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GEOLOGY, MINERALOGY

AND GEOCHEMISTRY

OF THE BORATE DEPOSITS AND ASSOCIATED ROCKS AT THE ·EMET VALLEY, ±Y,RKEY

by

£!tlIT HELVACI, B.Sc.! M.Se.

Thesis submitted to the University of Nottingham for the degree of Doctor of Philosophy, January, 1977.

,

BEST COpy •

, .AVAILABLE . Variable print quality

PAGE NUMBERS CUTOFF IN THE ORIGINAL

CONTENTS Page ABSTRACT Chapter I:

INTRODUCTION 1. 2. 3. 4. ,

Chapter II:

1 6 9

10

DISTRIBUTION AND CLASSIFICATION OF BORATE imI50~ITE AND MrNERALS 1. 2. 3.

Chapter III:

Area of present study Previous work The present study Acknowledgements

Geochemical behaviour of boron Distribution and classification of borate deposits and minerals Borate deposits and minerals in Turkey

23

GENERAL GEOLOGY. OF THE EMET DISTRICT 1. 2. 3.

Introduction Basement rocks and their petrography General stratigraphy of the sediments

la! Conglomerate

and

sandstone

b Lower limestone c Red formation d Borate zone e Upper limestone 4. Petrography and geochemistry of volcanic rocks ~a~ Classification of volcanic rocks b Petrography of volcanic rocks Spherulitic rhyolite Dacite Pyroxene andesite (c) Geochemistry of volcanic rocks 5. Structure 6. Thermal springs 7. Geological history Chapter IV:

12 13

27 32

34 34 35 35 36 36 39

39 40 40 41 42 42 49 54 56

PETROGRAPHY AND GEOCHEMISTRY OF''THE

SrnlMENT~ 1. 2.

Petrography of the sediments Geochemistry of the sediments (a) Introduction

59 68 68

Pase (b) Distributions, variations and inter-element correlations (c) Geochemistry of clay and tuff Si02 Al203, Ti02 and K20 Iron (Fe203 and FeO) MgO CaO, Mn and CO2 Na20 P205 H2O B203 S Cl Cr and Ni Cu

Zn As Br Sr Ba Ce Ph

Th and U Summary (d) Geochemistry of upper limestone Chapter V:

69 69 70 70 73 74 79 79 80 80 84 85 85 86 87 88

89 90 90

91 92 92 93

9495

DETAILED STRATIGRAPHY AND STRUCTURE OF THE

BORATE DEPOSITS

1. Introduction 2. Stratigraphy 3. Structure and thickness

119 123

13.4

MINERALOGY AND PETROGRAPHY OF THE EMET

BORATE DEPOSITS 1. Introduction 2. Textural relationships of borate and other minerals in the Emet borate deposits Calcium borates Colemanite Meyerhofferite i1

145 149 149 149 168

Page

3.

Chapter VII:

Sodium-calciumborates Ulexite Strontium borates Veatchite Tunellite Magnesium-calciumborates Hydroboracite Complex borates Teruggite Com~ound borates Cahnite Non-borate minerals Native sulphur Realgar Orpiment Celestite Gypsum Calcite Quartz Geographicaldistribution and mineral assemblages

173 173 177 177 177 180 180 184 184 187 187 190 190 190 192 194 194198 198 201

GEOCHEMISTRYOF THE BORATES AND OTHER

MINERALS

-

1. Introduction 2. Distributions,variations and interelement correlations B20 , CaO and H20 3 The elements Mg, Na, Sr, As and S The elements Si, Al, Ti, Fe, Mg, K, Mn and P The elements Cl, Cr, Ni, Cu, Zn, Sn, Ce, Pb and Th The elements Br, Ba and U 3. Interpretationof chemistry 4. Colour variations in celemanite and the other borates

205 209 213 221 226 228 229 230 232

ChaE!er VIII: ORIGIN AND DIAGENESIS OF THE EMET BORATE

DEPOSITS 1. 2.

