CHEMICAL ANALYSIS OF ROCKS AND MINERALS Geological ...

CHEMICAL ANALYSIS OF ROCKS AND MINERALS

NEW ANALYTICAL METHODS DEVELOPED FOR SOME MAJOR

AND MINOR COMPONENTS

Risto Saikkonen

Geological Survey of Finland

Espoo 1996

CHEMICAL ANALYSIS OF ROCKS AND MINERALSNEW ANALYTICAL METHODS DEYELOPED FOR SOME MAIOR


by

Risto Saikkonen

Academic Dissertation

To be presented with the permission of the Faculty of Science of the University of Helsinki

for public criticism in the Main l-ecture Hall A110 of the Department of Chemistry

(A.I. Virtasen aukio 1) at 12 noon on February zth, L996.


Chemical Laboratory

Espoo 1996


NEW ANALYTICAL l\1ETHODS DEVELOPED FOR SOl\1E MAJOR


by

Risto Saikkonen

Academic Dissertation

To be presented with the permission of the Faculty of Science of the University of Helsinki

for public criticism in the Main Lecture Hall AllO of the Department of Chemistry

CA.! . Virtasen aukio 1) at 12 noon on February 2th, 1996.


Chemical Laboratory

Espoo 1996

Saikkonen, Risto 1996. Chemical analysis of rocks and minerals - new analytical

methods developed for some major and minor components. Espoo: Geological Survey

of Finland. 47 pages,2 figures, 5 tables and one appendix.

The snrdy examines a number of geological samples the chemical analysis of which requires in-depth

knowledge of preparation, decomposition and determination techniques. Rock, mineral and meteorite samples

were analysed with modified classical wet-chemical methods and more modern instrumental methods

(Publications I-D. The Summary presents the first published total analysis of the Malampaka meteorite (an

olivine-bronzite chondrite). Chemical analyses of some mineral samples are also presented for the frrst time.

In the course of the work, analytical methods were developed and studied for rocks, minerals and other

geological materials such as meteorites. To establish the accuracy, precision and detection limits of these

methods, they were compared with existing methods using domestic and international reference samples.

The development and investigation of analytical methods for water, ferrous iron and carbon are presented in

separate publications (VI-VIID. The determinations of these components are discussed in the Summary in

those respects not dealt with above. Determinations of halogens, sulphur and loss on ignition are discussed

on the basis of the literature and practical experience.

Key words (Georef Thesaurus, AGI): chemical analysis, wet methods, atomic absorption, emission

spectroscopy, infrared spectroscopy, rocks, minerals, meteorites, chemical elements, water, ferrous iron,

carbon, halogens, sulfur, loss on ignition.

Risto Saikkonen


FIN-02150 Espoo

Finland

Y,ISBN 951-690-61 7-d1,".. ^--/i1<? L*'">' -l/nHelsinki 1996

o( t7 "'ry )Ytiopistopaino c/T1 /*e'?t'-t'FPikapaino

Saikkonen, Risto 1996. Chemical analysis of rocks and minerals - new analytical

methods developed for some major and minor components. Espoo: Geological Survey

of Finland. 47 pages, 2 figures, 5 tables and one appendix.

The study examines a number of geological sampies the chemical analysis of which requires in-depth

knowledge of preparation, decomposition and determination techniques . Rock, mineral and meteorite sampies

were analysed with modified classical wet-chemical methods and more modern instrumental methods

(Publications I-V) . The Summary presents the first published total analysis of the Malampaka meteorite (an

olivine-bronzite chondrite). Chemical analyses of some mineral sampies are also presented for the first time.

In the course of the work, analytical methods were developed and studied for rocks, minerals and other

geological materials such as meteorites. To establish the accuracy, precision and detection limits of these

methods, they were compared with existing methods using domestic and international reference sampies.

The development and investigation of analytical methods for water, ferrous iron and carbon are presented in

separate publications (VI-VIII) . The determinations of these components are discussed in the Summary in

those respects not dealt with above . Determinations of halogens, sulphur and loss on ignition are discussed

on the basis of the literature and practical experience.

Key words (Georef Thesaurus, AGI): chemical analysis, wet methods, atomic absorption, emission

spectroscopy, infrared spectroscopy, rocks, minerals, meteorites, chemical elements, water, ferrous iron,

carbon, halogens, sulfur, loss on ignition.

Risto Saikkonen


FIN-02150 Espoo

Finland

~ .. crtL ISBN 951-690-617-6 (~J ~ () nf'f I'Y' ='")

Helsinki 1996 C/l..., . ~ Yliopistopaino Pikapaino

FOREWORD

INTRODUCTION


AND CERTAIN SPECIAL SAMPLES

Sample preparation

Rock analysis

Mineral analysis

Analysis of special samples

ELEMENTS AND COMPONENTS REQIIIRING

INDIVIDUAL DETERMINATION

Determination of water

Determination of ferrous iron

Determination of carbon

Determination of halogens, sulphur and

loss on ignition

SUMMARY

ACKNOIü/LEDGEMENTS

REFERENCES

APPENDIX: chemical composition ....

4

L2

2.t

2.2

2.3

2.4

J

3.1

3.2

J.J

3.4

L2

L4

2L

22

24

24

26

29

30

35

38

4

39

1

2

2.1

2.2

2.3

2.4

3

3.1

3.2

3.3

3.4

4

3

CONTENTS

FOREWORD

INTRODUCTION


AND CERTAIN SPECIAL SAMPLES

Sampie preparation

Rock analysis

Mineral analysis

Analysis of special sampies

ELEMENTS AND COMPONENTS REQUIRING

INDIVIDUAL DETERMINATION

Determination of water

Determination of ferrous iron


Determination of halogens, sulphur and

loss on ignition

SUMMARY

ACKNOWLEDGEMENTS

REFERENCES

APPENDIX: chemical composition ....

4

7

12

12

14

21

22

24

24

26

29

30

35

38

39

FOREWORD

This work comprises the following papers published previously:

I Laajoki, K. and Saikkonen, R., 1977 . On the geology and geochemistry

of the Precambrian iron formations in Väyrytänkylä, south Puolanka area, Finland.

Part Geochemistry. Geological Survey of Finland, Bulletin 292,78-723.

11 Danielsson, R. and Saikkonen, R., 1985. Chemical analysis of USGS-

W-2, USGS-DNC-I and USGS-BIR-I standard rocks. Geological Survey of Finland,

Report of Investigation 70. 13 p.

UI Lahti, S. and Saikkonen, R., 1985. Bityite 2Ml from Eräjärvi compared

with related LiBe brittle micas. Bulletin of the Geological Society of Finland 57, Part

r-2. 207-215.

W Lahti, S. and Saikkonen, R., 1986. Kunzite from the Haapaluoma

pegmatite quarry, western Finland. Bulletin of the Geological Society of Finland 58,

Part2,47-52.

V Kinnunen, K. A. and Saikkonen, R., 1983. Kivesvaara C2 chondrite:

silicate petrography and chemical composition. Bulletin of the Geological Society of

Finland 55, Part t,35-49.

VI Saikkonen, Risto J., 1990. Determination of water in silicate rock

samples by combustion and infrared absorption. Bulletin of the Geological Society of

Finland 62, Pat l,7l-77.

VII Saikkonen, Risto J. and Rautiainen, Irja A., 1993. Determination of

ferrous iron in rock and mineral samples by three volumetric methods. Bulletin of the

Geological Society of Finland 65, Part I, 59-63.

4

FOREWORD

This work comprises the following papers published previously:

I Laajoki, K. and Saikkonen, R., 1977. On the geology and geochemistry

of the Precambrian iron formations in Väyrylänkylä, south Puolanka area , Finland.

Part Geochemistry . Geological Survey of Finland, Bulletin 292, 78-123.

11 Danielsson, R. and Saikkonen, R., 1985. Chemical analysis of USGS

W-2, USGS-DNC-1 and USGS-BIR-1 standard rocks . Geological Survey of Finland,

Report of Investigation 70. 13 p.

111 Lahti, S. and Saikkonen, R., 1985. Bityite 2M1 from Eräjärvi compared

with related Li-Be brittle micas. Bulletin of the Geological Society of Finland 57, Part

1-2, 207-215 .

IV Lahti, S. and Saikkonen, R., 1986. Kunzite from the Haapaluoma

pegmatite quarry , western Finland. Bulletin of the Geological Society of Finland 58,

Part 2, 47-52.

V Kinnunen, K. A. and Saikkonen, R., 1983. Kivesvaara C2 chondrite:

silicate petrography and chemical composition. Bulletin of the Geological Society of

Finland 55 , Part 1, 35-49.

VI Saikkonen, Risto J., 1990. Determination of water in silicate rock

sampies by combustion and infrared absorption. Bulletin of the Geological Society of

Finland 62, Part 1, 71-77 .

VII Saikkonen, Risto J. and Rautiainen, Irja A., 1993. Determination of

ferrous iron in rock and mineral sampies by three volumetrie methods. Bulletin of the

Geological Society of Finland 65 , Part 1, 59-63 .

)

VIII Saikkonen, Risto J. and Rautiainen, Irja A., 1990. Determination oftotal carbon and non-carbonate carbon in rock samples by an infrared absorption

method. Bulletin of the Geological Society of Finland 62, Part 2, L49-156.

These publications are referred to in the Summary with Roman numerals I-VIII.

Publication I deals with the geochemistry of the Precambrian sedimentary iron

formations at Väyrylänkylä, Puolanka, with the aid of total rock, partial rock and

mineral analyses.

Publication II presents new, previously unpublished analytical data on three reference

rock samples of the USGS, i.e., W-2 diabase, DNC-I diabase and BIR-I basalt. The

analytical data obtained are compared with those reported by geolaboratories abroad.

Publication III examines in detail the bityite mineral, Cä,.sr lq.o: Nao.oz (Lir.re Als.os

M9o.rs Feq.13) (Alr53 Bez.z, Si4.26) ors.ro (oH)4.s4 F€0.,u, which occurs in a

pegmatite vein at Eräjärvi. The mineral had not previously been described from

Finland.

Publication IV describes a purple, transparent spodumene from Peräseinäjoki, Finland,

which turned out to be a gem-quality kunzite.

Publication V is a study on the Kivesvaara meteorite found in Paltamo, northern

Finland, in 1968. In chemical and mineralogical composition and in structure the

meteorite is a rare C2-class carbon-bearing chondrite.

Publication VI describes a new method for determining water in rock and mineral

samples based on infra-red absorption.

5

VIII Saikkonen, Risto J. and Rautiainen, Irja A., 1990. Determination of

total carbon and non-carbonate carbon in rock sampies by an infra red absorption

method. Bulletin of the Geological Society of Finland 62, Part 2, 149-156.

These publications are referred to in the Summary with Roman numerals I-VIII.

Publication I deals with the geochemistry of the Precarnbrian sedirnentary iron

formations at Väyrylänkylä, Puolanka, with the aid of total rock, partial rock and

mineral analyses .

Publication II presents new, previously unpublished analytical data on three reference

rock sampies of the USGS , Le., W-2 diabase, DNC-1 diabase and BIR-1 basalt. The

analytical data obtained are compared with those reported by geolaboratories abroad.

Publication III examines in detail the bityite mineral, Cal.93 Ko.o3 Nao.02 (Li1.l9 A13.68

MgO.35 Feo.13) (Al l.53 Be2.21 Si4.26 ) 019.30 (OH) 4.54 FeO.161 which occurs in a

pegmatite vein at Eräjärvi . The mineral had not previously been described from

Finland.

Publication IV describes a purple, transparent spodumene from Peräseinäjoki, Finland,

which tumed out to be a gem-quality kunzite.

Publication V is a study on the Kivesvaara meteorite found in Paltamo, northem

Finland, in 1968. In chemical and mineralogical composition and in structure the

meteorite is a rare C2-class carbon-bearing chondrite.

Publication VI describes a new method for determining water in rock and mineral

sampies based on infra-red absorption.

6

Publication VII examines three methods for determining ferrous iron and discusses

their accuracy and precision, and possible sources of error-

hrblication VIII reports the determination of total carbon with infra-red absorption

spectrometry and that of non-carbonate carbon in a chemically pretreated sample using

the same method.

6

Publication VII examines three methods for detennining ferrous iron and discusses

their accuracy and precision, and possible sources of error.

Publication VIII reports the detennination of total carbon with infra-red absorption

spectrometry and that of non-carbonate carbon in a chemically pretreated sampIe using

the same method.

INTRODUCTION

The chemical analysis of rocks and minerals determines the concentrations of elements

and certain components. Geological investigations, which are often an integral part of

exploration for resources of raw materials in bedrock, require increasingly detailed

information on the chemical composition of rocks and minerals. Although often

covered, bedrock occurs everywhere on the globe. It is composed of different

lithologies (rocks), which in turn are composed of minerals. Most minerals, of which

over 2000 species are known, are crystalline compounds. The majority are rare and

thus unimportant as rock-forming constituents. The major minerals of rock types

number only a few tens and these are mainly silicates.

The established practice in classical rock analysis is to determine the composition of

13-18 elements. This type of analysis is called total analysis. Chemical analyses of

rocks are usually expressed as weight percents of oxides for the major elements. It is

assumed, in the absence of oxygen determinations, that the major cations are

accompanied by a stoichiometrically equivalent amount of oxygen. Most rocks are

silicate rocks composed of silicate minerals; total analysis is then called silicate analysis

and includes the following major and minor components: silica, titanium dioxide,

aluminium oxide, manganese oxide, iron(III) oxide, iron(Il) oxide, calcium oxide,

magnesium oxide, sodium oxide, potassium oxide, phosphorus pentoxide, carbon

dioxide, constitutional water and moisnrre water. These components are analysed

because they are the ones used in petrochemical calculations of the rocks and because

it is easier to compare rock analyses with each other if the same components are

determined and if they are reported in the same order (Lightfoot 1983, Mueller &

Saxena 1977). Sulphur, fluorine and chlorine concentrations and loss on ignition are

also often determined. The concentrations of major components usually exceed l%,

and those of minor components are in the range 1-0.01 Vo. The consentrations of trace

components are less than 0.01% and are frequently reported in parts per million, PPD,

or nglg. All the components included in the total analysis of rocks or minerals may be

called major components. Today, an ever increasing number of trace elements can be

determined (Table 1). For silicate minerals, the concentrations of components are

reported in the same way as they are for silicate rocks. The components of non-silicate

minerals and rocks may differ and these are often reported in order of importance.

