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CHEMICAL CONTROLS 0N TETRAHEDRAL
SITE OCCUPANCY IN AMPHIBOLES

Thesis for the Degree of M. S.
MICHIGAN STATE UNIVERSITY
STUART D. HANSON
.1971

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ABSTRACT
CHEMICAL CONTROLS ON TETRAHEDRAL
SITE OCCUPANCY IN AMPHIBOLES
BY

Stuart D. Hanson

Amphiboles from an amphibolite in Ontario, Canada, show a
range of compositional variation that is independent of the metamor-
phic grade as reflected in the plagioclase compositions. Composi-
tional changes in the amphibole include increases in Mg and Si
associated with decreases in A1 and Fe. As there are only two
mineral phases present in the amphibolite, amphibole and plagio—
clase, the Mg in the amphibole is the bulk Mg in the rock. The
Changes in composition suggest that the variation observed is not
directly associated with changes in temperature or pressure, but

is a direct function of the bulk chemical composition of the rock.

CHEMICAL CONTROLS ON TETRAHEDRAL
SITE OCCUPANCY IN AMPHIBOLES

BY

Stuart DP‘Hanson _

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Geology

1971

ACKNOWLEDGEMENTS

The writer wishes to thank Dr. Vogel for suggestions and aid
rendered throughout the course of the work and for the patience and
encouragement demonstrated during the time this work was being
accomplished.

Appreciation is also extended to Dr. R. Ehrlich, Dr. C. M.
Spooner and Dr. H. B. Stonehouse for aid and constructive criticism

offered during the work and on the manuscript.

ii

TABLE OF CONTENTS

Page

ACKNOWLEDGEMENTS ..................................... ii

LIST OF TABLES .......................................... iv

LIST OF FIGURES ......................................... v
Chapter

I. INTRODUCTION ................................... 1

II. METHOD ......................................... 2

III. PROCEDURE ..................................... 3

IV. DISCUSSION OF DATA ............................ 6

V. CONCLUSION ..................................... 15

LIST OF REFERENCES ........................ I ............ 17

APPENDIX ................................................ 19

iii

LIST OF TABLES
Page

TABLE 1. DATA .......................................... 6

iv

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

FIGURE

LIST OF FIGURES
Page

Metavolcanic zone in Cashel
Township. Ontario, Canada ..................... 8

Graphs of Si and Al in terms
of weight percent vs. plagio-
clase composition in terms of
anorthite Percent .............................. 9

Graph of amphibole Mg vs.
whole rock Mg in terms of
WBight Percent ................................ 11

Graph of amphibole Mg vs.
amphibole Si in terms of
weight Pel‘cen’c ................................ 12

Graph of amphibole Mg vs.
amphibole Al in terms of
weight percent ..................... _ ............ l3

Graph of amphibole Mg vs.
amphibole Fe in terms of
weight percent ................................. 14

INTRODUCTION

The purpose of this thesis is to determine whether there ex-
ists a systematic relationship governing the relative Al and Si oc-
cupancy of the tetrahedral site in amphiboles. The ionic radius
of Al allows the cation to coordinate with oxygen in either the Octa-
hedral or tetrahedral mode. The amphibole structure is composed
of double chain tetrahedral layers with cation layers in between.
The cations occur in a layer of three good octahedral sites labeled
M1, M2, and M3, a less perfect six— or eight-fold M4 site and a
single twelve-fold A site on the other side of the tetrahedral layer.
Al, as one of the smaller cations, has the Option in terms of size

of occupying the tetrahedral, or the M1, 2, or M3 octahedral Sites

(Gibbs, 1966).

Harry (1950) prOposed that a systematic relationship between
A1 and Si in amphibole tetrahedral sites may exist, and that it may
serve as an effective geothermometer in metamorphic rocks. Using
amphibole analyses selected from the literature, Harry observed an
increase in the Si as temperature increased. Engel and Engel (1962
a, b) found no such relationship in amphiboles when passing from
the amphibolite facies to the granulite facies. Dodge, Papike and
Mays (1968) suggested that the relationship might hold as modified
by pressure, and Leake (1965) suggested that composition and asso-

ciated minerals may also affect tetrahedral site occupation.

1

The major thrust of this paper is to select an amphibole-
bearing rock body whose composition is relatively constant and which
has been subjected to a metamorphic gradient. In such a case the
controls on A1, Si tetrahedral site occupancy can be determined.
On this basis a series of basic metavolcanics in Tudor, Grims-
thorpe and Cashel Townships, Ontario, Canada were selected. They
are described by Lumbers (1968, 1969) as largely mafic flows ori—
ginally basalt and andesite with minor inclusions of mafic pyroclas-
tics and felsic flows. Lumbers defines a regional metamorphic
gradient for the townships increasing from a greenshist facies in
Tudor and Grimsthorpe Townships to an amphibolite facies in the
central and northern parts of Cashel Township. He defined the gra-
dient on the basis of zoned albite, oligoclase and andesine isograds
which he extended from Limerick Township on the west into the
amphibolite band. These isograds are truncated by the metamorphic
aureole of the Westlemkoon Batholith in eastern Cashel Township.
For the purposes of this study this appeared to be an ideal area,
for apparently chemically similar rocks were subjected to a steep

metamorphic gradient .