The geological setting Source of the Boron, Arsenic, Sulphur, Calcium, Sodium, Magnesium and Strontium 3. Mineral phases formed penecontemporaneous1y with the clastic sediments Origin of the early formed colemanite 4. Diagenetic mineralization 5. Depositional and post-depositional history

iii

267 268 272 272 278 283

Page Chapter IX:

COMPARISON OF THE FORMATION OF CALCIUM BORATEs OF EMET WITH THE KfRKA DEPOSIT

AND OTHERS INTURKEY

1. Introduction 2. Kernite and other borate minerals from the Kirka deposit Kernite 3. Inyoite mineral from Bigadi~ deposits Chapter X:

287 291 292 296

.

ECONOMIC ASPECTS AND FUTURE PROSPECTS 1. Economic aspects 2. Future prospects

299

Chapter XI:

SUMMARY AND CONCLUSIONS

305

Appendix A:

SAMPLE COLLECTION AND PREPARATION 1. 2.

Collection Preparation

Appendix ~:

MAJOR ELEMENT ANALYSIS BY WET CHEMICAL METHODS

Appendix C:

MAJOR AND TRACE ELEMENTS ANALYSES BY X-RAY FLUORESdkNCE SPECTROMETRY

301

316 317 319

1. Introduction 2. Preparation of fusion beads 3. Preparation of powder pellets 4. Calibration procedure 5. Determination of unknowns 6. Corrections for contaminationsand interference

322 327 328 328 330 330

REFERENCES

332

tv

ABSTRACT

The Emet borate deposits are shown to be older and mineralogically more complex than previously thought.

They are

considered to have formed within the muds of separate or interconnected playa lakes, in areas of volcanic and seismic activity, fed partly by thermal springs and partly by streams draining the catchment areas, under arid or semi-arid climatic conditions during the Middle Oligocene. The borate minerals formed in two geochemically distinct sedimentary basins and are interbedded with limestone, marls, volcanic tuffs and clays, much of which appear to have been derived mostly from a volcanic terrain.

The borates show miner-

alogical and geochemical features in the two basins Which are suffiCiently different to suggest that the chemical compositions of ground and surface waters in the two basins dlffered at least from time to time.

Basement metamorphic rocks and Tertiary

limestone might also have been exposed and erosion of these may have contributed Ca and Sr to the lake waters. Sediments in the borate lakes are cyclical with both lateral and vertical facies changes.

The clastic sediments in both

basins are similar but are very much thicker in the northern basin.

The total Tertiary sedimentary thickness exceeds 750

metres.

The borate zone varies in thickness between 0-100 metres

and reaches its maximum thickness in the northern deposits. The Middle Oligocene sedimentary formations, including the borate zone, are far more f~ulted than previously thought. Thermal springs, which at present deposit travertine and sulphur, are active and widespread west of the Emet River. Colemanite predominates and occurs in many different forms. Other borates include meyerhofferite, ulexite, tunellite, teruggite, cahnite, hydroboracite and either veatchite or pveatchite. deposits.

Cahnite has not hitherto been identified from borate Calcite, gypsum, celestite, native sulphur, realgar

and orpiment are the principal associated minerals.

Montmorill-

onite and illite are the only clay mineral groups identified. Volcanic rocks, closely related to the Middle Oligocene lacustrine sediments, range from rhyolites to basalts and are very rich in potash relative to soda.

A complete transition

exists between tuffs and clays in the Emet borate zone sediments and is reflected in their geochemistry.

All tuffs, clays and

limestones are characterized by a relatively high concentration of B, As, S and Sr, and high Fe203:FeO ratios which indicate strongly oxidising conditions of sedimentation, with a very low rate of leaching. The deposits are characterized by high Ca borate (colemanite), very low Na, poor Cl and relatively high Mg, Sr, As and S concentrations compared with other borate deposits.

Like the

sediments, the borates are also characterized by a relatively high Fe203:FeO ratio, suggesting strongly oxidising conditions of precipitation.

The geochemical investigations suggest that the most likely sources of B, As and S were from the Tertiary volcanic rocks and associated thermal springs.

The major sources of Ca, Mg and Sr

are considered to be due to leaching of underlying basement rocks and Tertiary limestone by thermal springs. Investigation of the genesis of colemanite reveals no field evidence to unambiguously support its formation by replacement of ulexite or dehydration of inyoite after burial.

The early

colemanite nodules were probably formed directly from brines, penecontemporaneously

within the unconsolidated sediments below

the sediment/water interface, and continued to grow as the sediments were compacted.

