
the Chinkuashih gold-copper deposits, Taiwan. Acta
Nukundamu/Fiji. Mineral. Deposita, 1, 307•`316.
Geol. Taiwanica, no. 11, 31•`42.
FuKAHORI, Y. and SAKOGAICHI, K. (1990): Mineralization IANOVICI, V. and BORCOS, M. (1982): Romania, In Mineral
characteristics in the Cumbre area, Huanzala mining Deposits of Europe Vol. 2: Southeast Europe. (DUNN-
district, central Peru. Mining Geol., 40, 23•`33. ING, F. W., MYKURA, W. and SLATER, D., eds.), Lon-
GRAHAM, U. M., BLUTH, G. J. and OHMOTO, H. (1988): don, Inst. Mining Metall. Mineral. Soc., 55•`142.
Sulfide-sulfate chimneys on the East Pacific Rise, 11•‹ IMAI, H. (1941): On "wurtzite" from the Hosokura mine,
and 13•‹N latitudes. Part I. Can. Mineral., 26, Miyagi Prefecture. Jour. Geol. Soc. Japan, 48,
487•`504. 505•`515 (in Japanese).
GRANT, J. N., HALLS, C., SHEPPARD, S. M. F. and AVILA, IMAI, H. (1978): "Wurtzite" from the Hosokura mine, In
 41(5), 1991 Hydrothermal synthesis of wurtzite and sphalerite at T=350•‹-250•Ž 325

Geological Studies of the Mineral Deposits in Japan Mineral. Deposita, 24, 82•`91.

and East Asia. (IMAI, H., ed.), Tokyo, Univ. Tokyo MORRIS, H. T. (1968): The main Tintic mining district,

Press, 135•`143. Utah, In Ore Deposits in the United States,

IMAI, H., KAWASAKI, M., YAMAGUCHI, M. and TAKAHASHI, 1933•`1967. (RIDGE, J. D., ed.), New York, Amer. In-

M. (1985): Mineralization and paragenesis of the st. Mining Metall. Petrol. Eng. Inc., 1043•`1073.

Huanzala mine, central Peru. Econ. Geol., 80, MORVAI, G. (1982): Hungary, In Mineral Deposits of

461•`478. Europe Vol. 2: Southeast Europe. (DUNNING, F. W.,

ITO, T. and SAKURAI,K. (1947): Wada's Minerals of MYKURA, W. and SLATER, D., eds.), London, Inst.

Japan, 3rd ed., Mineral. Inst., Univ. Tokyo, 368p (in Mining Metall. Mineral. Soc., 13•`53.

Japanese). MOTOMURA,Y., IZAWA, E., TANAKA, T. and KIMURA, M.

JANG, Y. (1985): Experimentelle Untersuchngen zur (1989): Mineral compositions of the carbonate
Geochemie des Mangans in Sulfidlagerstatten. Un- chimneys from the Iheya Ridge, Okinawa Trough
published Ph. D. thesis, Univ. Heidelberg, 118p. (abst.). Program Joint Meet. Soc. Mining Geol.
KANBARA, H., SANGA, T., OHURA, T. and KuMITA, K. Japan, Mineral. Soc. Japan, and Japan. Assoc.
(1989): Mineralization of Shinano vein in the Toyoha Mineral. Petrol. Econ. Geol., 166 (in Japanese).
polymetallic vein-type deposits, Hokkaido, Japan. MYER, G. H. (1962): Hydrothermal wurtzite at

Mining Geol., 39, 107•`122 (in Japanese with Thomaston Dam, Conecticut. Amer. Mineral., 47,

English abstract). 977•`979.

Kiyosu, Y and NAKAI, N. (1971): Hydrothermal syntheses OHMOTO, H., MIZUKAMI, M., DRUMMOND, S. E., ELDIRIDGE,

of sphalerite and wurtzite. Jour. Japan. Assoc. C. S., PISUTHA-ARNOND, V. and LENAGH, T. C. (1983):

Mineral. Petrol. Econ. Geol., 66, 228•`236 (in Chemical processes of Kuroko formation. Econ.

Japanese with English abstract). Geol. Mon. 5, 570•`604.

Ko.11MA, S. (1990): A coprecipitation experiment on in- OLSON, R. A. (1984): Genesis of paleokarst and strata-

timate association of sphalerite and chalcopyrite and bound zinc-lead sulfide deposits in a Proterozoic

its bearings on the genesis of Kuroko ores. Mining dolostone, northern Baffin Island, Canada. Econ.