7

1 INTRODUCTION

The chemical analysis of rocks and minerals determines the concentrations of elements

and certain components . Geological investigations, which are often an integral part of

exploration for resources of raw materials in bedrock, require increasingly detailed

information on the chemical composition of rocks and minerals . Although often

covered, bedrock occurs everywhere on the globe. It is composed of different

lithologies (rocks), which in turn are composed of minerals . Most minerals , of which

over 2000 species are known, are crystalline compounds. The majority are rare and

thus unimportant as rock-forming constituents. The major minerals of rock types

number only a few tens and these are mainly silicates.

The established practice in classical rock analysis is to determine the composition of

13-18 elements . This type of analysis is called total analysis . Chemical analyses of

rocks are usually expressed as weight percents of oxides for the major elements. It is

assumed, in the absence of oxygen determinations , that the major cations are

accompanied by a stoichiometrically equivalent amount of oxygen. Most rocks are

silicate rocks composed of silicate minerals; total analysis is then called silicate analysis

and includes the following major and minor components: silica, titanium dioxide ,

aluminium oxide, manganese oxide, iron(lII) oxide, iron(ll) oxide, calcium oxide,

magnesium oxide, sodium oxide, potassium oxide, phosphorus pentoxide, carbon

dioxide, constitutional water and moisture water. These components are analysed

because they are the ones used in petrochemical calculations of the rocks and because

it is easier to compare rock analyses with each other if the same components are

determined and if they are reported in the same order (Lightfoot 1983 , Mueller &

Saxena 1977). Sulphur, fluorine and chlorine concentrations and loss on ignition are

also often determined. The concentrations of major components usually exceed 1 %,

and those of minor components are in the range 1-0.01 %. The concentrations of trace

components are less than 0.01 % and are frequently reported in parts per million, ppm,

or ng/g. All the components included in the total analysis of rocks or minerals may be

called major components . Today, an ever increasing number of trace elements can be

determined (Table 1). For silicate minerals, the concentrations of components are

reported in the same way as they are for silicate rocks. The components of non-silicate

minerals and rocks may differ and these are often reported in order of importance.

8

Mineral analyses are used to calculate the formula for the mineral being investigated,

to check the "purity" of the mineral, e.g. to establish the extent to which two minerals

are mixed with each other in solid solution, and to gauge large compositional variations

in minerals. The above also applies to special geological samples such as meteorites.

The elements determined at any one time depend on the purpose for which their

concentrations are used or needed (see Johnson & Maxwell 1981, Potts 1987).

Table I gives the total composition and several trace element concentrations of a

silicate rock, granite G-I, which was the first international reference rock sample

(Fairbairn 1951). The components of the total analysis are summed. The sum is one of

the criteria of the success of total analysis. It does not, however, guarantee that the

data on the single components are correct. Opinions differ about the magnitude of the

sum of a good analysis but 100% + 0.5% is universally considered acceptable. The

analysis sum should be corrected by subtracting the amount of oxygen corresponding

to sulphide sulphur and fluorine and chlorine, because the elements that occur as

sulphides, fluorides or chlorides are reported as oxides. The sulphide correction can be

done only if the mineral composition of the sample is known (Jeffery & Hutchison

1983).

The analytical method used here includes chemical pretreatment of the sample and the

method of determination plus the output of data. Sample preparation with its various

stages takes place between the analytical procedure and sampling. The method of

determination includes the pretreatrnent technique of a portion of the sample, the

instrumental or other determination and the output of data. The quality of the

analytical methods depends on the quality of all the contributing factors. The quality of

the methods can be assessed with various parameters deduced from the analytical data

obtained (see Johnson 1993, Potts 1993). Thanks to the rapid progress made in

instrumentation, automatics and data processing, well-equipped laboratories can now

produce more and more rock analyses with an increasing number of trace elements.

Assuring the quality of analytical data has thus become increasingly important, and

laboratories are required to report on and interpret the quality and applicability of their

analytical data. Correct use and interpretation of analytical data help guarantee the

success of geological investigations and interpretations.

8

Mineral analyses are used to calculate the formula for the mineral being investigated,

to check the "purity" of the mineral, e.g. to establish the extent to which two minerals

are mixed with each other in solid solution, and to gauge large compositional variations

in minerals. The above also applies to special geological sampies such as meteorites.

The elements determined at any one time depend on the purpose for which their

concentrations are used or needed (see Johnson & Maxwell 1981, Potts 1987).

Table 1 gives the total composition and several trace element concentrations of a

silicate rock, granite G-I, which was the first international reference rock sampie

(Fairbairn 1951). The components of the total analysis are summed. The sum is one of

the criteria of the success of total analysis. It does not, however, guarantee that the

data on the single components are correcL Opinions differ about the magnitude of the

sum of a good analysis but 100% ± 0.5% is universally considered acceptable. The

analysis sum should be corrected by subtracting the amount of oxygen corresponding

to sulphide sulphur and fluorine and chlorine, because the elements that occur as

sulphides, fluorides or chlorides are reported as oxides. The sulphide correction can be

done only if the mineral composition of the sampie is known (Jeffery & Hutchison

1983) .

The analytical method used here includes chemical pretreatment of the sampie and the

method of determination plus the output of data. Sampie preparation with its various

stages takes place between the analytical procedure and sampling. The method of

determination includes the pretreatment technique of a portion of the sampie, the

instrumental or other determination and the output of data. The quality of the

analytical methods depends on the quality of all the contributing factors. The quality of

the methods can be assessed with various parameters deduced from the analytical data

obtained (see Johnson 1993, Potts 1993). Thanks to the rapid progress made in

instrumentation, automatics and data processing, well-equipped laboratories can now

produce more and more rock analyses with an increasing number of trace elements.

Assuring the quality of analytical data has thus become increasingly important, and

laboratories are required to report on and interpret the quality and applicability of their

analytical data. Correct use and interpretation of analytical data help guarantee the

success of geological investigations and interpretations.

9

Table 1. Compositions of USGS granite sample, G-1, which was theint,ernational geological reference sample in the world (FairbairnL951) Numerical values for the concentrations of major, minor andconstituents are from the paper of Govindaraju (1989) .

firsts^! ^1gL AI.

Erace

Major and mj-norconstituents ?

Trace elements nglg

sio2Ti02A12O3

Fe2O3

FeOMnOMgoCaONarOKzoPzosHzo*Hzo'UU2

!

öOthers

Sum-olF, s, c1

Sufl\con.)

FerO, ,oo,

72 .5Lv . zo

L4.23n cÄ

0.030.351.373.335.5L0.080 .340.050.070.070.0r-o -29

r.öö:-3"0.03

1oo. 31

a. vf

0 -044o.70.00321.5

108030. 050. l-4

2000. 059

]-.73402.3

201.6

L22.4l-. 3t -22

6801q q

4.8L.t25.40. 0850.390. 0350 .02520. 002

1052L.3

0.155

AgAS

BBaBeBiBrccdCec1

Cr

DyErEuF9d

GdGeHfHgHoIInIrT.t

LiLu

Mo 5.8N59Nb 22.6Nd 57Ni 3.4Os 0.00011-Pb 46Pd 0.0019Pr L7Pt 0.08Rb 2L4Re 0.00063s 130sb 0.3Sc 2.8se 0.007Sm 8.3Sn 3.2Sr 248Ta 1.5Tb 0.58Th 5r-T1 L.23Ttn 0. 15u 3.4v18Yb1Zn 45ZT 2OL

From the early years of this century, the chemical analysis of rocks and minerals has

been made with classical wet-analytical methods. In classical analysis, elements are

precipitated from the solution as successive group precipitates and then determined

mainly with gravimetric methods. In the 1950s, rapid methods based largely on optical

spectroscopy, complexometric titration and flame emission were developed alongside

those of classical analysis. Modified classical methods and some rapid methods are still

9

Table 1. Compositions of USGS granite sampIe, G-1, which was the first

international geological reference sampIe in the world (Fairbairn et al.

1951) . Numerical values for the concentrations of major, minor and trace

constituents are from the paper of Govindaraju (1989) .

Major and minor constituents %

Si02 72 . 51 Ti02 0.26 AlP3 14 . 23 Fep3 0 .8 6 FeO 0.97 MnO 0.03 MgO 0.36 CaO l. 37 Nap 3.33 K20 5.51 P20S 0.08 HzO + 0.34 Hp' 0.05 COz 0.07 F 0.07 S 0.01 Others 0 . 29

Sum 100.34 - O/ F,S,Cl 0.03

SUlI\corr.) 100.31

Fez0 3 tOlal l. 95

Trace elements ng/g

Ag 0.044 As 0 . 7 Au 0.0032 B l.6 Ba 1080 Be 3 Bi 0.05 Br 0.14 C 200 Cd 0.059 Ce 173 Cl 40 Co 2.3 Cr 20 Cs l.6 Cu 12 Dy 2 . 4 Er l.3 Eu l. 22 F 680 Ga 19,5 Gd 4 . 8 Ge l.12 Hf 5.4 Hg 0.085 Ho 0 . 39 I 0.035 In 0.0252 Ir 0.002 La 105 Li 2l.3 Lu 0.156

Mo 6.8 N 59 Nb 22 . 6 Nd 57 Ni 3.4 Os 0.00011 Pb 46 Pd 0.0019 Pr 17 Pt 0 . 08 Rb 214 Re 0 . 00063 S 130 Sb 0 . 3 Sc 2.8 Se 0.007 Sm 8.3 Sn 3 . 2 Sr 248 Ta l.5 Tb 0.58 Th 51 Tl l. 23 Tm 0 . 15 U 3 . 4 V 18 Yb 1 Zn 45 Zr 201

From the early years of this century, the chemical analysis of rocks and minerals has

been made with classical wet-analytical methods. In classical analysis, elements are

precipitated from the solution as successive group precipitates and then determined

mainly with gravimetric methods . In the 1950s, rapid methods based largely on optical

spectroscopy, complexometric titration and flame emission were developed alongside

those of classical analysis. Modified classical methods and some rapid methods are still

10

used for the total analyses of reference rock and mineral samples required by

instruments and other non-routine samples and for determining the concentrations of

some elements and components. Since the 1960s, X-ray fluorescence spectrometry

(wavelength dispersive and energy dispersive), instrumental neutron activation analysis

and flame atomic absorption and emission spectrometry and graphite furnace AA

spectrometry, since the 1970s, plasma atomic emission spectrometry and since the

1980s, plasma mass spectrometry, have replaced many of the classical and rapid

methods. Today, chemical analyses of rocks and minerals are made on instruments

capable of determining up to 30-40 elements simultaneously or in rapid succession.

Among the techniques now in common use are the X-ray fluorescence analysis (XRF,

in this study WD-XRF), flame atomic absorption spectrometry (AAS) and inductively

coupled plasma atomic emission spectrometry GCP-AES).

However, not all the components of total rock and mineral analyses can be determined

with these instruments. The determinations of elements or components that cannot be

made with the above instruments, or which for some other reason are made separately,

are here called individual determinations. Water, ferrous iron and carbon are the most

common components analysed in this way. For rocks and minerals, halogen and

sulphur concentrations and loss on ignition are also often measured as individual

determinations.

The water in rocks and minerals occurs as moisture and constitutional or essential

water. There are several methods for determining water, the most cornmon of which

are those based on gravimetry, titrimetry and infra-red (IR) spectrometry (Section 3.1,

vD.

In rock and mineral samples, iron mostly occurs in oxidation states +II and +III.After the concentration of ferrous iron has been determined, the concentration of ferric

iron can be calculated as a difference: Fe(total) - Fe (ferrous) : Fe (fenic). Iron(II)

is usually determined by titrimetry or spectrophotometry. There are very few methods

for determining iron(III) (Section 3.2, VII).

Carbon occurs in rocks and minerals as carbonate carbon and non-carbonate carbon,

both of which are measured as individual determinations. The methods used for

10

used for the total analyses of reference rock and mineral sampies required by

instruments and other non-routine sampies and for determining the concentrations of

some elements and components . Since the 1960s, X-ray fluorescence spectrometry

(wavelength dispersive and energy dispersive), instrumental neutron activation analysis

and flame atomic absorption and emission spectrometry and graphite furnace AA

spectrometry, since the 1970s, plasma atomic emission spectrometry and since the

1980s, plasma mass spectrometry, have replaced many of the classical and rapid

methods. Today , chemical analyses of rocks and minerals are made on instruments

capable of determining up to 30-40 elements simultaneously or in rapid succession.

Among the techniques now in common use are the X-ray fluorescence analysis (XRF,

in this study WD-XRF) , flame atomic absorption spectrometry (AAS) and inductively

coupled plasma atomic emission spectrometry (ICP-AES).

However, not all the components of total rock and mineral analyses can be determined

with these instruments. The determinations of elements or components that cannot be

made with the above instruments, or which for some other reason are made separately ,

are here called individual determinations. Water, ferrous iron and carbon are the most

common components analysed in this way. For rocks and minerals , halogen and

sulphur concentrations and loss on ignition are also often measured as individual

determinations .

The water in rocks and minerals occurs as moisture and constitutional or essential

water. There are several methods for determining water, the most common of which

are those based on gravimetry, titrimetry and infra-red (IR) spectrometry (Section 3.1,

VI) .

In rock and mineral sampies, iron mostly occurs in oxidation states +11 and + IH .

After the concentration of ferrous iron has been determined, the concentration of ferric

iron can be calculated as a difference: Fe(total) - Fe (ferrous) = Fe (ferric). Iron(H)

is usually determined by titrimetry or spectrophotometry . There are very few methods

for determining iron(III) (Section 3.2, VII) .

Carbon occurs in rocks and minerals as carbonate carbon and non-carbonate carbon,

both of which are measured as individual determinations. The methods used for

11

determining the total carbon concentration are based on combustion of the sample, in

the course of which the elemental carbon converts into carbon dioxide and the total

carbon can be measured as carbon dioxide. The carbon concentration in carbonate is

obtained by liberating and measuring the carbon dioxide from carbonates. Non-

carbonate carbon can be obtained from the difference between total and carbonate

carbons but can also be determined individually. Non-carbonate carbon is composed of

graphite and organic carbon (Section 3.3, VIII).