Possibly the brines were never suffici-

ently concentrated to allow borate precipitation until the lakes were partially or wholly dried up. Later generations of colemanite occur in vughs, veins and as fibrous margins to colemanite nodules.

Other diagenetic

changes include the partial replacement of colemanite by hydroboracite, calcite, cahnite and a veatchite mineral.

When

weathered, colemanite is often almost completely replaced by calcite.

Realgar, celestite and sulphur appear to have been

deposited both during and after the formation of the borates. Quantitatively known reserves in the Emet district are more adequate but their quality is less assured.

The presence of

arsenic in both the sulphide and borate phases can present problems during mineral processing. are high-grade colemanite deposits

However, the Emet borates and should supply a substan-

tial quantity of the world's needs for many years.

CHAPTER I

INTRODUCTION

1.

Area of present study The Emet borate deposits are located in the middle of the

known borate deposits of western Anatolia, between Eski~ehir and Bigadiq borate districts

(Fig. 1).

They are in the west

of the province of Kttahya in the area between Gediz, Simav and Tav~anli.

The depositional

aligned north-south

basin of the borate beds is

and outcrops on the east side of the Koca

yay (Emet River) from Derekoy north almost to Killik. mining operations

are at Espey and Killik north of Emet town

and at Hisarcik village which is south of Emet. is transported

Themain

The borate

along the 30 kilometer road running north of

Emet to Emirler railway station.

The climate permits work to

be carried out throughout irE year. The Emet district contains the upland basin of the Emet River (Koca 9ay) which is almost entirely en~losed by higher land, except to the north near Koprucek where there is an outlet to the Tavsanli area and to the south east near Kaya I

village, leading to the Gediz area.

- 2 -

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1.1.1

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Cl)

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er

::.:::

Cl)

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Cl

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- 3 -

The Emet valley lies at altitudes of between 700 and 1000 metres, the river itself flowing at between 700 and 750 mEtres. The ranges lying to the west of the valley are higher and rise more steeply from the plateau than those to the east. The topography underlying

geology.

of the area is closely related to the In the west, the more resistant igneous

» rocks of Egrigoz and Katran mountains

at the northernmost

rise up to 2181 metres

part of the range.

To the south, the

volcanic

and metamorphic

metres.

The Kocadag ranges to the east of the Emet basin are

of metamorphic north-east

rocks of ~aphane mountain reach

origin and rise to only 1814 metres.

2121

North and

of Emet is another region of mainly metamorphic

and

volcanic rocks, the highest point at Kopr~cek Hill - an isolated andesite outcrop - being 1320 metres. The Ernet valley itself consists mainly of recent alluvium formations

and Middle Oligocene

lacustrine

sediments

contain-

ing borate deposits which outcrop at elevations of between 800 and 950 metres

(Plate 1).

The recent Gediz earthquake disturbances

to topography,

of 1970 resulted in severe

geology and landscape within the

Emet and Gediz valleys along the lines of NW-SE trending faults. The variations

in intensity of the earthquake depended

largely on the tectonic structure of the area and the rock types. EBih movements

resulted in features such as tension fissures

and landslides within the landscape; new thermal springs were generated by the movement of NW-SE trending faults. was caused to houses and mining properties; opencast workings but underground disturbed

(Plate 2; Fig. 2).

Much damage

landslips affected

operations were only slightly

-4 -

Plate 1.

General view of Middle Oligocene lacustrine formation in the Emet valley. Succession starts with lower limestone, continues with red formation, borate zone (foreground Hisarcik opencast mine-workings) and upper limestone. In the background metamorphic complex extending along a N-S direction. •

Plate 2.

The Derekoy village, south of Hisarcik, after the Gediz earthquake shocks. Photo shows the disturbances of earthquake.

II

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- 6 -

2.

Previous work The Ernet borate district is the most important source )f

calcium borates in the world.

Most of the deposits are owned

and operated by Etibank (Turkish mining and banking company). and on the northern border a small part of the deposits is owned and operated by the Turkish Borax Company at Espey and Killik. The Emet borate deposits were discovered accidentally by Dr. J. Gawlik whilst carrying out a survey of lignite deposits for M.T.A. (The Mineral Research and Exploration Institute of Turkey) in April, 1956.