METHOD
Leake (1965) suggested that the nature of the associated min-
erals could affect the elemental variations within the amphibole

structure. Therefore, in order to limit the number of possible

variables, amphibolites which contained only plagioclase and amphi-
bole were selected for testing. The advantage of using these am-
phibolites is that all the elements are partitioned between only two
mineral phases (amphibole and plagioclase) and such rocks are fairly
common over the whole area. Whole rock, plagioclase, and amphi-

bole major element analyses were done.

PROCEDURE

Samples were collected along the amphibolite belt in Cashel
Township and at one location on the Jordan Road in Tudor Town—
ship south of Cashel Township. Seventy samples were thin-sectioned
and examined microscOpically to insure that the amphibole and pla-
gioclase were the only primary phases present. From these, twenty-
six thin sections containing only the two phases were polished for
micrOprobe examination, and one hundred milligrams of each sample
was also prepared for X-ray fluorescence analysis.

The polished sections were analyzed on an ARL EMX electron
micrOprobe equipped with three channels. The beam was focused
to a diameter of approximately 0.5,: at an accelerating voltage of
15 kV and a specimen current of 0.020 flamps. The low specimen
current precluded the volatilization of significant amounts of Na from
the samples.

Nine thin sections from a geographic array approximately at

right angle to Lumbers' 1968 isograds and covering the entire area

4

were analyzed. Five point analyses per grain were made on two

grains of amphibole and two grains of plagioclase per sample. Point
analyses were carried out for Si, Al, Mg, Fe, Ca, Na, using SiOZ,

Al O MgO, Fe

2 3, albite and anorthite as standards. Two tra—

2 3’
verses were necessary for each grain to analyze for the six ele-
ments. Another continuous beam sweep was made of each grain
for Al and Si in order to insure the homogeneity necessary to dexnon-

strate equilibrium conditions.

The raw micrOprobe counts were then reduced to weight per-
cent analyses using a modification of the Bence and Albee, Electron
Probe Oxide Analysis Computer Program (Bence and Albee, 1968).
The program, named Mprobe, was originally written as Specimen
by Mrs. Kook Huber and debugged by L. G. Medaris and C. J.
Bowser (all from the University of Wisconsin at Madison) using
correction factors for ten elements and requiring count—ratio in-
put instead of raw micrOprobe counts. The program was further
modified and debugged by the author to accept raw micrOprobe data
and calculate weight percent analyses of up to fifteen elements from
an array of thirty—five elements using the Albee and Ray (1970)
correction factors (Appendix).

As only three elements could be analyzed onthe micrOprobe at one
time, it was decided to run three traverses of each amphibole grain and

two of each plagioclase grain. The first traverse in each case was

a continuous sweep of the entire grain which was recorded on an
X-Y plotter. If the grains in one sample were consistently homo-
geneous, this traverse would demonstrate that the rock was at or
near equilibrium. All samples measured were homogeneous with
the exception of the two southernmost, CA 7-4 and CA 7-1. For
the amphibole grains, the next two analyses consisted of five points,
each fifty/4 apart, with one traverse for Si, Mg and Fe and the

other for Al, Ca and Na. The elements chosen are the major con-

stituents of most amphiboles, and the larger the constituent percent-

age measured, the more accurate the weight percent analysis from
the modified Bence and Albee program. These six elements com-

prised an average of 94.5 percent of each sample and were never

less than 89.0 percent.
The use of Al, Ca and Na for plagioclase analysis also allowed

athree way cross-check of the determination. The three final de-
terminations were in each case i 1 percent.

The fluorescence samples were run on a General Electric X-

ray fluorescence unit in a helium atmosphere at 45 kV and 49.5

milliamps for 100 seconds for each of the elements Si, Al, Mg,
Ca, and K. Calibration curves were prepared based on five U. S.
Geological Survey standards run with the samples. Least square
curves Of best fit were calculated with the aid of the M.S.U. Agri-
cultural Experimentation Station least squares (LS) program. The
X-ray fluorescence of each sample provided a weight percent analy-

sis of the bulk composition in terms of Si, Al, Mg, Ca, and K.

 

 

 

 

 

 

 

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DISCUSSION OF DATA

Plagioclase compositions measured from An25 to An67, and
follow no consistent regional pattern (Figure l). The homogene-
ity of the plagioclase grains indicates that the metamorphic grade is
above that where the peristerites are stable. Lumbers' (1968) iso-
grads were derived from a consistent regional pattern of plagioclase
composition. The results reported here are inconsistent with such
a pattern. It is possible that post-metamorphic intrusions such as
the Westlemkoon Batholith to the east of the amphibolite metavolcanic
belt had a more extensive aureole effect or that Lumbers' (1968)
isograds are not accurate. The lack of a well defined metamorphic
gradient precluded evaluation of the response of amphibole compo—
sition to a gradient. However, there do exist ranges of amphibole
and plagioclase compositions (Table l), and those ranges provide
the Opportunity to test the response of amphibole composition to
slight changes in plagioclase composition in rocks with small bulk
composition variation.