Halogens can be analysed by XRF although individual determinations are also

frequently made with an ion-selective electrode, ion-chromatography and spectro-

photometry. Neutron activation is also used (Section 3.4). The total sulphur in a sample

can also be analysed by XRF, but it is most commonly measured as an individual

determination by combusting sulphur into oxide and measuring the amount of sulphur

dioxide thus formed. The sulphide and sulphate sulphurs in a sample can be analysed

individually with wet-chemical methods, too (Section 3.4). Loss on ignition (LOI) is

determined gravimetrically by igniting the sample at a high temperature (1000-120OC)

and measuring the loss in weight. LOI indicates the amount of volatile components in

the sample. These components include e.g. water (both moisture, HrO-, and essential

water, HrO*), carbon dioxide (COr, sulphur (S) and organic matter (Section 3.4).

CHEMICAL ANALYSES OF ROCK, MINERAL AND CERTAIN

SPECIAL SAMPLES

This section deals with the preparation and chemical analysis of rock and mineral

samples and certain special samples such as meteorites. An analytical package

containing modified classical methods and new methods is described, and a brief look

is taken at AAS, XRF and ICP-AES.

11

determining the total carbon concentration are based on combustion of the sample, in

the course of which the elemental carbon converts into carbon dioxide and the total

carbon can be measured as carbon dioxide. The carbon concentration in carbonate is

obtained by liberating and measuring the carbon dioxide from carbonates. Non

carbonate carbon can be obtained from the difference between total and carbonate

carbons but can also be determined individually. Non-carbonate carbon is composed of

graphite and organic carbon (Section 3.3, VIII).

Halogens can be analysed by XRF although individual determinations are also

frequently made with an ion-selective electrode, ion-chromatography and spectro

photometry. Neutron activation is also used (Section 3.4) . The total sulphur in a sampie

can also be analysed by XRF, but it is most commonly measured as an individual

determination by combusting sulphur into oxide and measuring the amount of sulphur

dioxide thus formed . The sulphide and sulphate sulphurs in a sample can be analysed

individually with wet-chemical methods, too (Section 3.4). Loss on ignition (LOI) is

determined gravimetrically by igniting the sample at a high temperature (lOOO-1200"C)

and measuring the loss in weight. LOI indicates the amount of volatile components in

the sample. These components include e.g. water (both moisture , H20 ·, and essential

water, H20 +) , carbon dioxide (C02), sulphur (S) and organic matter (Section 3.4) .

2 CHEMICAL ANALYSES OF ROCK, MINERAL AND CERTAIN

SPECIAL SAMPLES

This section deals with the preparation and chemical analysis of rock and mineral

sampies and certain special sampies such as meteorites. An analytical package

containing modified classical methods and new methods is described, and a brief look

is taken at AAS, XRF and ICP-AES.

t2

2.1 Sample preparation

Variations in the analytical results of rock, mineral and special samples such as

meteorites, are controlled by variations in the geology, mode of taking and transporting

the sample, preparation of the sample and analytical factors. Laboratories see to the

preparation and analysis of samples. Sample preparation is the procedure between

sampling and chemical analysis. Sampling has attracted considerable attention recently,

partly due to the intensification of exploration for gold. The "nugget" (or single

particle) phenomenon is a reminder of the importance of correct sample selection and

preparation. The result of a chemical analysis and the geological inferences drawn from

it are no better than the sample from which the data derive. The total error or

analytical variation in results is the sum of all sub-errors. (Richardson 1993).

In preparation, a field rock sample, the size of which depends on the grain size and

homogeneity of the material, is reduced to a size, shape and weight appropriate for

analysis. The field sample is usually cut in two with a rock cutter (or "guillotine"),

then crushed in a jaw crusher and/or roll mill and pulverized in a disc mill. At

intervals, the size of the sample is reduced by splitting it into portions of equal size and

taking only one of these for further treaftnent. The sample should, however, retain its

homogeneity throughout the milling. The sample thus obtained, with a weight of 30-

200 g and a grain size of 100-200 mesh (0.147-0.074 mm), should represent the parent

sample as closely as possible. Contamination due to machinery, the environment or

other samples is difficult to eliminate completely and should be kept as low as possible.

In trace element determinations in particular, error due to contamination may dominate

the preparation error. Other preparation errors include loss of sample and volatile

components and the oxidation of ferrous iron in crushing, milling and homogenization.

The finer a sample is ground the longer it is in contact with air, the more moisture it

gets from air and the larger the part of ferrous iron that is oxidized into ferric iron.

Heating a sample during milling also enhances the oxidation of ferric iron and may

result in loss of water of crystallization. Small samples such as minerals and meteorites

are usually crushed in steel or diamond mortars and ground manually in an agate

mortar (Saheurs et al. 1993).

12

2.1 SampIe preparation

Variations in the analytical results of rock, mineral and special sampIes such as

meteorites, are controlled by variations in the geology, mode of taking and transporting

the sampie, preparation of the sampie and analytical factors. Laboratories see to the

preparation and analysis of sampIes. SampIe preparation is the procedure between

sampling and chemical analysis. Sampling has attracted considerable attention recently,

partly due to the intensification of exploration for gold. The "nugget" (or single

particle) phenomenon is areminder of the importance of correct sampie selection and

preparation. The result of a chemical analysis and the geological inferences drawn from

it are no better than the sampie from which the data derive. The total error or

analytical variation in results is the sum of all sub-errors. (Richardson 1993).

In preparation, a field rock sampie, the size of which depends on the grain size and

homogeneity of the material, is reduced to a size, shape and weight appropriate for

analysis. The field sampie is usually cut in two with a rock cutter (or "guillotine"),

then crushed in a jaw crusher and/or roll mill and pulverized in a disc mill. At

intervals, the size of the sampie is reduced by splitting it into portions of equal size and

taking only one of these for further treatment. The sampIe should, however, retain its

homogeneity throughout the milling. The sampie thus obtained, with a weight of 30-

200 g and a grain size of 100-200 mesh (0.147-0.074 mm), should represent the parent

sampIe as closely as possible. Contamination due to machinery, the environment or

other sampIes is difficult to eliminate completely and should be kept as low as possible.

In trace element determinations in particular, error due to contamination may dominate

the preparation error. Other preparation errors include loss of sampIe and volatile

components and the oxidation of ferrous iron in crushing, milling and homogenization.

The finer a sampIe is ground the longer it is in contact with air, the more moisture it

gets from air and the larger the part of ferrous iron that is oxidized into ferric iron.

Heating a sampIe during milling also enhances the oxidation of ferric iron and may

result in loss of water of crystallization. Small sampies such as minerals and meteorites

are usually crushed in steel or diamond mortars and ground manually in an agate

mortar (Saheurs et al. 1993).

13

The separation of mineral grains from a rock sample begins with the crushing and

grinding of the sample to a particle size smaller than that of the smallest grain of the

mineral to be studied. The most common grain size is 100-200 mesh. The separation

of minerals is based on the difference between their magnetic properties and specific

gravities. Picking minerals under a microscope is a very useful technique. Tiny mineral

grains, e.g. zircon grains in micas or chlorite grains in feldspars, may occur as

inclusions in the mineral being studied. In such cases it is impossible to obtain pure

mineral maffer, and the mineral analysis has an error component (Hutchison L974,

Papers III and IV).

Meteorites are divided into three main groups: stony, iron-stony and iron meteorites.

Preparation of meteorite samples depends to a great extent on the concentration of

native iron in the meteorite, and thus it is often very difficult to obtain a representative

sample. Stony meteorites without native iron are crushed and milled like silicate rocks

(III). The fusion crust formed when a meteorite falls must first be removed. Stony

meteorites with metallic iron, and stony iron meteorites are often divided magnetically

and/or by picking under a microscope into metallic and stony portions that can be

analysed separately. Samples are taken from iron meteorites by drilling or crushing,

and their purity is checked under the microscope. Metallic portions and inclusions are

sometimes analysed separately. The total analysis is obtained by combining the

subanalyses once the proportion of inclusions in the meteorite has been calculated from

their surface areas (Easton 1972). The metallic portions of meteorites can be milled

together with the stony portions by grinding the sample at the temperature of liquid air

(Berrl' & Rudowski 1965). The metallic portions can be evaporated as chlorides with

a dry chlorine gas, in which case stony matter is obtained as a residue (Moss et al.

1961).

13

The separation of mineral grains from a rock sampIe begins with the crushing and

grinding of the sampie to a particle size smaller than that of the smallest grain of the

mineral to be studied. The most cornmon grain size is 100-200 mesh. The separation

of minerals is based on the difference between their magnetic properties and specific

gravities. Picking minerals under a microscope is a very useful technique. Tiny mineral

grains, e.g. zircon grains in micas or chlorite grains in feldspars, may occur as

inclusions in the mineral being studied . In such cases it is impossible to obtain pure

mineral matter, and the mineral analysis has an error component (Hutchison 1974,

Papers III and IV).

Meteorites are divided into three main groups : stony, iron-stony and iron meteorites.

Preparation of meteorite sampies depends to a great extent on the concentration of

native iron in the meteorite , and thus it is often very difficult to ob ta in a representative

sampie. Stony meteorites without native iron are crushed and milled like silicate rocks

(IH) . The fusion crust formed when a meteorite falls must first be removed. Stony

meteorites with metallic iron, and stony iron meteorites are often divided magnetically

and/or by picking under a microscope into metallic and stony portions that can be

analysed separately . Sampies are taken from iron meteorites by drilling or crushing,

and their purity is checked under the microscope. Metallic portions and inclusions are

sometimes analysed separately . The total analysis is obtained by combining the

subanalyses once the proportion of inclusions in the meteorite has been calculated from

their surface areas (Easton 1972). The metallic portions of meteorites can be milled

together with the stony portions by grinding the sampie at the temperature of liquid air

(Berry & Rudowski 1965). The metallic portions can be evaporated as chlorides with

a dry chlorine gas, in which case stony matter is obtained as a residue (Moss et al.

1961) .

L4

t, Rock analysis

For decades, the chemical analysis of rocks and minerals has been made with classical

wet methods in which the powdered sample is dissolved with the aid of fusion or acids.

In the classical analysis, elements are precipitated from the solute as successive groups

and their concentrations determined, commonly with gravimetric methods. Over the

years there have been many changes and refinements to the classical silicate analysis

(Dittler 1933, Hillebrand & al. 1953, Maxwell 1968, Jeffery & Hutchison 1983). In

the 1950s, rapid methods seeking to determine as many components as possible from

the same solute without separations and precipitations were developed parallel to the

classical analysis. These methods were largely based on optical spectroscopy,

complexometric titration and flame emission (Shapiro & Brannock 1956). Both classical

and rapid methods are still used for certain elements. Modified classical methods are

also used for the accurate total analyses of reference rock and mineral samples required

by analytical instruments. The first international reference rock samples were G-1,

granite and W-1, diabase (Fairbairn 1951). Today there ares over three hundred

international geological reference samples (rocks, minerals, soils, ores etc.)

(Govindaraju 1994). The Geological Survey of Finland (GSF) has participated in the

elaboration of many reference samples, with the author as a member the team of

chemists involved.

Figure 1 presents the modified classical methods employed in the chemical laboratory

of GSF and a scheme for the main component analysis of silicate rocks and minerals.

This scheme, which includes newer methods, has also been applied to other geological

samples, e.g. meteorites (I-V). Main component analysis consists of a main portion and

individual determinations. The procedure of the main portion is briefly as follows.

Powdered sample is dried at 110'C, and weighed to obtain the moisture (HzO-)

content. The sample is then fused with sodium carbonate in a platinum crucible at

1100"C. The fusion cake is dissolved in dilute hydrochloric acid, and silicon is

determined gravimetrically by separating it from the solute as silica hydrogel, which is

then ignited into silica for weighing. Mixed oxides, ammonia group or "R Or" are

precipitated from the filtrate with ammonia. The ignited and weighed oxide precipitate

(Al2O3, FeOr, TiO2, PrOr, etc.) is dissolved with pyrosulphate flux and the solution is

14

2.2 Rock analysis

For decades, the chemical analysis of rocks and minerals has been made with classical

wet methods in which the powdered sampie is dissolved with the aid of fusion or acids.

In the classical analysis, elements are precipitated from the solute as successive groups

and their concentrations determined, commonly with gravimetric methods. Over the

years there have been many changes and refinements to the classical silicate analysis

(Dittier 1933, Hillebrand & al. 1953, Maxwell 1968, Jeffery & Hutchison 1983) . In

the 1950s, rapid methods seeking to determine as many components as possible from

the same solute without separations and precipitations were developed parallel to the

classical analysis. These methods were largely based on optical spectroscopy ,

complexometric titration and flame emission (Shapiro & Brannock 1956). Both classical

and rapid methods are still used for certain elements. Modified classical methods are

also used for the accurate total analyses of reference rock and mineral sampies required

by analytical instruments. The first international reference rock sampies were G-1 ,

granite and W -1, diabase (Fairbairn 1951) . Today there ares over three hundred

international geological reference sampies (rocks, minerals , soils, ores etc .)

(Govindaraju 1994). The Geological Survey of Finland (GSF) has participated in the

elaboration of many reference sampies, with the author as a member the team of

chemists involved.

Figure 1 presents the modified classical methods employed in the chemical laboratory

of GSF and a scheme for the main component analysis of silicate rocks and minerals .

This scheme, which includes newer methods, has also been applied to other geological

sampies, e.g . meteorites (I-V). Main component analysis consists of a main portion and

individual determinations. The procedure of the main portion is briefly as follows .

Powdered sampie is dried at 110°C, and weighed to obtain the moisture (H20 ')

content. The sampie is then fused with sodium carbonate in a platinum crucible at

1100°C. The fusion cake is dissolved in dilute hydrochloric acid , and silicon is

determined gravimetrically by separating it from the solute as silica hydrogel , which is

then ignited into silica for weighing. Mixed oxides, ammonia group or "R20 3 " are

precipitated from the filtrate with ammonia. The ignited and weighed oxide precipitate

(AI2ü 3 , Fe2ü 3• Ti02 • P2Ü S' etc.) is dissolved with pyrosulphate flux and the solution is

15

made acidic with sulphuric acid. The residual silicon is determined from this solution

gravimetrically, and the total iron and titanium colorimetrically - iron as the yellow

ferric chloride complex and titanium with the Tiron reagent. The aluminium

concentration is obtained by subtracting from the total of the mixed oxides the

combined total of other elements present. Calcium is precipitated from the filtrate of

the hydroxide precipitate as oxalate, and magnesium is then precipitated as ammonium-

magnesium phosphate. Calcium is weighed as calcium carbonate or oxide, and

magnesium as magnesium pyrophosphate.