The only mineral recorded was coleman-

ite, a very common calcium borate known in the other Turkish H

borate deposits

(Gawlik, 1956, Meixner, 1952, 1953, Ozpeker,

1969). The Turkish Borax Company has been operating mines in the Espey and Killik areas since September 1956 and an extensive exploratory drilling programme was undertaken by M.T.A. in 1958 and 1959, on behalf of the Etibank Company, in the Hisarcik and Espey localities.

The deposits are mined by open pit mining

methods at Hisarcik and underground mining methods at Espey and Killik, which will be converted to opencast mining in the near future.

Table 1 gives the reserves (expressed in tonnes) in

this area. " A paper in Turkish (Ozpeker, 1969) which surveyed most of the

known Tupkiqh borate deposits provides the only published account of the geology of the Emet Valley.

It listed borate and other

minerals that occur in the Ernet deposits (Table 2). Teruggite from the Hisarcik deposit was subsequently identified and the crystal structure described by Negro, Kumbasar and Ungaretti, 1973;

several other minavals have been identified

during the present study.

-7-

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til

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til

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Cd

Cd

.........

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.~§ ~~

;:$0

E-tU ..._, ~ ·rl r-! rl

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E-i

- 8 -

Mineral Name

Formula

Colemanite

Ca2B601l·5H20

Espey, Gbktepe, Hisarcik, Hamamkoy

Ulexite

NaCaB509·8H2O

Goktepe, Hisarcik

Celestite

SrS04

Hisarcik

Realgar

AsS

Hisarcik

Orpiment

As2S

Hisarcik

Gypsum

3 CaS04·2H20

Calcite

CaC0

Table 2

3

Locality

Goktepe Espey, Goktepe, Hisarcik, Hamamkoy

" Minerals listed by Ozpeker in the Emet borate deposits.

-9-

3.

The present study The borate deposits in the Emet Valley were first visited

by the writer in the summer of 1972. visited subsequently

The deposits have been

in the summers of 1973 and 1974 for the

purpose of making detailed maps, observations samples.

and collecting

Most of the samples collected were obtained in the

open pit in the Hisarcik locality and in the underground

workings

of the Espey and Killik mines.

and

Specimens of sedimentary

vObanic rocks have also been collected from the deposits and adjacent area.

The results of drilling and subsequent explora-

tion by both companies have been made available to the writer and access to all mines and opencast workings has been freely granted. The major purpose of the present study is to contribute to the understanding

of geology, mineralogy,

of borate deposits.

geochemistry, and origin

The main aims of the present research can

be listed as follows. 1.

Detailed mapping of the Emet borate deposits and the

adjacent area. 2.

Detailed

geology and mineralogy

deposits and associated

3.

Geochemistry

sedimentary

of the Emet borate

rocks.

of the borate deposits and associated

and volcanic rocks.

4. The application of geological, mineralogical geochemical

data together with field observations

the origin and diagenesis associated rocks.

and

to explain

of the Emet borate deposits and

- 10 -

4. Acknowledgements The research project was made possible by the Turkish Ministry of Education Scholarship which the author gratefully acknowledges.

The author wishes to take this opportunity to

express his gratitude to the management and technical staff of •

Etibank's mineral production divisions for their generous assistance during visits to the Emet and Kirka borate deposits. The author is greatly indebted to Dr. R.J. Firman for his very considerable assistance, encouragement and supervision throughout the whole period of this study and for critically reading the manuscript. I am grateful to Professor the Lord Energlyn for his encouragement and for the facilities in the Department of Geology at the University of Nottingham; to members of staff and research stUdents for advice and help, and particularly to Dr. P.K. Harvey for his interest, encouragement and many rewarding discussions on geochemical work; Dr. R.B. Elliott, Dr. J.A.D. Dickson, Dr. D. Field and Mr. P. Redfern for their unfailing help in some aspects of the research work. The Technical Staff are thanked for their help in the preparation of research materials, in particular, Mr. D. Jones for his invaluable assistance in the production of photographs;

Mr. E. Mitchell for rock-crushing; Mr. R.D. Hendry and Mr. T. Foster for preparation of thin sections; Mr. J. Eyett and Mr. W. Wilson for their help with XRF and XRD works and Mr. I.H. Beaumont for his help during geochemical work in the silicates laboratory.