Plots of Si and Al weight percent in amphibole versus plagio-
clase composition showed no systematic change (Figure 2). This
lack of relationship between A1 and Si and the plagioclase composi-
tion indicates that the amounts of Al and Si in amphibole is inde-
pendent of plagioclase composition. Although these rocks do not

exhibit a wide range in whole rock composition, this suggests that

 

 

 

 

 

 

 

16A 7-! and
CA 7-4 META VOLCA NIC ROCKS
5. 75 miles I - Q . I 3 g
' MILES

Figure l. Metavolcanic zone in Cashel Township, Ontario, Canada.

 

 

 

 

 

 

 

 

20.0 I I 1
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/ 6.0 2%? CA 60 “
AL (3.3.8420
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l2.0 - CA 7-10 -
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' cum-40 0’94 0
8’ CA 2964 220
38.0 L. CA SO ..
0.4580
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20.0 40.0 60.0

AN%
Figure 2. Graphs of Si and Al in terms of weight percent vs.
plagioclase composition in terms of anorthite percent.

lO
compositional variation that does exist might be the significant con-
trol on amphibole components. From the chemical data, the fol-
lowing relationships are evident:

1. As amphibole Mg increased, whole rock Mg in-

creased (Figure 3);

2. As amphibole Si increased, amphibole Mg in-
creased (Figure 4);

3. As amphibole Mg increased, amphibole A1 showed
a general decrease (Figure 5);

4. As amphibole Mg increased, amphibole Fe de-
creased (Figure 6).

The plagioclase composition of the samples exhibits no sys-
tematic relationship to any other variable. The amphibole Al versus
amphibole Mg plot suggests that two pOpulations with Mg increasing
with Al exist; however, this conclusion is not supported by the other
diagrams associating Al and Mg with other elements.

The data show that all available Mg went to the amphibole
which is necessitated by the fact that amphibole and plagioclase are
the only phases present. As Mg, Fe and some of the Al occupy
the octahedral sites in an amphibole, Mg's increase at the expense
of the Al indicates that it must be preferentially accepted into that
site. As total whole rock Mg increases in the bulk composition,
it also increases in the amphibole. These amphiboles have a lower

total charge in the octahedral site. This lower charge could be

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15

balanced by an increase of Ca in the A sites or by an increase of
Si in the tetrahedral sites. The increase in Si associated with the
increase in Mg in the amphibole and the constantly high Ca levels
demonstrate that the latter is the case. ' The closer spatial asso-
ciation of the tetrahedral sites and the octahedral sites and the
twelve-fold coordination of the A sites compared with the six-fold
coordination of the octahedral sites also suggest that a charge gain
in the tetrahedral site could balance an octahedral charge loss with

less structural strain than could the A site substitution.

CONCLUSION

The increase of Mg in amphibole in the amphibolite is a direct
function of the bulk Mg content of the rock. This increase, asso-
ciated with the decrease of Fe and Al, suggests that Mg is accepted
into the octahedral site preferentially with respect to Fe and Al.
That this increase in Mg is also associated with an increase in Si
while Ca remains constant indicates that the tetrahedral sites are
required to make up the octahedral site charge deficits associated
with an increase of Mg. Therefore, the major conclusion of this
paper is that the Si content of the tetrahedral site in amphiboles--
the Al/Si ratio--is not directly associated with temperature and

pressure conditions during cooling or during later metamorphic

events. The amphibole composition of these plagioclase amphibole

rocks is a direct function of their bulk rock composition. It seems

16
by pressure or temperature. It is also worthwhile to point out
here the importance of using whole rock analyses along with indi-
vidual mineral analyses, for without this type of analysis pairing,

an erroneous conclusion could have been made.

LIST OF REFERENCES

LIST OF REFERENCES

Albee, Arden L. and Lily Ray (1970) "Correction factors for elec-
tron probe microanalysis of silicates, oxides, carbonates,

phosphates, and sulfates". Analytical Chemistry, 42, 1408-
1414.

Bence, A.E. and Arden L. Albee (1968) "Empirical correction fac-

tors for the electron microanalysis of silicates and oxides".
J. Geol., 76, 382-403.

Deer, W. A., R. A. Howie and J. Zussman (1962) Rock-Forming
Minerals. John Wiley and Sons, Inc., New York, New
York, vol. 2, pp. 203-210 and 234-320.

 

Dodge, F. C. W., J. J. Papike, and R. E. Mays (1968) "Horn-
blendes from granitic rocks of the central Sierra Nevada
Batholith, California". J. Petrology, 9, 378-410.

Engel, A. E. J. and Celeste G. Engel (1962a) "Hornblendes

formed during progressive metamorphism of amphibolites,
northwest Adirondack Mountains, New YOrk”. Geol.

Soc.
America Bull., 73, 1499-1514.

(1962b) "Progressive metamorphism of amphibolite, north-
west Adirondack Mountains, New York". pp. 37-82 in
Engel, A. E. J., James, H. L., and Leonard, B. F.,
Editors, Petrologic studies: A volume in honor of A. F.
Buddington. Geol. Soc. America, 660p.

Ernst, W. G. (1968) Amphiboles. Springer-Verlag New York Inc.,
New York, New York, 125p.

Hallimond, A. F. (1943) "On the graphical representation of the
calciferous amphiboles”. Am. Min., 28, 65-89.

Harry, W. T. (1950) "Aluminum replacing silicon in some silicate
lattices". Min. Mag., 29, 142-149.