The second subsample is dissolved in hydrofluoric, nitric and perchloric acids.

Concentrations of sodium and potassium are determined from the solute thus obtained

by flame emission spectrophotometry GAES) (Asklund et al. 1966) or flame AAS

(Van Loon i980). Those of manganese and phosphorus are determined colorimetrically

as pennanganate (Langmyhr & Graff 1965) and molybdovanado phosphoric acid

complex (Shapiro & Brannock 1956).

The sample is analysed for water (Section 3.1, VD, ferrous iron (Section 3.2, VII),

carbon dioxide (Section 3.3, VIII), native carbon (Section 3.3, VIII), sulphur, fluorine

and chlorine as independent determinations. The water content of the sample is

measured by the IR method (VD. The constitutional water is obtained by subtracting

the moisture water from the total water (VD. The concentration of ferric iron is

calculated by subtracting the concentration of ferrous iron from that of total iron (VII).

This scheme for the complete chemical analysis of silicate rocks is an outcome of

continuous development. Several geoanalysts have published their rock analytical

methods and schemes (see e.g. Washington 1932,Hillebrand et al. 1953, Peck 1964,

Maxwell 1968, Kirschenbaum 1983).

Most routine chemical analyses of rocks and minerals are culrently made with

instruments permitting the simultaneous or rapid successive determination of several

elements. Instruments in common use include the X-ray fluorescence spectrometer, the

atomic absorption spectrometer and the inductively coupled plasma spectrometer.

15

made acidic with sulphuric acid. The residual silicon is determined from this solution

gravimetrically, and the total iron and titanium colorimetrically - iron as the yellow

ferric chloride complex and titanium with the Tiron reagent. The aluminium

concentration is obtained by subtracting from the total of the mixed oxides the

combined total of other elements present. Calcium is precipitated from the filtrate of

the hydroxide precipitate as oxalate, and magnesium is then precipitated as amrnonium

magnesium phosphate. Calcium is weighed as calcium carbonate or oxide , and

magnesium as magnesium pyrophosphate.

The second subsampie is dissolved in hydrofluoric, nitric and perchloric acids .

Concentrations of sodium and potassium are determined from the solute thus obtained

by flame emission spectrophotometry (FAES) (Asklund et al. 1966) or flame AAS

(V an Loon 1980) . Those of manganese and phosphorus are determined colorimetrically

as permanganate (Langmyhr & Graff 1965) and molybdovanado phosphoric acid

complex (Shapiro & Brannock 1956).

The sampie is analysed for water (Section 3.1 , VI), ferrous iron (Section 3.2, VII) ,

carbon dioxide (Section 3.3, VIII) , native carbon (Seetion 3.3, VIII) , sulphur, fluorine

and chlorine as independent determinations. The water conte nt of the sampie is

measured by the IR method (VI) . The constitutional water is obtained by subtracting

the moisture water from the total water (VI). The concentration of ferric iron is

calculated by subtracting the concentration of ferrous iron from that of total iron (VII) .

This scheme for the complete chemical analysis of silicate rocks is an outcome of

continuous development. Several geoanalysts have published their rock analytical

methods and schemes (see e.g. Washington 1932, Hillebrand et al. 1953, Peck 1964,

Maxwell 1968, Kirschenbaum 1983) .

Most routine chemical analyses of rocks and minerals are currently made with

instruments permitting the simultaneous or rapid successive determination of several

elements. Instruments in cornmon use include the X -ray fluorescence spectrometer, the

atomic absorption spectrometer and the inductively coupled plasma spectrometer.

t6

Figure 1. The scheme for the main componenE analysis of sj-licate rocksanä minerals used at the Geological Survey of Fin1and. Conventional "mainportion" analysis and components requiring indj.vidual determination.NI4AIN PORTION" A}iIALYSIS :

Silicale rock or mineral

Heat at (10soc)

H"O-t-

Fuse t^titsh Na2CO3

DissolTe wigh concentrated HCL

Tvaporat'eDissolle in 1O? Hc1

Filter

fesidue

fouble dehydration

sioz

Tiltrate

lrecinitate with NH4oH

Filter

frecipitateI

R,O" ignitedt' 'Fuse with Potassium

I

Dissolve in diluteDehydrate,Edd H2o

I

FiLeer

fesidueResidual SiO2

PrecipiUat,efiltratelith

(NHo) rC2or

Pyrosulphate

H2SO1 (1+1),

K2S20?

Gravi-metri-ca1ly

Precipitatet-CaCrOrt--CaO

Preci.pitate

filtratePrecipi.tate with

fMo) tir"on

FiJ-E1ate

DiscardfirErateTtor (colorimet,rically)

Fe2o3,o, (colorimetrically)

AlrO, calculation:

3 RaO3-(ä recovered SiO2 + I Fe2O3 - + ? TiO2 + e" P2Q5 + others) = t AlzOr

COMPONE}{|S REQUIRING IITDIVIDUAT DETERMINATION :

Silicate rock or mineralDissolveHF-HNO3-Irel04

l'[s (mrol poo

Mgo

clNa2O FeOKzo

PzosIUnO

Hzo*c,sPyro-lyti-cally

Colori-metri-cally

FAAS Titri-or met,ri-FAES ca1ly

Ion- Colori-selective metri-electrode cally

16

Figure 1. The scheme for the main component analysis of silicate rocks and minerals used at the Geological Survey of Finland. Conventional "main portion" analysis and components requiring individual determination.

"MAIN PORTION" ANALYSIS:

~esidue

silicaTe rock or

Heat at (105°C) 1

H,O· 1-

Fuse wi th Na2C03 1

mineral

Dissolve with concentrated HCI 1

~vaporate

Dissolre in 10% HCI

Filter

liltrate

1 ~ouble dehydration

Si02 Precipitate with NHPH 1

lrecipitate

R203 igni ted 1

Filter

Precipitate

liltrate

wi th (NH4 ) 2CP4 1

Fuse with Potassium Pyrosulphate K2S20 7 1

Dissolve in dilute H2S04 (1+1) I

Dehydrate , add H,O 1 -

lrecipitate

CaC20 , 1 -

liltrate

Precipitate with (NH4 ) ,HP04 1 -

Filter

~esidue

Residual Si02

Al203 calculation:

CaO

liltrate precipttate

Ti02 (colorimetrically) 1

Fe203 '0' (colorimetrically)

~g (NH4 ) P04

MgO

% R~.o3 - (% recovered S i02 + % Fe203 "" + % Ti02 + % P20 S + others)

COMPONENTS REQUIRING INDIVIDUAL DETERMINATION:

Silicate rock or mineral Dissolve

I I I I HF-HN03-HCI04

I I I I P20 S Na20 FeO CO2 H2O+ F MnO K20 C, S

Colori - FAAS Titri- Gravi- Pyro- Ion-metri- or metri- metri- lyti- selective cally FAES cally cally cally electrode

Filtfate

Discard

I I Cl

Colori -metri-cally

17

Samples can be analysed for several major, minor and trace elements by XRF.

Powdered sample is converted into a glass disk by fusion or is compressed with a

binder into a briquette. Geological samples can be analysed by XRF for Si, Ti, Al,

Fe,o,, Mn, Mg, Ca, Na, K, P, S, F, Cl and many other elements (Table 2) (Potts 1993,

Longerich 1995).

For flame AAS and ICP-AES analyses, the sample is brought into solution. The

resulting solution is usually made with lithium metaborate fusion or acids. Samples are

analysed successively for Si, Al, Mn, Mg, Ca, Na and K by AAS from the same

sample solution (Table 2) (Angino & Billings 1972, Slavin 1982).

In the 1970s and '80s the present author and his colleagues in GSF developed an

analytical scheme for rock and mineral samples based on flame AAS (Fig. 2). In this

scheme the bulk of silicon is removed from the solution with a single precipitation, and

the filtrate (0.5 g1250 ml made acidic with HCI) is analysed colorimetrically for

residual silicon and by flame AAS for aluminium and manganese. Total iron, calcium

and magnesium often require dilution. In the same years the flame AAS or flame AES

methods for several elements, e.g. Li, Rb, Cs, Be, Sr, Cr, Co, Ni, Cu, Znand Cd, in

a filtrate and in HF-HNO3-HCIO4 solution were developed by the present author and

his colleagues. The standard solutions are made taking into account the interference

caused by the matrix and ionization (Saikkonen 1967, 1968, t969, L970a, 1970b and

Papers II, III, IV and V).

In ICP-AES analyses lithium metaborate is commonly used as flux. The fusion cake is

dissolved in dilute nitric or hydrochloric acid. Perhaps the most widely used method of

dissolution is the acid digestion using mixtures of HF-HCIO* and/or HNO3, HCl,

H2SO4 acids in an open vessel from which silicon evaporates as SiFo. Decomposition

is more effective when done in a closed vessel at pressure. Silicon then remains in

solution and so can be determined. The solute is directed into a hot plasma and, with

the aid of standard solutions, the concentrations of up to 40 elements are determined

simultaneously from the emitting radiation with a spectrometer. For total analyses,

samples can be analysed for Si, Ti, Al, Fe,o,, Mn, Mg, Ca, Na, K and P by ICP-AES

(Table 2) (Thompson & Walsh 1989, Jarvis & Jarvis 1992).

17

Sarnples can be analysed for several major, minor and trace elements by XRF.

Powdered sampie is converted into a glass disk by fusion or is compressed with a

binder into a briquette. Geological sampies can be analysed by XRF for Si , Ti , Al ,

Fe10l' Mn, Mg, Ca, Na, K, P, S, F , Cl and many other elements (Table 2) (Potts 1993 ,

Longerich 1995).

For flame AAS and ICP-AES analyses, the sampIe is brought into solution. The

resulting solution is usually made with lithium metaborate fusion or acids . Sampies are

analysed successively for Si , Al , Mn, Mg, Ca, Na and K by AAS from the same

sampie solution (Table 2) (Angino & Billings 1972, Slavin 1982).

In the 1970s and ' 80s the present author and his colleagues in GSF developed an

analytical scheme for rock and mineral sampies based on flame AAS (Fig. 2). In this

scheme the bulk of silicon is removed from the solution with a single precipitation, and

the filtrate (0.5 g/250 ml made acidic with HCI) is analysed colorimetrically for

residual silicon and by flame AAS for aluminium and manganese . Total iron, calcium

and magnesium often require dilution. In the same years the flame AAS or flame AES

methods for several elements , e .g. Li , Rb, Cs, Be, Sr, Cr, Co, Ni, Cu, Zn and Cd, in

a filtrate and in HF-HN03-HCI04 solution were developed by the present author and

his colleagues. The standard solutions are made taking into account the interference

caused by the matrix and ionization (Saikkonen 1967, 1968, 1969, 1970a, 1970b and

Papers II, III , IV and V) .

In ICP-AES analyses lithium metaborate is commonly used as flux . The fusion cake is

dissolved in dilute nitric or hydrochloric acid. Perhaps the most widely used method of

dissolution is the acid digestion using mixtures of HF-HCI04 and/or HN03 , HCI ,

H2S04 acids in an open vessel from which silicon evaporates as SiF4 . Decomposition

is more effective when done in a closed vessel at pressure. Silicon then remains in

solution and so can be determined. The solute is directed into a hot plasma and, with

the aid of standard solutions, the concentrations of up to 40 elements are determined

simultaneously from the emitting radiation with a spectrometer. For total analyses ,

sampies can be analysed for Si, Ti , Al , Fe101 ' Mn, Mg, Ca, Na, K and P by ICP-AES

(Table 2) (Thompson & Walsh 1989, Jarvis & Jarvis 1992).

18

Figure 2. A scheme for main component analysis of silicate rocks andminerals developed at the Geological Survey of Finland in the 1970s and-80s. ,'Main'r portion analysis with flame AAS from the solution after oneprecipitatj-on of silicon. ComponenEs requiring individual determination.

Silicale rock or mineral

Heat at (1-05"C)

HrO-t-

Fuse with Na2CO3

Dissolle wj-th concentrated HCI

fvaporateDissolle in L0? Hel

Filter

fesidue

ine dehVdration

sio2 1.

filtrate

sio2 2.

Colori-metri-ca1ly

COMPONENTS REQUTRING INDIVIDUAL DETERMINATION :

Silicate rock or mineraf

DissolveHF-HNO3-HCl04

A12O3, Fe2O36, l4nO, MgO, CaO

Flame AAS*

Pzos

Colori-metri-cally

Na20Kzo

FAASorFAES

Titri-metrr-cally

Gravi-metri-calIy

Hzo*crs

{rro-Iyti-cally

c1

Ion- Coloriselective meUri-electsrode cally

* with fl-ame AAS orSr, Cr, Co, Ni, Cu,

flame AES, alsoZt, Cd, etc.

18

Figure 2. A scheme for main component analysis of silicate rocks and minerals developed at the Geological Survey of Finland in the 1970s and '80s . "Main" portion analysis with flame AAS from the solution after one precipitation of silicon. Components requiring individual determination.

~esidue

?ne dehydration

Si02 1.

SilicaTe rock or

Heat at (105°C ) I

HO· 1

2

Fuse wi th Na2C03 I

mineral

Dissolie with concentrated HCl

fvaporate

DissOlie in 10% HCl

Filter

Colorimetrically

liltrate

Flame AAS*

COMPONENTS REQUIRING INDIVIDUAL DETERMINATION:

Silicate rock or mineral

Dissolve I I I I HF-HN03-HC104

I I I I PPs Nap FeO CO2 HP+ F

K20 C, S

Colori- FAAS * Titri- Gravi- Pyro- Ion-metri- or metri- metri- lyti- selective cally FAES * cally cally cally electrode

I I Cl

Colori-metri-cally

* with flame AAS or flame AES, also trace elements: Li, Rb, Cs, Be, Sr , Cr, Co, Ni, Cu, Zn, Cd, etc.

Table 2.referencemodif i-edStandard

t9

Element oxide concentrations (?) of t.he international rocksample !{-2 (diabase) ,' accordj.ng Eo tshe literature, with

classj-cal and some other methods, XRF, flame AAS and ICP-AES.deviations calculated from six successive determinat,ions.

CLASSb rcP-AESc

sio2

A1,;,Fe2O3,o.

Fe2O3

FeO

MnO

Mgo

r\q2v

Kzo

Pzos

Hzo*

Hzo-

\.v2

F

c1

52 .441 n4

L.528.31

10. 87

2 .1-4

0.620. r_3

0.55n ??