Geol., 40, 147•`158. Geol., 79, 1056•`1103.

KOSKI, R. A., CLAUGUE, D. A. and OUDIN, E. (1984): OSTWALD, W. (1897): Studien uber die Bildung and Um-

Mineralogy and chemistry of massive sulfide deposits wandlung fester Korper. 1. Abhandlung: Ubersat-

from the Juan de Fuca Ridge. Geol. Soc. Amer. tigung and Uberkaltung. Zeit. Physik. Chem., 22,

Bull., 95, 930•`945. 289•`300.

LINDGREN,W. (1928): Mineral Deposits. New York, OUDIN, E. (1983): Hydrothermal sulfide deposits of the

McGraw-Hill, 1049p. East Pacific Rise (21•‹N) Part 1: Descriptive

LOUCKS, R. R., LEMISH, J. and DAMON, P. E. (1988): mineralogy. Mar. Mining, 4, 39•`72.

Polymetallic epithermal fissure vein mineralization, PANKRATZ,L. B. and KING, E. G. (1965): High-
Topia, Durango, Mexico: Part 1. Distinct geology, temperature heat contents and entropies of two zinc
geochronology, hydrothermal alteration and vein sulfides and four solid solutions of zinc and iron
mineralogv. Pcon. Geol.. 83. 1499•`1528. sulfides. U. S. Bureau of Mines, Rept. Invest., 6708.
MAEDA, H. and ITO, Y. (1989): Bismuth-bearing minerals PARADIS, S., JONASSON, 1. R., LE CHEMINANT, G. M. and

from the Inakuraishi ore deposits, southwestern Hok- WATKINSON, D. H. (1988): Two zinc-rich chimneys

kaido, Japan. Mining Geol., 39, 223•`229. from the plume site, Southern Juan de Fuca Ridge.

MARCHIG, V., ROSCH, H., LALOU, C., BRICHET, E. and Can. Mineral., 26, 637•`654.

OUDIN, E. (1988): Mineralogical zonation and PETER, J. M. and SCOTT, S. D. (1988): Mineralogy,

radiochronological relations in a large sulfide composition, and fluid inclusion microthermometry

chimney from the East Pacific Rise at 18•‹25' S. Can. of seafloor hydrothermal deposits in the southern

Mineral., 26, 541•`554. trough of Guaymas Basin, Gulf of California. Can.

MEYER, C., SHEA, E P. and GODDARD, C. C., Jr. (1968): Mineral. 26, 567•`587.

Ore deposits at Butte, Montana, In Ore Deposits in PLAYFORD, P. E. (1975): Narlarla lead-zinc deposits,

the United States, 1933•`1967. (RIDGE, J. D., ed.), Kimberley district, In Economic Geology of

New York, Amer. Inst. Mining Metall. Petrol. Eng. Australia and Papua New Guinea. (KNIGHT, C. L.,

Inc., 1373•`1416. ed.), Aust. Inst. Mining Metall., 535•`536.

MISSACK, E., STOFFERS, P. and EL GORESY, A. (1989): RAMDOHR, P. (1980): The Ore Minerals and Their In-
Mineralogy, parageneses, and phase relations of cop- tergrowths, 2nd ed., Oxford, Pergamon Press,
per-iron sulfides in the Atlantis II deep, Red Sea. 2005p.
 326 S. KonMA and H. OHMOTO

EOLOGY RoimoeR, E. (1968): The noncolloidal origin of "col- sphalerite-wurtzite transition in isomorphous mix-

loform" textures in sphalerite ores. Econ. Geol., 63, tures of the system ZnS-MnS-CdS-FeS. Geochem.

451•`471. Intern., 15, 33•`41.

SAITO,T., HAYASHI,K. and OHMOTO,H. (1989): Forma- THOMPSON, R. M. (1950): Mineral occurrences in western

tion process of Zn-S system minerals in the Canada. Amer. Mineral., 35, 451•`455.

Hosokura mine (abst.). Program Joint Meet. Soc. TIVEY, M. D. and DELANEY, J. R. (1985): Sulfide deposits

Mining Geol. Japan, Mineral. Soc. Japan, and from the Endeavour Segment of the Juan de Fuca

Japan. Assoc. Mineral. Petrol. Econ. Geol., 129 (in Ridge. Mar. Mining, 5, 165•`179.