17

18

Leake, Bernard E. (1965) "The relationship between composition
of calciferous amphibole and grade of metamorphism”.
pp. 299-318 in Pitcher, W. S. and Flinn, G. W., Editors,
Controls of Metamorphism, John Wiley and Sons, Inc. ,
New York, New York, 368p.

Lipman, Peter W. (1964) "Mineralogy and petrogenesis of amphi-
boles from Gibson Peak Pluton, northern California". Am.
Min., 49, 1321-1330.

Cooper, A. F and J. F. Lovering (1970) "Greenschist Amphi—
boles from Haast River, New Zealand". Contr. 1\/Iinera1.
and Petrol., 27, 11-24.

Lumbers, S. B. (1968) "Geology of Cashel Township". Ontario De-
partment of Mines, Geological Report 71, Toronto, Ontario
Canada, 54p.

(1969) "Geology of Limerick and Tudor Townships". Ontario
Department of Mines, Geological Report 67, Toronto, On-
tario, Canada, 110p.

APPENDIX

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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_______;_n__ FI IT COLUMI IROUPIICS FOR JP TO 'IrTFPI VALUES, A S C'INJ CARD A 67
3 HIV BE USED IE IECF ,SARY. - -“ ~w ~~«--~- .A ..... 63" -_
C A 69
3 ptprg_ CARD . 429 O9 _OH IEICHT PER CE“T IV FIRST EIGHT COLUMNS WITH A 70
3 FIJR DECIHAL PLACcS Ir KHOII II. E. CARD IIVE UILT II CASE TAO). ‘”“A"’7I“’““‘
c A 72
_ C C113572.~}._5,.ANQ75_(IE_INCLUDED) APE IPPPATIO POR PICH POINT A 73
3 AUALYSPD. -—-a~m~ A11174-___A
c A 75
C ___mu_m_ A 76
REA?) 6'5: (‘4‘[1J)IJ=1035711311357 K"__77_"——
REAI) 65, ((AX(!.J).J=l.55).1=1.$5) A 73
_~ PRIIIT 51___ A 79
PI.-A3 67. HPT.NE. KV. CASE.<APLIL).L 17NE)“‘”'~~-~“—-"m—~~—~—————~u “A_"8D“"“
NIH=0 A 81
Q1_ 9 JTB=1.IPT A 82
II (NE-10) 1.1.2 A as
1 PI:AO 00, (ID(I).I=1. 91.18NIKI.K=1.NE) A 84
PI“ )_ 6R7 (CQ(I).I=1, IE) A 85
III "AD 68, ISTIII‘I).I=LHE) .1 ""'*“*—*“'- -—*---—~~—~---1-—1a5*-—
GO TO 3 A 87
2 PEAO 71.7(ID!1).};1.8).(RN(K).K=1.“L) A 88
PEAU 71. (CT'I).I=1. IIL) ‘*A 89
RLAD 71. ISTDIII.I=1.NEI A 9O
__ 3 “_n_ A H: 1, NE *__7 A 91
4 (RIM): CRINI-HHIH) ”’“‘“—“——’——"_335-~—~mv~fi-—-~———~~-~-~_r_._92m_-_C
”U (a JK=10NE ‘ 93
no" fL_Jl;_=__1 1....35 ‘ 94
II IXEIIJK) ELFIJLII 5.6.5 A 95
5 CONTINUE A 96
6 .IZIUKIHOL- _____._ __ ‘ 97
DO 7 JH=1.NE " ‘A“-—98 ___
lR:JZ(JM) 'A 99
7 P(JH)= ICRIUHQ/STOIJH116rTRILPI A 100
DU 8 1:1‘. 3 K 11'].
IF ICASE- COUFIII) 8.10.8 A 102
$-CQNTINUE A 103
o CUHTIVUE " '“’"A‘*10¢“—“‘
IF (NU”-HPT) 10.50.50 A 105
15 ISQLICE:} A 106
IF IISHITCH- 4) 11. 5c. 11 A-‘IU7—-““
11 TOT: O. O A 108
PHII;T 52. CASE A 109
PU”:NUH+1 ‘“' "‘ “‘ “““—"“‘“”T'A"f1u“"-'
TOTIT n.o A 111
ATP:O,O A 112

 

 

__~-EE(JL?QLO3..__m

re 12 1:1.NE

1? C(I)=U.U

r0 1'5 JBIoNE
CFAT(J)=R(J)A m.
CC”C(J)=CRAT(J)
DC 13 K=1t35

HIE JYEL<J)fELElKll_l§qut1§H_m_u.