0.0679 ppm

205 ppm

190 ppm

52.60+0.101.04+0.01

15 .5]-t0. 13

10.75+0.031 .41+0 . 04

8.39t0.020.15+0.005 .63+0. 06

LO.74t0.022 .11+0 . 01

0.63+0.010.l-1+0.000 . 58r0. 02

0.15+0.00

52.95!O.t71 . 0610. 01

l-5.3910.1-9

10.85+0.09

0.15t0.006.28t0.07

11 .3310.022 .1110.030 .5510. 0l-

0 .1410. 0l-

52.47+O.45l-. 0610. 0l-

14 . 83+0. L4

10.60+0. 01

0.16+0.006.24+0.05

10. 98r0. 02

2 .18+0. 0l-

0 .6010. 0L

az -zz+u . zL

r-OStO.Or1-5 .4010 . 13

l-0.98i0.32

0.15+0. 00

5.0310.041-0.8010.01z.z1+u.u5^...^^^v. of +u. uz

0 -24+0 . 02

a. Potts et al. Lg92 b. GSF, analysed by the presenE auEhor (Paper

rI), c. faboratory usGsR/xRF (Flanagan 1984), d. laboratory BIo/AAS(Flanag:an 1984) , e. laboratory UIIID/ICP-AES (Flanagan ]-984) .

The compositions of and some information on rock and mineral samples analysed in the

chemical laboratory are stored in the database of GSF. The rock and mineral analysis

data base, KALTIE, contains 3274 chemical analyses of Finnish rocks and minerals,

which were obtained in L905-1992 with classical and instrumental methods. The

general information (number of sample and analysis, location, rock types, geologist,

analyst, publication) and the analysis information (main and trace constituents, method

of chemical analysis) on the rocks and minerals are stored in this relational database

(Gustafsson & Saikkonen 1994).

19

Table 2. Element oxide concentrations (%) of the international rock

reference sampIe W-2 (diabase); according to the literature, with

modified classical and some other methods, XRF, flame AAS and ICP-AES .

Standard deviations calculated from six successive determinations.

LIT . a CLASS b XRP< AASd ICP-AESe

SiOz 52.44 52.60±0.10 52 . 95±0.17 52.47±0.45 52.22±0 . 21

TiOz 1. 06 1. 04±0. 01 1.06±0.01 1 . 06±0 . 01 1.05±0.01

Alz03 15.35 15 . 51±0 . 13 15.39±0.19 14.83±0.14 15.40±0.13

FeZ03tot 10 . 74 10.75±0.03 10 . 85±0.09 10 . 60±0 . 01 10.98±0 . 32

FeZ03 1. 52 1. 41±0. 04

FeO 8.31 8.39±0 . 02

MnO 0.16 0.16±0.00 0.16±0.00 0.16±0.00 0.15±0 . 00

MgO 6 . 37 6.63±0.06 6 . 28±0.07 6.24±0.05 6 . 03±0 . 04

CaO 10.87 10.74±0.02 1l.33±0.02 10.98±0.02 10.80±0.01

NazO 2.14 2.11±0.01 2.11±0.03 2.18±0.01 2 . 24±0 . 05

KzO 0.62 0.63±0.01 0.65±0 . 01 0.60±0.01 0.61±0.02

P20S 0.13 0.11±0.00 0.14±0.01 0.24±0.02

H2O+ 0.55 0.58±0.02

H2O· 0 . 23 0 . 15±0.00

CO2 0.06

S 79 ppm

F 205 ppm

Cl 190 ppm

a. Potts et al. 1992 b . GSF, analysed by the present author (Paper

II), c . laboratory USGSR/XRF (Flanagan 1984), d. laboratory BIO/AAS

(Flanagan 1984), e. laboratory UIND/ICP-AES (Flanagan 1984).

The compositions of and some infonnation on rock and mineral sampies analysed in the

chemical laboratory are stored in the database of GSF. The rock and mineral analysis

data base, KALTIE, contains 3274 chemical analyses of Finnish rocks and minerals,

which were obtained in 1905-1992 with classical and instrumental methods. The

general infonnation (number of sampie and analysis, location, rock types, geologist,

analyst, publication) and the analysis information (main and trace constituents, method

of chemical analysis) on the rocks and minerals are stored in this relational database

(Gustafsson & Saikkonen 1994).

20

The main-portion analysis and the analysis of the components requiring individual

determination (Fig. 1) were tested and investigated in publication II. Agreement

between the results of this study and the "best estimates" given by F.J. Flanagan was

good (Flanagan 1984). The coefficient of variation of the data for ten constituents was

O.l-l% and for two constituents over l%. (Table 2).The precision of the classical

silicate analysis has also been assessed by Flanagan and Kirschenbaum (1984), who

analysed reference rock samples for 15 elements or components using classical

chemical methods. According to them, the variation of the determinations (CV : 0.2-

L%) wtll be the same for sample portions analysed as a group or analysed over some

time interval.

The precision of a technique depends upon many factors e.g. sample preparation,

matrix and interference effects and their correction, and instrumental drift during an

operation. The precision for an element is generally related to the concentration.

Comparison of the precision of different techniques is therefore difficult. The

precisions of XRF, flame AAS and ICP-AES presented here were taken from the

literature and so are comparable only to some degree.

The precisions of XRF rock analyses are about the same as those of the classical

silicate analysis (CV : 0.2-I%) for Si, Ti, Al, Fe,o,, Mn, Mg, Ca, Na and K, when

samples are made into glass disks after fusion with a specified lithium

tetraborate/metaborate flux (Ramsey et al. 1995). It is well known that the lightest

elements (particularly Na, Mg, Al, and Si) do not usually yield highly accurate and

precise results when from pressed pellets because of mineralogical effects. The

precisions for the heavy major elements, K, Ca, Ti, Mn, and Fe, are very similar to

those obtained with a more accurate and precise sample preparation by fusion

(Longerich 1995). According to the data obtained at the chemical laboratory of the

GSF, the coefficients of variation of XRF determinations are < I% for Si, Ti, Al, Fe,

Mg, Ca and Na, and 1-3 % for Mn, K and P (method code 175X: multi-element, over

40 elements, determination from powder pellets of sample) (Maija Hagel-Brunnström

1995, unpublished results).

For the AAS determinations, the coefficients of variation are about O.I-3% for major

elements analysed after fusion decomposition or an acid attack (Potts L987, Table 2).

20

The main-portion analysis and the analysis of the components requiring individual

determination (Fig. 1) were tested and investigated in publication 11 . Agreement

between the results of this study and the "best estimates" given by F.J. Flanagan was

good (Flanagan 1984) . The coefficient of variation of the data for ten constituents was

0.1-1 % and for two constituents over 1 %. (Table 2) .The precision of the classical

silicate analysis has also been assessed by Flanagan and Kirschenbaum (1984) , who

analysed reference rock sampies for 15 elements or components using classical

chemical methods . According to them, the variation of the determinations (CV = 0.2-

1 %) will be the same for sampie portions analysed as a group or analysed over some

time interval.

The precision of a technique depends upon many factors e.g. sampie preparation,

matrix and interference effects and their correction, and instrumental drift during an

operation. The precision for an element is generally related to the concentration.

Comparison of the precision of different techniques is therefore difficult. The

precisions of XRF, flame AAS and ICP-AES presented here were taken from the

literature and so are comparable only to some degree.

The precisions of XRF rock analyses are about the same as those of the classical

silicate analysis (CV = 0.2-1 %) for Si, Ti, Al, Felot , Mn, Mg , Ca, Na and K, when

sampies are made into glass disks after fusion with a specified lithium

tetraborate/metaborate flux (Ramsey et al. 1995). It is weH known that the lightest

elements (particularIy Na, Mg, Al , and Si) do not usually yield highly accurate and

precise results when from pressed pellets because of mineralogical effects. The

precisions for the heavy major elements, K, Ca, Ti, Mn, and Fe, are very similar to

those obtained with a more accurate and precise sampie preparation by fusion

(Longerich 1995). According to the data obtained at the chemical laboratory of the

GSF, the coefficients of variation of XRF determinations are < 1 % for Si, Ti, Al, Fe,

Mg, Ca and Na, and 1-3% for Mn, K and P (method code 175X: multi-element, over

40 elements, determination from powder pellets of sampie) (Maija Hagel-Brunnström

1995, unpublished results).

For the AAS determinations, the coefficients of variation are about 0.1-3% for major

elements analysed after fusion decomposition or an acid attack (Potts 1987, Table 2).

2l

In paper II the GSF's coefficients of variation are 0.7% for A1,0.2% for Mg,0.6%

for Ca, 0.3% for Na and 0.3% for K. The precision for the major elements is about

0.3-2% for ICP-AES with fusion and an acid attack (Jarvis & Jarvis 1992, Ramsey et

al. 1995). The GSF's coefficients of variation for ICP-AES with HF-HNO3-HCI-

HCIO4 attack (method code 311P) are < l% for Ti, Al, Fe, Mn, Mg and Ca, and >

t% for Na, K and P (Riitta Juvonen 1995, unpublished results).

As shown in Table 2, not all the components of the total analysis of rocks and minerals

can be analysed by XRF, flame AAS and ICP-AES. The analytical procedure of

individual determinations is dealt with in Section 3.

2.3 Mineral analysis

Mineral analyses are used to classify minerals and distinguish between them, to

calculate their formulae, identify them and compare separate analyses of the same

mineral. Several textbooks are available on the decomposition of minerals (e.g. Sulzek

& Povondra 1989, Bock 1979, Chao & Sandszolone 1992).

The chemical analysis of silicate minerals is similar to that of rocks although the

samples often have to be treated individually. The components analysed depend on the

number of elements the mineral contains, the purpose of the analysis and the amount

of material available. The components are reported in order of importance (Hey 1973,

Samchuk & Pilipenko 1987). A substantial proportion of mineral analyses are currently

made as microanalyses (electron probe microanalysis and ion microprobe analysis), in

which quantitative analysis on the surface of a polished thin section or the well-polished

surface of a sample yields data on the concentrations of major, minor and trace

elements, the accuracy of which depends on the reference and control samples available

(Potts 1993).

The present author has analysed over 100 mineral samples at the GSF, the data on

some of which have not been published before. The chemical analyses of 63 mineral

21

In paper II the GSF's coefficients of variation are 0.1 % for Al , 0.2% for Mg, 0.6 %

for Ca, 0 .3 % for Na and 0.3% for K. The precision for the major elements is about

0.3-2% for ICP-AES with fusion and an acid attack (Jarvis & Jarvis 1992, Ramsey et

al. 1995). The GSF ' s coefficients of variation for ICP-AES with HF-HN03-HCI

HCI04 attack (method code 311P) are < 1 % for Ti, Al, Fe, Mn, Mg and Ca, and >

1 % for Na, K and P (Riitta Juvonen 1995, unpublished results) .

As shown in Table 2, not all the components of the total analysis of rocks and minerals

can be analysed by XRF, flame AAS and ICP-AES. The analytical procedure of

individual determinations is dealt with in Section 3.

2.3 Mineral analysis

Mineral analyses are used to classify minerals and distinguish between them, to

calculate their formulae , identify them and compare separate analyses of the same

mineral. Several textbooks are available on the decomposition of minerals (e .g. Sulzek

& Povondra 1989, Bock 1979, Chao & Sandszolone 1992).

The chemical analysis of silicate minerals is similar to that of rocks although the

sampIes often have to be treated individually. The components analysed depend on the

number of elements the mineral contains, the purpose of the analysis and the amount

of material available. The components are reported in order of importance (Hey 1973 ,

Samchuk & Pilipenko 1987). A substantial proportion of mineral analyses are currently

made as microanalyses (electron probe microanalysis and ion microprobe analysis) , in

which quantitative analysis on the surface of a polished thin section or the well-polished

surface of a sampie yields data on the concentrations of major, minor and trace

elements, the accuracy of which depends on the reference and control sampies available

(Potts 1993).

The present author has analysed over 100 mineral sampIes at the GSF, the data on

some of which have not been published before. The chemical analyses of 63 mineral

2.4

22

samples are listed in tabular form in the Appendix. The determinations were made with

the modified classical methods described above, flame AAS and methods for individual

determination (I-VIII). Analyses of bityite and kunzite minerals are dealt with in Papers

III and IV.

Analysis of special samples

Meteorites are rather difficult to analyse chemically. Preparing a representative sample

tends to be a demanding task as meteorites are frequently very heterogeneous.

Powdered meteorites can be analysed for many major, minor and trace element

components with the classical and instrumental methods used for rock and mineral

samples (Jarosewich 1966, Saikkonen 1967, Fuchs et al. 1973, Hughes & Hannaker

1978, Adler 1986, Paper III). One of the developers of the analytical procedure for

chondrites (a group of stony meteorites) was the Finn, Birger Wiik (Wiik L956, L972).

Table 3 gives the chemical analysis of the Malampaka stony meteorite, an olivine-

bronzite chondrite in type, made by the present author (Graham et al. 1985). This

analysis has not been published before. The determination methods were very similar

to those used to analyse the Kivesvaara meteorite (Paper V).

The metallic iron of meteorites is analyed by dissolving the metal phase with

mercury(Il) chloride or copperfl) potassium chloride (Habashy 1961, Moss et aL. L967 ,

Fuchs et al. 7973). Iron, nickel, cobalt and copper can be determined from the

dissolved metal phase with various wet-chemical methods. In the analysis of the

Malanpaka meteorite, metallic nickel and cobolt were determined by flame AAS, and

metallic iron with colorimetric method.

Some chondrite meteorites contain metal, silicate, sulphide and phosphide phases and

other uncommon phases (Wedepohl 1978). These phases can be separated from each

other with successive dissolutions and analysed for their elements after ion exchange

separation (Shima 1974, Hughes & Hannaker 1978). Stony iron meteorites are often

divided magnetically into metal and stone phases before analysis.

22

sampies are listed in tabular fonn in the Appendix. The detenninations were made with

the modified classical methods described above, flame AAS and methods for individual

detennination (I-VIII). Analyses of bityite and kunzite minerals are dealt with in Papers

III and IV.

2.4 Analysis of special sam pies

Meteorites are rather difficult to analyse chemically. Preparing a representative sampie

tends to be ademanding task as meteorites are frequently very heterogeneous.