Japanese). TIVEY, M. D. and DELANEY, J. R. (1986): Growth of large

SAKURAI,K. (1973): Sakurai's Mineral Specimens. Dr. K. sulphide structures on the Endeavour Segment of the

Sakurai Memoir. Vol., 177p (in Japanese). Juan de Fuca Ridge. Earth Planet. Sci. Lett., 77,

SCHULZ, O. (1968): Die synsedimentare Mineralparagenese 303•`317.

im oberen Wettersteinkalk der Pb-Zn-Lagerstatte TOLMAN, C. F. and AMBROSE, J. W. (1934): The rich ores

Bleiberg-Kreuth (Karnten). Tschermaks Mineral. of Goldfield, Nevada. Econ. Geol., 29, 255•`279.

Petrogr. Mitt., 12, 230•`289. TRUESDELL, A. H. (1984): Introduction to chemical calcula-

Sco'r , S. D. (1974): Experimental methods in sulfide syn- tions, In Reviews in Economic Geology, Vol. 1

thesis, In Reviews in Mineralogy Vol.1, Sulfide (HENLEY, R. W. TRUESDELL, A. H. and BARTON, P. B.,
mineralogy. (RIBBE, P. H., ed.), Blacksburg, Jr., eds.), Soc. Econ. Geol., 1•`8.

Mineral. Soc. Amer., S1•`S38. UMPLEBY, J. B. (1917): Geology and ore deposits of the
SCOTT, S. D. and BARNES, H. L. (1972): Sphalerite-wurt- Mackay region, Idaho. U. S. Geol. Surv., Prof. Pap.
zite equilibria and stoichiometry. Geochim. 97, 129p.
Cosmochim. Acta. 36. 1275•`1295. URABE, T. (1974): Mineralogical aspects of the Kuroko

SHAL.IMOVA, K. V. and MOROZOVA, N. K. (1965): Effect of deposits in Japan and their implications. Mineral.

excess zinc on the crystal structure of ZnS. Soviet Denosita. 9. 309•`324.

Phys. Crystallogr., 9, 471•`472. URABE, T. and KANAZAWA,Y. (1989): Present-day Kuroko

SMITH, F. G. (1955): Structure of zinc sulfide minerals. mineralzation at Izena Cauldron, Okinawa Trough,
Amer. Mineral., 40, 658•`675. Japan, 3; Mineral paragenesis and textures (abst.).
SMITH, F. G., DASGUPTA, S. K. and HILL, V. G. (1957): Mining Geol., 39, 50 (in Japanese).
Manganoan ferroan wurtzite from Llallagua, Bolivia URABE, T., AUZENDE, J. M., DEPLUS, C., EISSEN, J. P.,

(1). Can. Mineral.. 6. 128•`135. GRIMAUD, D., HUCHON, P., ISHIBASHI, J., JOSHIMA, M.,

SUGAKI, A., UENO, H., SHIMADA, N., KUSACHI, I., LAGABRIELLE, Y., MEVEL, C., NAKA, J., RUELLAN, E.,

KITAKAZE, A., HAYASHI, K., KOJIMA, S. and SANJINES, TANAKA, T. and TANAHASHI, M. (1990): Hydrothermal

O. V. (1983): Geological study on the polymetallic deposits at the central spreading axis of the North Fiji

ore deposits in the Potosi district, Bolivia. Sci. Rept. Basin (SW Pacific): Preliminary report of Nautile

Tohoku Univ., Ser. 3, 15, 409•`460. dives of STARMER Cruise. Mining Geol., 40,

SUGAKI, A., UENO, H., SHIMADA, N., KUSACHI, I., 117•`124 (in Japanese with English abstract).

KITAKAZE, A., HAYASHI, K., KOJIMA, S., SANJINES, O. WATANABE, M. (1941a): Prismatic zinc sulphide minerals
V., SANCHE7, A. C. and VELARDE, O. V. (1984): from the Ohmori gold deposit, Fukushima Prefec-
Geological study on the polymetallic ore deposits in ture. Jour. Japan. Assoc. Mineral. Petrol. Econ.
the Quechisla district, Bolivia. Sci. Rept. Tohoku. Geol., 25, 213-229 (in Japanese).
Univ., Ser. 3, 16, 130•`194. WATANABE, M. (1941b): Mode of occurrence of fluorite

SUNAGAWA, 1. (1984): Growth of crystals in nature, In and some zinc sulphide minerals in the Tomiyasu

Material Science of the Earth's Interior. (SUNAGAWA, gold mine (11). Jour. Japan. Assoc. Mineral. Petrol.

1., ed.), Tokyo, Terrapub, 63•`105. Econ. Geol., 26, 287•`298 (in Japanese).