 

_ 15 F‘EH(J)=K

13 CLHIIhUE
14 TCTwT=TOTNT+CFAT(J)

PFINT 55} (IE(I

)
PFINT 56; (xEL(I

1
= ‘E)
I

“H"

i

 

,__fl____u_”m£htxt_oa;fiWAIPER_WW____11_.2______flflwqu,,HWW”__WHWM_H_N__"_221_W

-119200 26 H=1:NE_~“

.-_“_J=3T“1L§)uflau_, 2__ _“,H_” M

, = b)

) I .
PRINT 571 (CFAT<1 . 1 NE>__
IF (IszTCH.3) 13 36 16

13 IF (IszTCHo?) 18 17.18

6

I
a
)_
n
o

_~_17_FEAD 53. HT3 __ __1__Mwu-u_nnh_‘n_223_,Mni H__"nr_q-wu__22w2h1-_u

PFINT 59} “TR
wLTPERawTR/dFACT

TCINTzTOTNTokTR
18 N:O

!:HEM(M)
DO 22 K=1QNE

 

- IF (xv-15) 26:20.21
23 381M): QB(M)+A(I, )*CONC(K)

GO T0222 3" ...... w_-..m__ww_nmmw-,wm.*v33_mm~.__n__2____3

21 BB<M1=aB(M>;Ax(I J)rCOVC(K)
22 CCHTINUE
If (KV 15) 23 23. 24

 

23 FB(M)= °B(M)+W(l)*WTR
60 T0 25
‘24 FB(M)= QB(M)¢A 'X(I)*HTR

 

i
i
E
I
I
E

lx>n>>

» vb
(A
A

 

25 n(4)=1, /T0TthRB(H)
26 CGYTINUE
F0127_5$13351_

b:>)J>->)>
1
i
i
l
I
v

 

 

 

 

CO!C(M)=CRAT(M)*9(”)
TOT: T0T+C014C(M)

 

 

 

 

 

lfiwilthEtlll_2§133j33
3n TOT=TOT+HTR

TOTAI=TOT

701:3.0

 

 

I

.______mu’38(M)=g. o -ukw"___u_fi__1____”222___ 153
27 CO'TlNUE 154
PRINT so. (c3N3<l).Isl.NE)
[:1 “‘_“__ _-“‘l A _ 156
29 IF («asrcc w<11~CcI>>-.oos1) 29733730 157
29 l=l+1 158

 

 

D0 31 1:1.VE
31 C(I)= CONC(I)
\:_'J+1*

134
135

 

 

 

[F (q‘ 10) 1903’: 32
32 pRINT 61
60 To 9

167

>J-)1)->a>x->J-x-’->x>)->z>1->J>J->:>It’d»x->
p
\a
U:

*5
0*
a»

136—_—

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

31 €01=5.A A 169
Dal‘fiflflfi ___MH“11 A 1”
34 SU {:‘EU'HCOWCLH Mfl“ W _-__._A.._,1.7l._.__ -
Su1=GQA+NTR A 172
____11_ 11h_vu:cu 6611(1W('):1=1;8) .111__ 1 1 _ 1 A 175
Duncu :43 (CON7(KLA).KLA:1,NE),HTR "g“”174 “
PRINT as. SJH A 175
no,3§“A=1.flam_. _____ A 176
I:JEA(M) A 177 ’
35 AIAPFR<M)=(CAA7<H)/FACT<I))~1000.0 A 178
.g__,h«_._mhufiBR‘NI 63,m(ATH7ERJ})AI:1ANE)m____ -1" 11Mh_m__nflwfl__ __ A 179
so To a ”"A 180
35 Mai A 181
37 no AiuflaLLEE A 153
1=fleq(fl, "“ A _183
no 4d K=1.NE A 184
‘-=1'E.,1LD - H A 185
IF («v-15) 3n.38.3° ””””""“" ’ A““1ao**"—‘
3% RB(M)=WB<M)+A(I.J>*anC(K) A 187
(“1.111-140 ._.,.__--- A 188
39 98(M)=nB(M>.Ax(1.J).Cowc<K) A ‘189‘“"“‘
4A CONTINUE A 190
"flwjf_15v~15).31a4111? A 191
41 {*Btn) =°B(H)+H( I )A'NTR ___ —W— _-M ._.______1- -..m_____-____.‘__1192___.1_._
no In 43 A 193
49 thM)=ana)gwxgx)erR __ A 194
43 R(M)=1,/T0TATIHB(M) I’il95fi_~"
44 CONTINUE A 196
no 45‘n=1,ue v A 197
covc<n)=CRAr(n)AB<P) ‘ " “““”” A“”198““‘—*
ror=ToT+CONCAM> A 199
"HJMIEQJG A 200
45 cosrtmue ' A '201
PRINT an; tanC(I>,l:1.NE) A 202
!F_Lh-4) 16137,50 . A 203
46 “3";4-1 hi- ___________,,,____V_ "-—___'-'fi”""_-r‘”zu‘4'—"‘_—
TOTNTzTOT ‘ 2”5
TOT§§;gj A 206
so To 37 A 207'
47 IF (TOT-1.00) ‘8049049 A 208
4" mane-JCT A 2’09
FRINI s9; vrp ""*“”“_“‘fl‘ “"““‘ A 210
VA'PEszyR/AFACI A 211
PR1N1_§4. VATPFR - A 212
Far 91 ‘ . A 213
TO’NT=1,00 A 214
T07:6 A 215
60 TC 37 A 216
49 PRINT 59; wrn A 217
f Gngfi 30F A 218
5a PRINT 62. NJM A 219
c ’ A 220
51 rogMAIW51H1L7x.58fl_gl§fipFR08E ANALYSES 0F MINERALS HITH UNKNOWN co A 221
1~prstryors//) ' “‘m“‘““”“”"”"“’_""”“ "“““”“““"“““‘“““_”T“‘222““”*“
59 FornAT (1Hc,9x,A6) A 223
51 ForHAt (1ors.4) A 224