- 11 -

Dr. R.H. Bate of the British Museum examined fossils from the Upper Limestone and I am most grateful to him for his assistance.

Dr. M.G. Barker in the Chemistry Department is

thanked for his kind help with single crystal work. Mr. F. Akdogan in the Mechanical Engineering Department is also thanked for his kind help with some programming. I would like to thank Miss A.M. Hargreaves and Mrs. J. Pearson who typed this thesis as fast as it was written and Mrs. J. Wilkinson for cartographic assistance.

Finally, my

gratitude goes to Miss R.A. Lockwood, not only for her help with maps and diagrams, but also for many other considerable contributions too numerous to mention.

- 12 -

CHAPI'ER II

DISTRIBUTION

AND CLASSIFICATION

OF BORATE DEPOSITS AND

MINERALS

1.

Geochemical

behaviour

of boron

Boron has a very low atomic weight both metallic

and non-metallic

(10.811) and presents

properties.

It is one 9f' the

most mobile and least abundant elements, the average amount of boron in the Earth's crust being estimated at less than 10 parts per million.

However,

it is found in minerals which

occur in nearly all geologic environments

and it forms many

unusual compounds with unusual properties

due to its dual

nature.

Because of the high ionic potential

(i = 13.0) B3+ is

unlikely to exist as a free ion. Boron occurs in several plutonic and metamorphic usually in the mineral tourmaline Goldschmidt,

1954).

detrital tourmaline clays.

In sedimentary

(Rankama and Sahama, 1950; rocks it occurs mainly in

and as a trace or minor element in illitic

The marine argillaceous

sediments contain relatively

larger amounts of boron than the non-marine (Landergren,

1945).

rocks,

argillaceous

sediments

It has also been claimed that there is a

- 13 -

direct relationship

between

.;heboron in the sediments and the

salinity of the water where they were deposited.

The average

values accepted by most authors for marine sediments are in the range of 110 to 120ppm B (Goldschmidt,

1954).

There are consid-

erable amounts of boron in the sea water (4.6ppm B) (Sverdrup, Johnson and Fleming, 1942).

The concentration

of boron in lake

and thermal spring waters varies widely and most of them are associated with volcanic activity. The greatest the non-marine

concentration

of borate minerals is found in

evaporite deposits, but the rest of the continental

clastic sediments are usually extremely low in boron. quantities

of boron are concentrated

borate minerals;

in deposits of hydrated

these deposits occur in closed basins and under

arid conditions within areas of volcanic activity. minerals precipitate

The boron

as a result of the concentration

tion of natural boron-bearing sedimentary

Large

by evapora-

waters in both non-marine

and marine

environments.

In connection with the studies on problems of the geochemical abundance

of boron in the Earth's crust, its cyclic

behaviour was discussed by previous authors such as Goldschmidt, Landergren,

Harder and Watanabe.

in the Earth's

Although boron is not abundant

crust, the cycle and concentration

crust have been reasonably well established

2.

Distribution

and classification

of boron in the

(Fig. 3).

of borate deposits and

minerals Borate minerals,not

necessarily

in a number of places in the world.

of commercial value,occur They are found in Turkey

- 14 -

Humid

area

,

t Meleo~

,

Arid area Atmosphere

t

/

Solar

IT)

{

/

Ocean

Sea

,

I

I

(Subsidence)

---

(Uplilft)

~ I (I>~P~~y' Schists

~Tfj'\

5Z&-~ .L:~~ 1«" 3-"'''-

'>: \\

~I/ ~

J

J 1

Br@

\V

~

,Plutonic

magma,;

(acid to intermediate in composition)

~

genc;:-:--'IS)

Granite

r

l 7

K-Na salts

Do lornite

~

~~. 0 ,

m

Boron metasomatism

-

t

Limestone

~

Gabbro

'iol ~

Basic magma

Fig.3.

t /

c'llcrhy

IT]

Scheme for the cycle and concentration of boron. The geochemical abundance of boron in rocks is cited according to Goldschmidt~ Landergren and Harder. (After Watanabe, 1964;. 1 - average content of boron in rocks (g/ton); 2 - exogenic concentration of boron (%); 3 - endogenic concentration of boron (%); SIS - sassolite; Ux - u1exite; Cl - colemanite; Pd - pandermite; Ke - kernite; In - inderite; Be - boracite; Sz - szaibelyite; L - ludwigite; K - kotoite; J - "jimboite" [Mn (BO ) ]; Dt _ datolite; Ax - axinite; 3 3 2 T - tourmaline; Br - braunite.