Powdered meteorites can be analysed for many major, minor and trace element

components with the classical and instrumental methods used for rock and mineral

sampies (Jarosewich 1966, Saikkonen 1967, Fuchs et al. 1973, Hughes & Hannaker

1978, Adler 1986, Paper III). One of the developers of the analytical procedure for

chondrites (a group of stony meteorites) was the Finn, Birger Wiik (Wiik 1956, 1972).

Table 3 gives the chemical analysis of the Malampaka stony meteorite, an olivine

bronzite chondrite in type , made by the present author (Graharn et al. 1985) . This

analysis has not been published before. The detennination methods were very similar

to those used to analyse the Kivesvaara meteorite (Paper V).

The metallic iron of meteorites is analyed by dissolving the metal phase with

mercury(II) chloride or copper(l) potassium chloride (Habashy 1961, Moss et al. 1967,

Fuchs et al. 1973). Iron, nickel, cobalt and copper can be detennined from the

dissolved metal phase with various wet-chemical methods . In the analysis of the

Malanpaka meteorite , metallic nickel and cobolt were detennined by flame AAS, and

metallic iron with colorimetric method.

Some chondrite meteorites contain metal, silicate, sulphide and phosphide phases and

other uncommon phases (Wedepohl 1978). These phases can be separated from each

other with successive dissolutions and analysed for their elements after ion exchange

separation (Shirna 1974, Hughes & Hannaker 1978) . Stony iron meteorites are often

divided magnetically into metal and stone phases before analysis.

23

Table 3. Analysis of the Malampaka stony meteorit,e (olivine-bronzitechondrite). Arralysed by the present autshor. Arralytical methods: modifiedclassical methods (gravimetric, titrimetsric, colorimetric), atomicabsorption spectrometry and other methods (see paper V and Graham et al.198s) .

Species wE ?' EIemenLs wt*

sio2Mgo

FeO

Af 2v3

CaO

Na20

Cr2O3

l,Ino

Hzo*

Pzos

vd

TiO2

Kzo

Total stsone

material

Fe

NiCo

Metallj-c grainsFeS

Sulphide StrainsTotal

35.4z5.o

LL.42.291. 55

1.00o -47

0.300.200.180.L2o.L20. r-0

76.7

F€-siMg

s

NiA1

Ca

Na

Cr

Mn

cK

Co

P

TiCu

H.

Part totalor

Totsa1

35 .3

L6.6L4.2r..89r_.88

L.20I.Il-

0.740.320.23o.L20-080 .080 .080. 07

0.010 .02

44.915.1

100 ?

16 .1t.760. 08

17.95.195. 19

>>.ö

*

f

calculated from H2O'

calculated 100 - part, total

In the analysis of iron

separately (Moss et al.

meteorites

1961).

the metal phase and its inclusions can be treated

23

Table 3. Analysis of the Malampaka stony meteorite (olivine-bronzite

ehondrite) . Analysed b y the present author . Analytieal methods : modified

elassieal methods (gravimetrie, titrimetrie, eolorimetrie), atomie

absorption speetrometry and other methods (see paper V and Graham et al.

1985) .

Species wt % Elements wt %

Si02 35.4 Fe tOl 36.3

MgO 23 . 6 Si 16.6

FeO 11. 4 Mg 14 . 2

A1203 2 . 29 S 1. 89

CaO 1. 55 Ni 1. 88

Na20 1. 00 Al 1. 20

Cr203 0 . 47 Ca 1.11

MnO 0 . 30 Na 0 . 74

HP+ 0 . 20 Cr 0.32

pps 0.18 Mn 0.23

Ctot 0.12 C 0 . 12

Ti02 0.12 K 0 . 08

Kp ~ Co 0.08

P 0 . 08

Total stone 7 6 . 7 Ti 0.07

material Cu 0.01

H· 0 . 02

Fe 16 . 1

Ni 1. 76 Part total 84 . 9

Co ~ 0# 15 . 1

Metallic grains 17.9 Total 100 %

FeS 2.:..ll Sulphide grains 5.19 * ealeulated from HP+

Total 99 . 8 # caleulated 100 - part total

In the analysis of iron meteorites the metal phase and its inclusions can be treated

separately (Moss et al. 1961).

24

Before 1969, meteorites were the only extraterrestrial material available for scientific

study. After the successful Apollo flights, samples from the Moon became available to

research teams. Among them was that of Birger Wiik, of which the present author was

a member (Wiik L975, 1986). The flrst flight, Apollo 11, was in 1969, and Finland

was the first country outside the USA to obtain lunar samples for chemical analysis

(Wiik & Ojanperä 1970).

3 ELEMENTS AND COMPONENTS REQTIIRING INDIVIDUAL

DETERMINATION

3.1 Determination of water

According to the constiütional classification, the water in rocks and minerals is bound

chemically and physically. The chemically bound water is constitutional water, or

water of crystallizltion. The water of crystallization occurs in minerals as bound water

or zeolite water. The physically bound water is adsorbed on mineral surfaces or

constitutionally absorbed, or it occurs in fluid inclusions within the mineral (Pyper

1985). In conventional rock and mineral analyses, a distinction is made between bound

water, here called water of crystallization, HzO*, and free water or moisture water,

HrO-. The temperature reported in the determination is usually 105-110"C. The water

liberated at this temperature is referred to as moisture water, HrO-; the remainder is

water of crystallization, HtO*. Note that the water of crystallization that may be

liberated at the above temperature is calculated as moisture water. Correspondingly, the

water liberated at high temperatures from fluid inclusions is calculated as water ofcrystallization. Total water is the sum of moisture and crystallization waters (HzO., :H2O- + HrO*).

24

Before 1969, meteorites were the only extraterrestrial material available for scientific

study. After the successful Apollo flights, sampies from the Moon became available to

research teams. Among them was that of Birger Wiik, of which the present author was

a member (Wiik 1975, 1986). The first flight, Apollo 11, was in 1969, and Finland

was the first country outside the USA to obtain lunar sampies for chemical analysis

(Wiik & Ojanperä 1970).

3 ELEMENTS AND COMPONENTS REQUIRING INDIVIDUAL

DETERMINATION

3.1 Determination of water

According to the constitutional c1assifIcation, the water in rocks and minerals is bound

chemically and physically. The chemically bound water is constitutional water, or

water of crystallization. The water of crystallization occurs in minerals as bound water

or zeolite water. The physically bound water is adsorbed on mineral surfaces or

constitutionally absorbed, or it occurs in fluid inc1usions within the mineral (Pyper

1985). In conventional rock and mineral analyses , a distinction is made between bound

water, here called water of crystallization, H20 +, and free water or moisture water,

H20 ". The temperature reported in the determination is usually lO5-110°e. The water

liberated at this temperature is referred to as moisture water, H20 "; the remainder is

water of crystallization, H20 +. Note that the water of crystallization that may be

liberated at the above temperature is calculated as moisture water. Correspondingl y, the

water liberated at high temperatures from fluid inc1usions is calculated as water of

crystallization. Total water is the sum of moisture and crystallization waters (H20 ror =

H20 " + H20 +).

25

Metamorphic and sedimentary rocks usually contain small amounts of elemental

hydrogen that, under oxidizing analytical conditions, are converted into water and

included in the water of crystallization. The hydroxide group (OH), which occurs in

several minerals such as amphiboles and micas, evaporates from the minerals on

heating as water (Baur 1978).

In most of the classical and more recent methods for determining concentrations of

total and crystallization waters, the sample is heated at high temperature with or

without a flux. As a rule, the water is liberated from rocks without a flux if the

temperature is sufficiently high, 1100oC, and the time of heating sufficiently long

(Skinner et al. 1981). Some minerals, e.g. talc, topaz, staurolite, chondrodite, epidote

and cordierite, need a flux and high temperature for water to evaporate (Riley 1958).

Flux must also be used for the analvsis of many micas and rocks rich in micas

(Kuzuhisa 1991).

Concentrations of total and crystallization waters are usually determined with

gravimetric, titrimetric or IRS methods. The gravimetric methods, including the

classical Penfield method still in common use (see publication VI), are based on

weighing the water expelled and collected from the sample on heating (Volborth 1969,

Delong 1981). Analytical methods based on Karl-Fisher titration are also frequently

used (Troll & Farzaneh 1980, Westrich 1987). A number of instruments and methods

based on IR detection of the water expelled from the sample on heating have been

developed (Din & Jones 1978, Skinner et al. 1981).

A new infrared absorption method for rock and mineral samples is described in

publication VI. To determine the total water, an air-dry powdered sample is ignited at

1100"C in a nitrogen aünosphere without a flux or with PrOr-flux. The water liberated

is directed through an IR cell for measurement. The water of crystallization is

determined in the same way but the sample is heated at 110"C before the measurement.

The moisture water is determined at 110"C. The results have been compared with

those of the Penfield method and found compatible. Similar results have been obtained

from international geological reference samples. The new method has several

advantages: operation is simple and unvarying; it is also faster than the old Penfield-

method; the carbon dioxide liberated from samples does not interfere with the

25

Metamorphie and sedimentary rocks usually contain small amounts of elemental

hydrogen that, under oxidizing analytical conditions, are converted into water and

included in the water of crystallization. The hydroxide group (OR), whieh occurs in

several minerals such as amphiboles and micas, evaporates from the minerals on

heating as water (Baur 1978).

In most of the classieal and more recent methods for determining concentrations of

total and erystallization waters, the sampie is heated at high temperature with or

without a flux . As a rule, the water is liberated from rocks without a flux if the

temperature is suffieiently high, 1l00°C, and the time of heating sufficiently long

(Skinner et al. 1981). Some minerals, e.g. tale , topaz, staurolite, chondrodite, epidote

and cordierite, need a flux and high temperature for water to evaporate (Riley 1958).

Flux must also be used for the analysis of many micas and rocks rieh in mieas

(Kutzuhisa 1991) .

Coneentrations of total and crystallization waters are usually determined with

gravimetrie, titrimetrie or IRS methods. The gravimetrie methods, including the

classieal Penfield method still in common use (see publication VI), are based on

weighing the water expelled and collected from the sampie on heating (Volborth 1969,

DeLong 1981). Analytieal methods based on Karl-Fisher titration are also frequently

used (Troll & Farzaneh 1980, Westrich 1987). A number of instruments and methods

based on IR detection of the water expelled from the sampie on heating have been

developed (Din & Jones 1978, Skinner et al. 1981) .

A new infrared absorption method for rock and mineral sampies is described in

publication VI. To determine the total water, an air-dry powdered sampie is ignited at

1100°C in a nitrogen atmosphere without a flux or with P20s-flux. The water liberated

is directed through an IR cell for measurement. The water of crystallization is

determined in the same way but the sampie is heated at 110°C before the measurement.

The moisture water is determined at 110°C. The results have been compared with

those of the Penfield method and found compatible. Similar results have been obtained

from international geological reference sampies. The new method has several

advantages: operation is simple and unvarying; it is also faster than the old Penfield

method; the carbon dioxide liberated from sampies does not interfere with the

26

determination; nor does fluorine cause error in the water results when the sample in the

combustion boat is covered with quartz powder (Paper VI, Saikkonen 1990).

3.2 Determination of ferrous iron

Iron occurs in rocks and minerals in oxidation states of +II and +III and in very small

amounts as native iron. Knowledge of ferrous and ferric iron concentrations is

important for geochemical and petrological studies, for instance, when calculating rock

nonns and investigating magmatic processes. Meteorites usually contain native iron; in

iron meteorites it is the main component (Mueller 1978).

For the determination of ferrous iron, the rock, mineral or special sample is usually

dissolved. With the Mössbauer spectrometer the ratio of ferrous to ferric iron can be

determined on a solid sample direct. However, the method needs refining, particularly

for rock samples (Bancroft et aI. t977). There are far fewer methods for determining

ferric than ferrous iron, and the ferric iron concentration is usually calculated as the

difference between total and ferrous irons. Several methods are available for

determining total iron, and the procedure is generally fatly easy. Detailed descriptions

of the analytical methods for ferrous, ferric and total iron and their history have been

published by Maxwell (1968) and Sulzec & Povondra (1989).

As a technical procedure, the determination of ferrous iron may be straightforward but

it may still pose an awkward analytical problem. Most analytical errors arise during the

preparation and decomposition of samples. Ferrous iron may be oxidized into ferric

iron in the course of grinding. To prevent oxidation, the grinding should be done in an

inert liquid, e.g. acetone, as this prevents air from reaching the sample and also

reduces heat generation. The metallic iron in grinding vessels causes an error by

reducing some of the ferric iron into ferrous iron. Such contamination can be avoided

by grinding the sample in an agate mortar. Tungsten carbide, which is often used in

grinders, also acts as a reductant, making the concentration of ferrous iron higher than

it is in reality. If the sample is ground mechanically, the grinding time should be as

26

determination; nor does fluorine cause eITor in the water results when the sampie in the

combustion boat is covered with quartz powder (Paper VI, Saikkonen 1990) .

3.2 Determination of ferrous iron

Iron occurs in rocks and minerals in oxidation states of + II and + III and in very small

amounts as native iron. Knowledge of ferrous and ferric iron concentrations is

important for geochemical and petrological studies, for instance, when calculating rock

norms and investigating magmatic processes. Meteorites usually contain native iran; in

iran meteorites it is the main component (Mueller 1978).

For the determination of ferrous iron, the rock, mineral or special sampie is usually

dissolved. With the Mössbauer spectrometer the ratio of ferrous to ferric iron can be

determined on asolid sampie direct. However, the method needs refining, particularly

for rock sampies (Bancraft et al. 1977). There are far fewer methods for determining

ferric than ferrous iron, and the ferric iron concentration is usually calculated as the

difference between total and ferrous irons. Several methods are available for

determining total iran, and the procedure is generally fairly easy. Detailed descriptions

of the analytical methods for ferrous, ferric and total iran and their history have been

published by Maxwell (1968) and Sulzec & Povondra (1989).

As a technical pracedure, the determination of ferrous iron may be straightforward but

it may still pose an awkward analytical problem. Most analytical errors arise during the

preparation and decomposition of sampies. Ferrous iron may be oxidized into ferric

iron in the course of grinding. To prevent oxidation, the grinding should be done in an

inert liquid, e .g. acetone, as this prevents air fram reaching the sampie and also

reduces heat generation. The metallic iron in grinding vessels causes an error by

reducing some of the ferric iron into ferrous iron. Such contamination can be avoided

by grinding the sampie in an agate mortar. Tungsten carbide, which is often used in

grinders, also acts as a reductant, making the concentration of ferrous iron higher than

it is in reality. If the sampie is ground mechanically, the grinding time should be as

27

short as possible to minimize oxidation. The grain size of the sample should be about

80 mesh, i.e. less than 0.175 mm, for the sample to dissolve in acids. A good grinding

vessel is one that prevents excessive heating (Rice 1982, Whipple et al. 1984, Paper

ur).