 

 

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7-”..._—__.—_"_._. -_-..—--

54 FOFHAT (10F8.4/5F8.4)
53 rochr (8x,19A4,/)

“55“‘0““‘T <?X:6HELtMEATs;“x;1€IA575x)y'“‘—

57 ‘onwbr (2x,1oHCOUNTRAIIO.2x,15(F8,4))
Sn FOAWAT (7X.3HSUM:1¥.F8.4)

"59 rowan! ¢2x.5HAA1ER,7x.Fa.Z)**"'

66 FO£4AT (7X:SHCCNCEVT.A4XA15(78.4))

élmFOFVAT_(17¥,34fl»TdF AarvE VALUES FAIL To CQVVEQGE,
6) FO-CHAT (IHOD9x063dTOTAL NUMBER OF “I‘JEUALS AXMLYSEDH-Mf

63 FOPMAT (2X:12HntLoAT.PFRC./5X.6HX 1050:5Xo13(f3,4))

54 FonAAT (?Xa1?nNTP.AT.9FRC..F8.4)
65 ForAAr (87(14F5.2/).7FS,2)
55 FOGAAT (8A4)

6? FOCWAT,(3l4-A601§§§meu

'_”6n Focwhr <10F3.1)

69 FOGHAT (5A4.10F4.2)
_75 FoonAr <8A4.1JF4.2/5F4,2)
71 FJDAAr (1or5.1/§F8.1> ‘
END

* 236—

2?5
226

,277_m_

228
279
2301“ W
231
232
233“
234
235

237
238

239-“”~W

240
241

‘242'A_”"’

243

.. _______~1.08 5.19-1.5? 1.1a~1.09—1.é3~1.07 1.00 1.07 1.04 1.01 1.06 1.09 1.13
1.15 1.14 1.17 1.17 1.18 1.34 1.27 1.23 1.10 1.42 1.39 1.39 1.39 1.41

__.—__._~_1.44 1.49-1.51.1.55.1.55.1.§7.1.58 1.43-1.00 1.89 1.40 1.23 1.11 1.07 _
1. 02 1. 08 1. 03 1.10 1.05 1.07 1.10 1.10 1.19 1. 09 1.14 1.15 1. 41 1. 33