- 15 -

(Western Ana'~olia), U.S.S.R. United States

(California),

(Inder district), Canada, Argentina,

the Western Chile, Bolivia,

Peru, Tibet, China, India, Iran, Syria, New Zealand, New Guinea, Italy, Japan, Germany and Great Britain. Although boron is one of the rarer and more unevenly distributed

elements in the Earth's crust, there are extra-

ordinary concentrations in some localized

of boron deposits on an industrial

areas.

scale

All the United States, South American,

Turkish and many other commercial borate deposits are brackishfresh water deposits associated with volcanic activity. of relatively minerals

large amounts of boron present in sea water, borate

are also formed in marine evaporites,

Permian salts arla~ce Contact metasomatic

amount in Yorkshire

e.g. Stassfurt

Permian deposits.

borate deposits in skarns adjacent to granites

have great economic importance in the Soviet Union. occurences

of borate minerals

no economic value.

Similar

in the Isle of Skye, Scotland, have

The thermal spring waters from South America

and Japan and volcanic exhalation

of volcanic regions from Tuscany

in Italy also contain an appreciable Although

Because

amount of boron.

borate deposits formed in various environments

and very different

conditions,

the~onomicallymost

important

deposits are very closely related to the recent extensive volcanic activity along orogenic belts, characterized

by andesitic-

rhyolitic magmas, in the arid or semi-arid climates and nonmarine evaporite period.

environments

(closed basins) during the Tertiary

The main source of boron appears to have been volcanic

emanations

from such magma (Fig. 4).

Several authors have suggested various genetic classifications for the known major borate deposits in the world (Meixner, 1953;

- 16 -

- 1'1' -

Shabynin,

1957; Watanabe,

1964; Aristarain

The latest classification Hurlbut

(1972).

and Hurlbut,

19'/2).

has been done by Aristarain

and

They suggested the borate deposits are related

to three principal

geological

A. Deposits

environments:-

related to intrusive rocks

B. Deposits related to volcanic activity C. Deposits The deposits,

related to marine sediments

types A and B are the most important

economically, e.g. type A in U.S.S.R. and type B in Turkey and California

deposits.

The largest production

comes from type B of borate deposits.

of boron minerals

All Turkish borate

deposits appear to be associated with volcanic activity, classified

in type B.

detailed subdivision Deposits

Aristarain

and Hurlbut

(1972) give a more

for volcanic activity deposits,

type B:-

related to volcanic activity

1. Steam vents (= soffioni) natural and drilled, recovered

as sassolite

(Tuscany, Italy)

2. Thermal spring solutions Spring, California,

(Japan; Sulphur Bank

U.S.A.)

3. Thermal spring deposits (Jujuy, Argentina;

Chetco,

U.S.A. )

4. Mud flow (Jujuy, Argentina) 5. Desert Lake (brine) (Searles Lake, U.S.A.) 6. Playa (= marsh) on or near surface (NeVada, U.S.A.; Tibet; Bolivia; Peru)

7. Old playa, buried, highly deformed, low to no chemical changes (Salta, Argentina) 8. Old playa or lake deposit, buried, highly deformed, low to moderate Bigadiy,

chemical changes (Emet, Kirka,

Kestelek etc., Turkey; California,

Salta, Argentina)

U.SgA.;

- 18 -

All of these e~~amples are non-marine and are Tertiary younger in age.

or

Marine borate deposits associated with volcanic

activity have not been recorded. The composition and structure of borate minerals vary from one place to another

a

great deal, but they mainly occur as

Ca, Ca-Na, Na, Mg and Sr borates. are the major constitutions deposits.

The Ca and Na borate minerals

of most economic non-marine borate

The important borate minerals with their chemical

compositions and geological environments are listed in Table 3.

-

19

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