Ferrous iron is easily oxidized when a sample is dissolved in acids. To prevent this,

the sample should be dissolved in an inert atmosphere, e.g. oxygen-free nitrogen or

carbon dioxide gas. The effect of atmospheric oxygen can be minimized by painstaking

and careful work at all stages of decomposition. If a known amount of oxidant is used

in decomposition to oxidize the dissolving ferrous iron into ferric iron, no inert

affnosphere is needed. The oxidizing or reducing components in the sample alter the

true ferrous iron/ferric iron ratio during the decomposition. These oxidizing elements

include manganese (III), chromium (VI) and vanadium (V). Native iron, sulphur (II)

and organic matter are reducing agents (Fritz & Popp 1985, Kane & Skeen t993).

The weak point in acid decomposition is that some iron-bearing minerals dissolve

poorly in acids; not even prolonged leach in the much-used hydrofluoric-sulphuric acid

mixture can guarantee complete decomposition of the sample. Tourmaline, staurolite,

ilmenite, magnetite, chromite and a number of other less common minerals do not

dissolve at all, or only partially, during acid treatment. Prolonged boiling in acid easily

results in the oxidation of ferrous iron, as concentrated sulphuric acid is a very

effective oxidant. It might be advisable to repeat the acid decomposition and to try and

dissolve the residue once again. When the author used a decomposition bomb for rock

samples, a portion of ferrous iron oxidized, probably because the dissolution vessel was

not tight enough. A sample can also be brought into solution with a flux such as

sodium fluoroborate, lithium metaborate or lithium tetraborate. According to Kiss

(1984), the constitutional oxygen in the flux may act as an oxidizer for ferrous iron.

The concentration of ferrous iron in rock and mineral samples is usually determined

from dissolved sample. Exceptions to this rule are Mössbauer spectrometric

measurements, which use powdered sample (Dryar et al. 1987, Fudali 1988). The

concentration of ferrous iron in sample solute can be determined titrimetrically

(Whipple Ig74, Kiss 1977, Graff 1983), spectrometrically (Kiss 1984, Bruce & Bower

19g7, Endo etal. 1992, Flock & Koch 1993) or polarographically (Beyer etal. L975,

27

short as possible to minimize oxidation. The grain size of the sampie should be about

80 mesh, i.e. less than 0.175 mm, for the sampie to dissolve in acids. A good grinding

vessel is one that prevents excessive heating (Rice 1982, Whippie et al. 1984, Paper

VII).

Ferrous iron is easily oxidized when a sampie is dissolved in acids . To prevent this,

the sampie should be dissolved in an inert atmosphere, e .g. oxygen-free nitrogen or

carbon dioxide gas . The effect of atmospheric oxygen can be minimized by painstaking

and careful work at all stages of decomposition. If a known amount of oxidant is used

in decomposition to oxidize the dissolving ferrous iron into ferric iron, no inert

atmosphere is needed. The oxidizing or reducing components in the sampie alter the

true ferrous ironlferric iron ratio during the decomposition. These oxidizing elements

include mangane se (I1I) , chromium (VI) and vanadium (V). Native iron, sulphur (Il)

and organic matter are reducing agents (Fritz & Popp 1985, Kane & Skeen 1993).

The weak point in acid decomposition is that some iron-bearing minerals dissolve

poorly in acids; not even prolonged leach in the much-used hydrofluoric-sulphuric acid

mixture can guarantee complete decomposition of the sampie. Tourmaline, staurolite,

ilmenite, magnetite, chromite and a number of other less common minerals do not

dissolve at all, or only partially, during acid treatment. Prolonged boiling in acid easily

results in the oxidation of ferrous iron, as concentrated sulphuric acid is a very

effective oxidant. It might be advisable to repeat the acid decomposition and to try and

dissolve the residue once again. When the author used a decomposition bomb for rock

sampies, a portion of ferrous iron oxidized, probably because the dissolution vessel was

not tight enough. A sampie can also be brought into solution with a flux such as

sodium fluoroborate, lithium metaborate or lithium tetraborate. According to Kiss

(1984), the constitutional oxygen in the flux may act as an oxidizer for ferrous iron.

The concentration of ferrous iron in rock and mineral sampies is usually determined

from dissolved sampie . Exceptions to this rule are Mössbauer spectrometric

measurements , which use powdered sampie (Dryar et al. 1987, Fudali 1988). The

concentration of ferrous iron in sampie solute can be determined titrimetrically

(Whippie 1974, Kiss 1977, Graff 1983) , spectrometrically (Kiss 1984, Bruce & Bower

1987, Endo et al. 1992, Flock & Koch 1993) or polarographically (Bey er et al. 1975 ,

28

Moore L979). Great care must be taken to ensure that the oxidation state of ferrous

iron remains unchanged while the measuring solution is prepared and also during the

measurement.

Titration of ferrous iron is undertaken as a visual or potentiometric oxidation/reduction

procedure, most commonly using potassium dichromate solution as the titrant. If the

sample is dissolved in the presence of an excess oxidant, the residual oxidant can be

titrated with a ferrous iron solution of known strength. This solution is often titrated

with a potassium dichromate solution. The concentration of ferrous iron in the sample

can then be calculated from the data thus obtained.

It is still difficult to determine concentrations of ferrous iron in minerals that do nor go

readily into solution and in rocks containing these minerals, as there is no entirely

satisfactory analytical method for that purpose. One of the most useful available for

determining ferrous iron in small mineral samples is probably the micromethod

introduced by Kiss. In it a mineral sample weighing a few milligrams is placed in aquartz vessel and dissolved in cerium(IV)/phosphoric acid at 325"C. The concentration

of ferrous iron is then measured indirectly by potentiometric titration of the excess

cerium (IV) with ferrous iron solution (Kiss L9S7).

In contrast, several methods are available for the satisfactory determination of ferrous

iron in readily soluble rocks and minerals. All have high enough accuracy and

precision but their rapidity for the routine analysis of large series of samples could be

better.

Publication VII compares three titrimetric methods making use of 13 GSF and 3linternational geological reference samples. These are the method of Amonette & Scott

(1991), the modified method of Wilson (Wilson 1955, Whipple 1974) and the modified

method of Pratt (Jackson et al. 1987). All the methods are useful for samples that can

be dissolved in acids and do not contain oxidizing or reducing components. The

sulphur in acid-soluble sulphides in particular causes large errors in the method ofAmonette & Scott and also in that of Wilson. In Pratt-s procedure, soluble S(II) as

hydrogen sulphide gas does not interfere. The modified method of Pratt is the mosr

useful of the three for determining ferrous iron in unknown rock samples (Paper VII).

28

Moore 1979) . Great care must be taken to ensure that the oxidation state of ferrous

iran remains unchanged while the measuring solution is prepared and also during the

measurement.

Titration of ferrous iron is undertaken as a visual or potentiometric oxidationlreduction

procedure, most commonly using potassium diehromate solution as the titrant. If the

sampie is dissolved in the presence of an excess oxidant, the residual oxidant can be

titrated with a ferrous iron solution of known strength. This solution is often titrated

with a potassium diehromate solution. The concentration of ferrous iron in the sampie

can then be calculated from the data thus obtained.

It is still difficult to determine concentrations of ferrous iron in minerals that do not go

readily into solution and in rocks containing these minerals, as there is no entirely

satisfactory analytical method for that purpose . One of the most useful available far

determining ferrous iran in small mineral sampies is probably the micromethod

introduced by Kiss. In it a mineral sampie weighing a few milligrarns is placed in a

quartz vessel and dissolved in cerium(IV)/phosphoric acid at 325°C. The concentration

of ferrous iron is then measured indirectly by potentiometrie titration of the excess

cerium (IV) with ferrous iron solution (Kiss 1987) .

In contrast, several methods are available for the satisfactory determination of ferrous

iron in readily soluble rocks and minerals. All have high enough accuracy and

precision but their rapidity for the routine analysis of large series of sampies could be

better.

Publication VII compares three titrimetrie methods making use of 13 GSF and 31

international geological reference sampies . These are the method of Amonette & Scott

(1991), the modified method of Wilson (Wilson 1955, Whippie 1974) and the modified

method of Pratt (Jackson et al. 1987). All the methods are useful for sampies that can

be dissolved in acids and do not contain oxidizing or reducing components. The

sulphur in acid-soluble sulphides in particular causes large errors in the method of

Amonette & Scott and also in that of Wilson. In Pratt' s procedure, soluble S(II) as

hydrogen sulphide gas does not interfere . The modified method of Pratt is the most

useful of the three for determining ferrous iron in unknown rock sampies (Paper VII) .

3.3

29


Carbon, which is present in rocks and minerals in concentrations ranging from several

percent to a few ppm, most often occurs as a carbonate such as calcite, dolomite or

siderite. The amount of other carbon-bearing material, i.e. graphite and organic

carbon, is usually low, but in graphite schists the concentration of graphite carbon is

commonly several percent or even tens of percent (toukola-Ruskeeniemi 1992). Some

minerals have constitutional elemental carbon or CO or CN groups (Zemann 1978).

Fluid inclusions of metamorphic rocks often contain carbon dioxide and hydrocarbons

as gas or liquid (Roedder 1984).

In rock and mineral analyses, carbon is most often determined as carbonate carbon

(COt and total carbon. The concentration of non-carbonate carbon is obtained by

subtracting the concentration of carbonate carbon from that of total carbon. The non-

carbonate carbon is either graphite or other forms of element carbon derived from

organic matter (kventhal & Shaw 1980).

Most of the analytical methods are based on the decomposition of carbonates with acid,

ignition of the sample at high temperature or wet-oxidation of carbon, and the

gravimetric, titrimetric, colorimetric or IR spectrometric determination of the carbon

dioxide thus generated @aper WII, Saikkonen 1994). The carbonate and non-carbonate

carbons can be separated from each other by removing the carbonate carbon with acid

decomposition. Attempts have been made to separate the carbon phases with thermal

decomposition but the procedure is difficutt (Charles & Simmons 1986, Saikkonen

1993).

In the study discussed in Paper VIII, total and non-carbonate carbon were determined

with the IR carbon analyser, CR-12 (LECO Corporation). Before the non-carbonate

carbon was measured, the carbonate carbon was removed from the sample by acid

treatrnent. Twenty international geological reference samples and 13 GSF rock

reference samples were analysed for this study. The results were highly satisfactory,

particularly when compared with those reported for the 20 international reference

samples. The concentrations of carbonate and non-carbonate carbons obtained for the

29

3.3 Determination of carbon

Carbon, which is present in rocks and minerals in concentrations ranging from several

percent to a few ppm, most often occurs as a carbonate such as calcite, dolomite or

siderite. The amount of other carbon-bearing material , i.e. graphite and organic

carbon, is usually low, but in graphite schists the concentration of graphite carbon is

commonly several percent or even tens of percent (Loukola-Ruskeeniemi 1992) . Some

minerals have constitutional elemental carbon or CO or CN groups (Zemann 1978).

Fluid inclusions of metamorphic rocks often contain carbon dioxide and hydrocarbons

as gas or liquid (Roedder 1984) .

In rock and mineral analyses , carbon is most often detennined as carbonate carbon

(C02) and total carbon. The concentration of non-carbonate carbon is obtained by

subtracting the concentration of carbonate carbon from that of total carbon. The non

carbonate carbon is either graphite or other fonns of element carbon derived from

organic matter (Leventhal & Shaw 1980).

Most of the analytical methods are based on the decomposition of carbonates with acid ,

ignition of the sampie at high temperature or wet-oxidation of carbon, and the

gravimetric, titrimetrie , colorimetric or IR spectrometric detennination of the carbon

dioxide thus generated (Paper VIII, Saikkonen 1994). The carbonate and non-carbonate

carbons can be separated from each other by removing the carbonate carbon with acid

decomposition. Attempts have been made to separate the carbon phases with thennal

decomposition but the procedure is difficult (Charles & Simmons 1986, Saikkonen

1993).

In the study discussed in Paper VIII, total and non-carbonate carbon were determined

with the IR carbon analyser, CR-12 (LECO Corporation). Before the non-carbonate

carbon was measured, the carbonate carbon was removed from the sampie by acid

treatment. Twenty international geological reference sampies and 13 GSF rock

reference sampies were analysed for this study. The results were highly satisfactory,

particularly when compared with those reported for the 20 international reference

sampies . The concentrations of carbonate and non-carbonate carbons obtained for the

3.4

30

GSF reference samples were compatible with the gravimetric data. The precision of the

results, which was about L%,5% or l0% with a carbon concentration of about 10%,

I% or 0.1%, respectively, was good and consistent with the trend towards a relatively

low standard deviation at high concentrations but high deviation at low concentrations.

Once the CR-12 instrument is set up and has stabilized, the operation is easy. It is also

rapid: about 70 determinations of total carbon and 40 determinations of the non-

carbonate carbon can be made by one analyst daily, compared with 10 determinations

with the gravimetric method. The method is suitable for determining the carbon content

of ancient sediments and of igneous and metamorphic rock samples containing more

than 0.01 % C. A sample size of 0.5-1.0 g is recommended.

Determination of halogens, sulphur and loss on ignition

Determination of halogens

The mean concentrations of fluorine, chlorine, bromine and iodine in silicate rocks are

shown in Table 4. The most common fluorine-bearing minerals are biotite, apatite and

fluorite. Scapolite and sodalite are chlorine-bearing silicate minerals. Bromine is a

relatively rare element, but in marine sediments with organic component and in

sedimentary rocks its concentrations may exceed 100 ppm (Koljonen 1992).Iodine, the

rarest of the halogens, has the highest concentrations in marine sediments and

sedimentary rocks. It occurs in various minerals, most cornmonly as silver, copper

iodides, lead iodides and calcium iodate, or lauüarite, one of the most important iodine

minerals in sediments (Wedepohl 1978).

The detection limits of different methods for halogens in rocks and minerals are listed

in Table 5.

30

GSF reference sampies were compatible with the gravimetrie data. The precision of the

results, which was about 1 %, 5% or 10% with a carbon concentration of about 10%,

1 % or O. 1 %, respectively, was good and consistent with the trend towards a relatively

low standard deviation at high concentrations but high deviation at low concentrations .