1 27.1. 23.1.39.1..30.1.30.1.35.1 37..1...11.1. 45 1.48.1150.1.51.1.50_L57-
2. 84 2. 29 1. 01 1.95 1.51 1. 31 1. 21 1.13 1.17 1.09 1.05 1.09 1.10 1.14
- L16 1.15.1.1} 1.10 1.10.1.00.1 51 1.42-1. 30 1.42_1. 40 1.40 1.39_1.41--
1. 44 1. 49 1. 51 1.93 1. 54 1. 00 1. 91 .93 3.17 1.18 1.00 1.02 1.39 1.27
,........-_1.18 1. 21.1.12 1.18 1.11.1.i3_1.10.1.15 1.18 1.15_1.20 1.21-1.6°.1159--
- 1. 43 1. 42 1. 47 1. 44 1. 43 1.43 1. 45 1. ca 1. 52 1. 55 1. 57 1.58 1.07 1.07
.4 93.3 00.1.25-_1me0.1.33.1.2°._1.1.9.1.21-1.11.L0.-L 10- 1.11.1114“
.13 1.15 1.13 1.18 1.18 1. 74 1. 63 1. 51 1. 44 1. 42 1.40 L 39 1. 39 1. 41
_......_ 1. 44 1. 48 1. 51.1.53 1.51.1.01 1. 00-..75 4.11 1.35 1. 09.1. 04 1.00 1. 34
- 1. 22 1. 24 1.13 1.28 1.11 1.12 1.10 1.15 1.17 L 14 1.19 1.20 1. 30 1. 24
1.55 1. 49 1 40 1.43 1 42.1.42-1.44 -1.17.1.51 1. 53 1. 50 1.56 1. 00 1. 66 -
7. 49 4 51 1. 39 1.11 1. 08 0. 99 L 00 L 75 1.25 1.13 1. 08 L 10 L 11 1.14
_...._.___1 11.1.15.1.12.1412.1.13.1.21.1.21.1.18.1.15 1.42.1139.1.39- 1.38.1.L10
L 49 L 47 1. 51 1.62 1. 59 1. 01 L 00 8.00 4. 85 1. 46 1.16 1.08 1. 02 1.01
1.01.1.28-1.15.1.09.1.11.1.12.1.15.1.14.1.10 1.13-1.18 1.19 1-32.1.25--
1.21 1.17 1.45 1.42 1.41 1.41 1.43 1.46 1.59 1.52 1.54 1.55 1.67 1.66
_........31-49-3.20.1.19-0.98-0.95.0.91.0-92.0.90.1.00,1.26_1.10.1.13-1.10.1-12-..
1.11 1.11 1. 0- 1.13 1.13 1.18 1.13 1. 09 1.07 L 43 1. 39 1. 38 1. 30 1. 37
1-41.1 42.1.41.1.10-1.40.1.11.1.10.1+21.1.8z_-1.13.1.1E.1101.1100.11.&..
o. 95 1. 01 1. 06 1.25 1.15 1.12 1.14 1.12 1.13 1.10 1.14 1.14 1. 20 1.?0
11- 1 40.1.38.1.39 1.41 1. 44 1.46 1.47 1.47 1.43 1.44 -
3.10 5. 75 1. 05 1. 20 1.14 1. 05 1.03 0. 99 1. 05 0. 99 1. 00 1.17 1.14 1.10
_-—-____.~1.1ifl1. 15 1.17 1.10 1.11.1.33.1.20.1.21.1 18 1. 49.1.15 1. 43 1.42.1._43.-
1. 45 1. 48 1. 49 1.51 1. 51 1. 50 1. 51 3 .12 7. 20 1. 83 1. 34 1.18 1. 00 1. 03
9_93.1.02.0.90.0.92-1+00_1.09.1.11.1..9.1.10.1.02.1.11.1.11.1.32.1.25
1.17 1.15 1. 29 1.27 1. 27 1. 35 L 30 1.38 1. 40 1.42 1.43 1.43 1.41 1.42
._____..._-4.13 8.70 2.11.1.56 1. 28.1.12 1. 00-1.0 0.1. 03 0.90-0.91 5 °0 1.09.1403---
1. 08 1. 09 1. 00 1.09 1. 09 1. 38 1.30 1.2 3 1.18 1. 21 1. 23 1.23 1.23 1.25
_.___...._.1. 28 1. 39 1.45 1. 41 1. 40.1.32.1. 37 5-25 9. 74 2. 39 1. 63 1.37-1.1z-1.09..
1. 00 1. 03 0. 94 E. 90 0. 89 0. 94 1. 00 0. 99 1. 07 1.03 1. 07 1.06 1.40 1. 32
_——_——1 2L1T1L14LL104404.18_1.20-1124_L28.1$111374 324.35.14.35...
0. 07 2 .32 2. 07 1. 70 1. 44 1. 23 L 13 1. 44 1.05 0. 90 0. 92 0.91 0. 88 0. 98
L 01.1. 62.1. on 1.18 1. 02.1.42.1.38_1.29 1. 231.21.1.18 1.18 1.17 1.18-
1. 25 1. 29 1. 3? L 34 1. 38 1. 38 1. 38 0. 90 2. 34 2. 86 1.89 1. 53 1.27 1.16
1.05 1. 05 0. 9s 3. 91 0.90 0.87 0. 8 0.94.1.00 0. 98.1. 00 1. 05 1.51.1. 41..
1. 31 1.25 1.15 1.10 1.15 1. 14 1.10 1.18 1.25 1. 29 1. 31 1.36 1. 35 1. 35
a 17 2 SWBJLWWZWDJ9913 4_£..91.£.21.fl_.9.0_.
0. 84 0.97 1. 05 1. 04 1. 08 1. 00 1. 49 1.38 1. 31 1. 23 1.20 1.19 1.18 1.19
_.........1. 2l 1. 24 -1.3i.1.3 4 1 .35.1.11.1 40 9. 50.2,51 1. °8-2. 19 1.72 1.35.1._?§.
' 1. 09 1. 08 0. 9s 0. 91 0. 91 0. 89 0. 8? 0. 83 0. 80 0.90 1.00 1.00 1.02 1.50
13 1.31.1 11_1.15 1.14.1.14.1.1E.1.10.1 19 1.20_1.27-1.29-1.35-1.31...
11.11 2. 02 2. 45 g. 30 1. 83 1. 45 1. 28 1.12 1.10 0. 97 0. 92 0 .92 0. 90 0. 90
0L8? n 83.0.70.0.93.1.nn.1.09.1.51.1111.1.35.1.18.1.15.1 15.1.1A.1.15_
1.17 1. i9 1. 25 1.20 1. 27 1.30 1. 352L 82 3. 51 1. 90 0. 93 6.88 0. 82 1. 57
1. 39.1. 25-1.03 a. 94 0.92.0.90.0.91-0.90 0. 91 0. 89-0 .92.0. 92.1.00.1. 00...
1. 79 1. 00 1.13 1.09 1. on 1. E8 1. 08 1.10 1.12 1.13 1.15 1.10 1.37 1.33
-._._____48.11.4. 60 1. 32.1. 00 0.90.0.80_1 05.1.40- 1. 30 1.06 0.97 0.95-8192.0.94
0. 92 0 .93 0. 91 n. 74 0. 94 1. L4 1. 00 0.90 1. 08 1.10 1.12 L 11 1.10 1.11
____L12.1.15_1.10_1.11_1.18.1.41.L311A.00.L45 .1. 38.1.11 5.13. 9 7.11.82.11.96...
1. 35 1. 33 1. 09 n. 99 0. 90 0. 94 0. 90 0. 94 0. 95 0. 93 0. 90 9 .97 1. 09 1. 04
_.........1. 0; 0. 97.1-17 1.15 1.15.1.13 1.14.1.10_1. 18 1. 20 1.21 1.72 1. 46.1.42
10. 34 4 .90 1. 49 1.11 1. 02 0. 92 0. 91 1.41 1.37 1.11 1. 02 0. 98 0. 90 0. 97
0. 96 0. 97 0. 94 0.08 0. 98.1.12.1. 07 1. 03 1. 00 1. 21 1.18 1.17 1.16 1.16...
1.13 1. 70 1. 27 1.23 1. 24 1. 49 1. 45 7.38 2.19 1. 95 1. 73 1. 01 1. 20 1.15
I]. 9BLMMJ8JJULEMAQWL 9? "(-18L1L59J:q9_14__8 .1.L3..6._..
1. 27 1.18 1. 01 n. 98 0. 97 0. 97 0. 98 1.11 1.13 L 12 1.12 1.11 1.11 L 10
-.....-...2.07-2.21.1.95-1.JA.1.12.1.20-1.1A-8.22.0.97-0.85 0.79-0.80-0.§A.Q.93 ..