TAKAHASHI, I. and NAMBU, M. (1951): Geology and ore WATANABE, M. and NAKANO, N. (1936): Mode of occur-

deposits of the Abeshiro mine, Aomori Prefecture. rence of jordanite, wurtzite and rhodochrosite in ores

Jour. Japan. Assoc. Mineral. Petrol. Econ. Geol., from the Yunosawa mine, Aomori Prefecture. Jour.

35, 35•`46 (in Japanese with English abstract). Japan. Assoc. Mineral. Petrol. Econ. Geol., 15,

TAUSON, V. L., CHERNYSHEV, L. V. and MAKEYEV, A. B. 269•`281 (in Japanese).

(1977): Phase relations and structural characteristics WEED, W. H. (1912): Geology and ore deposits of the
of mixed crystals in the system ZnS-MnS. Geochem. Butte district, Montana. U.S. Geol. Surv., Prof.
Intern., 14, 33•`45. Pap. 74, 262p.
TAUSON, V. L. and CHERNYSHEV,L. V. (1978): The WILLIAMS, S. A. (1968): Complex silver ores from Morey,
 41(5), 1991 Hydrothermal synthesis of wurtzite and sphalerite at T=350•‹-250•Ž 327

Nevada. Can. Mineral., 9, 478•`484. (1984): Massive sulfide deposits at 21•‹N East Pacific

YOSHIKAWA,K. (1975): Wurtzite from the Jyokoku mine. Rise: Chemical composition, stable isotopes, and

Rept. Geol. Surv. Hokkaido, no. 47, 111•`112 (in phase equilibria. Geol. Soc. Amer. Bull., 95,

Japanese). 922•`929.

ZIERENBERG,R. A., SHANKS, W. C., III and BISHOFF, J. L.

350°∼250℃ に おけ る ウ ル ツ鉱 お よ び 閃 亜 鉛 鉱 の 熱 水 合 成

小 島 晶 二 ・大 本 洋

要 旨:出 発 物 質 に 閃 亜 鉛 鉱 を 用 い,温 度 勾配 運 搬法 に よ 文 献 調 査 に よ り,ウ ル ツ鉱 は 相 対 的 に 若 い年 代(と くに

り350°,300°お よび250℃ で ウル ツ 鉱 な ら び に 閃 亜 鉛 鉱 第 三 紀,第 四 紀)の 浅 所 陸成 鉱 床 な らび に 海 底 熱 水鉱 床

の 熱 水 合 成 が 試 み ら れ た.亜 鉛 に 富 む 溶 液(1mZnCI2 では か な り普 遍 的 に 見 られ る こ とが 明 らか に され た.こ

+1mNH4C1)が 運 搬 媒 体 と して 用 い ら れ た 場 合,300° う した 鉱 床 に 対 して は 鉱化 作 用 の 際 に天 水 ま た は 海 水 と

お よ び250℃ の 実 験 に お い て のみ 繊 維 状 ウル ツ鉱 が 閃 亜 の混 合 に よ る急 速 冷却 の よ うな鉱 化 溶液 に お け る急 激 な

鉛 鉱 と と も に 生 成 され た が,亜 鉛 を溶 存 し な い 溶 媒(1 物 理 化 学 的 変 化 が 起 こ った と考 え られ る.ま た,ウ ル ツ

mNH4Cl)を 用 い た 実 験 で は 閃亜 鉛 鉱 の み が 生 じた.ま 鉱 結 晶は しば しば上 記 変化 に よ り生 じた と思 わ れ る繊 維

た,ウ ル ツ鉱 の生 成 は 出発 物 質 では あ る閃 亜 鉛 鉱 の 組 成 状 また は 放 射 状 組 織 を 呈 す る.え られ た 実 験 デ ー タ と鉱

や 磁 硫 鉄 鉱,閃 マ ソ ガ ン鉱 の添 加 に よ り影 響 され な い. 床 に おけ る ウ ル ツ鉱 の 産 状 は 熱 水 性 ウル ツ鉱 が 高 過 飽 和

これ ら の結 果 は ウ ル ツ鉱 の溶 解 度 が閃 亜 鉛 鉱 の そ れ に 比 溶 液 か ら生 成 され た 準 安 定 鉱 物 で あ る こ とを示 唆 して い
べ て 高 い とす る熱 力 学 的 予 察 と一 致 す る. る.

熱 水 性 鉱 床 に おけ る ウ ル ツ鉱 の産 出 に関 す る包 括 的 な