 

 

_.__—_._-_

 

 

 

                

 

 

 

 

 

 

—____..-__ .

....-_....1.01

0.92 0.92 0.84 3.91 6.91 1.53-1.40 1.29 1.21 1.03 1 00
1.09 1.13 1.15 1.15 1.14 1.14 1.13 7.44 2.39 2.10 1.58

0.98 0.84 8.80 0.81 0.84 -0.91,_0.91 0.92 0.88 0 91
1. 33 1. 24 1. 01 1.00 1.00 0. 99 1. 01 1. 02 1.11 1.14 1.15

7 84.2.38 2.19 1.01.1.55.1.34.1.28.1.r4.1.:0-0187 0. 81.

 

0. 89 0. 93 0. 89 0. 8i 0. 91 1.03 L 48 1.30 1. 27 1.02 c. 99
1. 03 1.11 1.15 1.10.1.15 1.17 1.12 8.21 2. 4i 2. 26 1.5?
1. 04 1.00 0.87 0. 81 0. 78 0 85 o. 85 0.88 o. 91 0.88 0. 9c
1. 3: 1. 28 1. 01 0. 98 1.00 0. 99_1. 00 1.02 1. 04 1.11 1.13

8.97 2. 40 1. 01 1. 60 1. 48 1. 43 1. 27 1.07 1.01 0. 87 0. 81

r

0.82-0 87 0. 85 0.19.0.88.1.59.11§1.1.44- 1. 32.0.97. 0. 95

 

L 00 1. 02 1. 04 1.09 L 12 1.17 1.14 9.98 2.53 1.01 1. 69
-1. 09 1. 02 0. 87 0. 80- 0. 77 0. 72 0. 77- 0.8 0 0. 81 0. 82 0 66
L 49 1. 30 0. 9s 6 .93 0. 93 0. 92 0. 95 0. 98 1. 00 1. 01 1. 03
_.{0 82 2. 00 -L 03 E. 83.1. 47.1.20 1.25.1. 12 1.04 0. 88 0. 80
0. 7 9.80 0. 79 .84 0. 84 1. 54 1. 40 1. 42 1. 30 0. 96 0. 93

.0.9i.1.90_1. 05- 1.01.1100.1_17.1.1A11.48 2. 68-1.04 0.84

 

........-_1. 39.1. 35 0. 90

.._ 0.71 0.08 0.72

L 19 1. 00 0. 88 .81 0.78 0. 73 0.72 0. 75 0. 74 0. 77 0. 60
_ _ .93.0. 91.0 .90 0.90.0-91 0. 95 0. 96-1. 00
14.99 3.05 1.14 .89 0.85 1.30 1.21 1.08 1.13 0.93 0.84
.12-o.79 1.10 1.80-1.35-1.24-0.97 0.94
,9 3..34844(151.29

CSID'D‘D'DI'

0.92 0.93 0. 93 7 1. 00 1. 22 1.1835.
0.82.0.85-0 81.0..0.0.91.0.91.0.Bfi_1.85 0. 35-0.82 0

 

0119.0.84--

1.01 1.00
1.59 1.37
11.90 1.00

1.13 1.17

0.76 0,78

0.90.0.96

1.40 1.56
5.80.1.05
1.07 1.10
0.77-0.73
0.92 0.90
1.55-1.21
0.82 1.48
1.01-1.18
0.80 0.75
5.93-0.91
1.12 0.90

1.00--
1.17
1.41..
1.14
0082..
1.01
1.22--
1.51
1.15--
0.893
0.90.-
1.31
1.49--
1.14
0.77
0.91

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1.34
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0.74
0.91..
0.94

6 4 131.85.. 1.1. S -1...02..

1.04 0.98 1. 04 1. 05 1. 07 1.35 L 07 1. 05 1. 05 1. 05 1. 05 1.04 1.00 0.99
._.....-_.39. 59 5.17 1. 73 1. 25 1.10.0 98 0.20-1.80 0.85 0.80 0. 82 0. 92 0. 90 0. 89
0. 86 0. 85 0. 82 0.84 0. 84 1.18 L 10 1.05 1. 00 1.10 1. 07 1. 05 1. 03 1. 05

1.07 1 00 1. 05-1.05.1.01.1.01.1.00...... .....

 

 

 

 

 

 

- ....._ .—___.

 

 

 

 

 

 

 

 

 

 

 

 

- - ._-_ ,._.__.___

H7H————.. _-__—__——-

155.1 03 1.4 0 1-08 1.04 1.
.09 1.12 1. 09 1.14 1.15 1. 28 1. 21 1.18 1.14 1.33 1.
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