Once the CR-12 instrument is set up and has stabilized, the operation is easy. It is also

rapid: about 70 determinations of total carbon and 40 determinations of the non

carbonate carbon can be made by one analyst daily, compared with 10 determinations

with the gravimetrie method. The method is suitable for determining the carbon content

of ancient sediments and of igneous and metamorphie rock sampies containing more

than 0.01 % C. A sampIe size of 0.5-1.0 g is recommended.

3.4 Determination of halogens, sulphur and loss on ignition

Determination of halogens

The mean concentrations of fluorine, chlorine, bromine and iodine in silicate rocks are

shown in Table 4. The most common fluorine-bearing minerals are biotite, apatite and

fluorite . Scapolite and sodalite are chlorine-bearing silicate minerals . Bromine is a

relatively rare element, but in marine sediments with organie component and in

sedimentary rocks its concentrations may exceed 100 ppm (Koljonen 1992). lodine, the

rarest of the halogens, has the highest concentrations in marine sediments and

sedimentary rocks. lt occurs in various minerals, most commonly as silver, copper

iodides, lead iodides and calcium iodate, or lautarite, one of the most important iodine

minerals in sediments (Wedepohl 1978).

The detection limits of different methods for halogens in rocks and minerals are listed

in Table 5.

31

Table 4. Mean halogen concentratsions (ppm) inHutchison l-983) and halogen concentrations insample, l4Ac-1 (marine mud) (Govindaraju 1989)

silicate rocks (Jeffery a

an inEernationaL reference

Ultra-mafic

Mafic InEer-mediate

Granitic Alkaline l,lAc- 1

FluorineChlorineBromineIodine

r- zv100-400o.L-20.1-0.4

300- 500

100-400o -L-20.1--0.4

500-r.000r.00-4000.2-20. L-0.4

200-2000L00 -4 00

o.5-20.1-0.4

500-2000 770

200-2000 3.1?252

380

Table 5. Detection timits of different methods for halogens (PPm inrock). Met,hods: ion-specific elecErode, IS; ion-chromatography, IC; XRF;

neutron activaEion, NAA,' spectrophotometry, CK; and "otshers", oTI{-

Samples were decomposed with fusion and trhe elements separated by

pyrohydrolyse or ion-exchange chromatography. XRF determinations were

made on briguetted samPles.

ISfusiona.

ICpyroh.

XRF

briq.NAA CK

pyroh. fusion

FluorineChlorineBromineIodine

20-4040-1000.1 h.

ztJ - 5u

20-5055 00

50

8

5k.

10 e.20 f. s

1 i. 0.00.04 1.

2.90.20.1

v-j.

a. Hoffstettser et a1., L99L b. HaJ-l et a}., 1985 c. Pottrs, L993 d-

Langenauer et a1., !g92 e. Fuge and Andrews, 1985 f. Hoffstetter etäf., 1991 s. separation by distillation and ion-specific electrode,Elsheimer, L98'7 h. separation by ion-exchange chromatography and ion-specific elecurode, Akaiva et a}., 1980 i. Pyen etr a1., 1980 j. mass

specgrometer, Heuman et aI, 1983 k. COSCrove, L97O 1. FUge et al.,t978 -

31

Table 4. Mean halogen concentrations (ppm) in silicate rocks (Jeffery &

Hutchison 1983) and halogen concentrations in an international reference

sample, MAG-1 (marine mud) (Govindaraju 1989) .

Ultra- Mafic Inter- Granitic Alkaline MAG-1 mafic mediate

Fluorine 1-20 300-500 500-1000 200-2000 500-2000 770 Chlorine 100-400 100-400 100-400 100-400 200-2000 3 . 1% Bromine 0.1-2 0 . 1-2 0 . 2-2 0.5-2 252 Iodine 0.1-0.4 0.1-0.4 0.1-0 .4 0.1-0.4 380

Table 5. Detection limits of different methods for halogens (ppm in

rock) . Methods: ion-specific electrode, I8; ion-chromatography, IC; XRF;

neutron activation, NAA; spectrophotometry, CK; and "others", OTH.

8amples were decomposed with fusion and the elements separated by

pyrohydrolyse or ion-exchange chromatography . XRF determinations were

made on briquetted samples.

Fluorine

Chlorine

Bromine

Iodine

I8

fusion

a.

20-40

IC

pyroh.

b .

20-50

40-100 20-50

0.1 h .

XRF

briq.

c.

5600

50

8

6 k.

NAA

pyroh.

d .

2 . 9

0.2

0 . 1

CK

fusion

10

20

1

e.

f.

i.

0.04 1.

OTH

5 g.

0.0 j.

a. Hoffstetter et al., 1991 b. Hall et al., 1986 c. Potts, 1993 d.

Langenauer et al., 1992 e. Fuge and Andrews, 1985 f. Hoffstetter et

al., 1991 g. separation by distillation and ion-specific electrode,

Elsheimer, 1987 h. separation by ion-exchange chromatography and ion

specific electrode, Akaiva et al., 1980 i. pyen et al., 1980 j. mass

spectrometer, Heuman et al, 1983 k. Coscrove, 1970 1. Fuge et al.,

1978.

32

Rocks and minerals can be analysed for fluorine and chlorine with a number of

methods. Normal silicate rock samples can easily be analysed with an ion-specific

electrode (Fabbri & Donati 1981, Stecher 1983, Yuchi et al. 1988, Rice 1988), by ion

chromatography (Conrad & Brownlee 1988, Hall et al. 1986, Kennedy et al. 1983,

Wilson & Kent L982, Ewarns et al. 1981, Gent & Wilson 1985), XRF (koni et al.

1982, Langenauer et al. 1992) or spectrophotometry (Fuge & Andrews 1985,

Adelantado et al. 1985, Hoffstetter et al. 1991). Low concentrations (<20 ppm) are

more difficult to determine; the sample must be bigger, and fluorine and chlorine must

be separated from the sample matrix and concentrated. Bromine and iodine can be

determined by spectrophotometry @yen et al. 1980, Fuge et al. 1978), XRF (Ullman

& Tisue 1983, Croscove 1970) or activation analysis (Langenauer et al. 1992).

In Chemical Laboratory of the GSF, fluorine concentrations of rocks and minerals are

determined with an ion-specific electrode from a solute produced with sodium

hydroxide fusion. The corresponding chlorine determinations are made by

spectrophotometry. The sample is dissolved with sodium carbonate fusion. Both

methods gave satisfactory results when compared with those reported for several GSF

and international reference samples (Rautiainen & Saikkonen, unpublished results).

Determination of sulphur

Sulphur occurs in rocks as sulphides, sulpho-salts, sulphates, native sulphur or organic

sulphur. Sulphide minerals such as pyrrhotite (Fe,-"S) and pyrite (FeSr) are presenr in

low abundances (0.01-0.1%) in almost all rocks. Many sulphide minerals form ores as

a result of various geological processes. Sulphate minerals, the most coürmon of which

are gypsum (CaSOo * 2H2O), alum (KAlSOo * 12 }lz0) and barite (BaSOo), are

abundant in marine sediments and sedimentary rocks. Soluble sulphates and gaseous

sulphur compounds occur in mineral inclusions. Elementary sulphur is formed through

32

Rocks and minerals can be analysed for fluorine and chlorine with a number of

methods. Normal silicate rock sampies can easily be analysed with an ion-specific

electrode (Fabbri & Donati 1981, Stecher 1983, Yuchi et al. 1988, Rice 1988), by ion

chromatography (Conrad & Brownlee 1988, Hall et al. 1986, Kennedy et al. 1983,

Wilson & Kent 1982, Ewans et al. 1981, Gent & Wilson 1985), XRF (Leoni et al.

1982, Langenauer et al. 1992) or spectrophotometry (Fuge & Andrews 1985 ,

Adelantado et al. 1985, Hoffstetter et al. 1991). Low concentrations «20 ppm) are

more difficult to determine; the sampie must be bigger, and fluorine and chlorine must

be separated from the sampie matrix and concentrated. Bromine and iodine can be

determined by spectrophotometry (Pyen et al. 1980, Fuge et al. 1978), XRF (Ullman

& Tisue 1983, Croscove 1970) or activation analysis (Langenauer et al. 1992) .

In Chemical Laboratory of the GSF, fluorine concentrations of rocks and minerals are

detennined with an ion-specific electrode from a solute produced with sodium

hydroxide fusion. The corresponding chlorine detenninations are made by

spectrophotometry. The sampie is dissolved with sodium carbonate fusion . Both

methods gave satisfactory results when compared with those reported for several GSF

and international reference sampies (Rautiainen & Saikkonen, unpublished results).

Determination of sulphur

Sulphur occurs in rocks as sulphides, sulpho-salts, sulphates, native sulphur or organic

sulphur. Sulphide minerals such as pyrrhotite (Fe1_xS) and pyrite (FeS2) are present in

low abundances (0.01-0.1 %) in almost all rocks. Many sulphide minerals fonn ores as

a result of various geological processes . Sulphate minerals, the most common of which

are gypsum (CaS04 * 2H20) , alum (KAIS04 * 12 H20) and barite (BaS04) , are

abundant in marine sediments and sedimentary rocks. Soluble sulphates and gaseous

sulphur compounds occur in mineral inclusions. Elementary sulphur is formed through

33

the bacterial reduction of sulphates or the oxidation of volcanic hydrogen sulphide gas.

Organic sulphur compounds (e.g. S-aminoacids) are formed through sulphate reduction

(Wuesch 1978).

The sulphur in rocks and minerals is determined from pulverized samples. Excessive

grinding may oxidize part of the sulphides into sulphur dioxide, which is then expelled

from the sample. Sulphide may oxidize into sulphate, causing an error in the

concentration of sulphide zulphur in the sample.

Selective leaches are used for quantitative determinations of different sulphur forms

(Rice et al. 1993). The success of the determination depends on the mineral

composition and grain size of the sample, the degree of crystallization of the sulphide

minerals, the concentration of ferric iron in the sample, and the degree of diagenesis

or metamorphism of sediments and sedimentary rocks. The sample must, therefore, be

thoroughly examined before analysis. Information on the mineral and elemental

composition of the sample also facilitates performance of the analysis (Canfield et al.

1986, Tuttle et al. 1986, Jackson et al. 1987). In rock and mineral analysis, it is often

sufficient to determine totat sulphur (S.) when the sulphur concentration is low,

<0.L%. If sulphate and sulphide sulphurs are measured independently, their

concentrations are given as sulphur trioxide and native sulphur. In general, total

sulphur is reported as native sulphur. Sulphide correction must then be made for the

oxides of the analysis by subtracting the amount of oxygen corresponding to the

amount of sulphur from the sum of the oxides if other elements occurring as sulphides,

e.g. iron, have been reported as oxides. The correction is unnecessary if the sulphate

sulphur is reported as SOr. The sulphide correction is feasible only if information is

available on the mineral composition and analytical conditions. Pyrite does not go into

solution in the conventional determination of ferrous iron with the Pratt method.

Therefore, the ferrous iron of pyrite is often erroneously reported in the analysis as

Fe3*. In the classical methods of sulphur determination, the sample is usually dissolved

by fusion with sodium carbonate, and the total sulphur is oxidized into sulphate and

precipitated as barium sulphate. This method is not suitable for low concentrations, as

the BaSOa precipitate may include impurities. Sample can also be heated at a high

temperature in oxygen or air flux, often in the presence of an oxidant. Sulphur is then

oxidized into sulphur dioxide and trioxide. The gases are absorbed into a suitable

33

the bacterial reduction of sulphates or the oxidation of volcanic hydrogen sulphide gas.

Organic sulphur compounds (e .g. S-aminoacids) are formed through sulphate reduction

(Wuesch 1978).

The sulphur in rocks and minerals is determined from pulverized sampIes. Excessive

grinding may oxidize part of the sulphides into sulphur dioxide, which is then expelled

from the sampIe. Sulphide may oxidize into sulphate , causing an error in the

concentration of sulphide sulphur in the sampIe .

Selective leaches are used for quantitative determinations of different sulphur forms

(Rice et al. 1993). The success of the determination depends on the mineral

composition and grain size of the sampIe , the degree of crystallization of the sulphide

minerals , the concentration of ferric iron in the sampIe, and the degree of diagenesis

or metamorphism of sediments and sedimentary rocks . The sampIe must, therefore, be

thoroughly examined before analysis. Information on the mineral and elemental

composition of the sampIe also facilitates performance of the analysis (Canfield et al.

1986, Tuttle et al. 1986, Jackson et al. 1987). In rock and mineral analysis, it is often

sufficient to determine total sulphur (StoJ when the sulphur concentration is low,

< 0.1 %. If sulphate and sulphide sulphurs are measured independently , their

concentrations are given as sulphur trioxide and native sulphur. In general, total

sulphur is reported as native sulphur. Sulphide correction must then be made for the

oxides of the analysis by subtracting the amount of oxygen corresponding to the

amount of sulphur from the sum of the oxides if other elements occurring as sulphides ,

e.g . iron, have been reported as oxides . The correction is unnecessary if the sulphate

sulphur is reported as S03' The sulphide correction is feasible only if information is

available on the mineral composition and analytical conditions . Pyrite does not go into

solution in the conventional determination of ferrous iron with the Prau method.

Therefore, the ferrous iron of pyrite is often erroneously reported in the analysis as

Fe3+. In the classical methods of sulphur determination, the sampIe is usually dissolved

by fusion with sodium carbonate, and the total sulphur is oxidized into sulphate and

precipitated as barium sulphate. This method is not suitable for low concentrations, as

the BaS04 precipitate may include impurities. SampIe can also be heated at a high

temperature in oxygen or air flux, often in the presence of an oxidant. Sulphur is then

oxidized into sulphur dioxide and trioxide . The gases are absorbed into a suitable

34

solution and the sulphur oxides determined spectrophotometrically, gravimetrically or

titrimetricalty (Johnson & Maxwell l98l).

The sulphur concentration of rocks and minerals is usually measured with more or less

automated analysers. An X-ray fluorescence spectrometer is useful for the rapid

determination of several elements simultaneously. The powdered sample to be analysed

is compressed into a briquette or converted into a glassJike fusion preparate. For the

briquette, the detection limit of sulphur in routine determinations is about 20 ppm

(Potts L993). The disadvantage of this preparate is that correct sulphur data cannot be

obtained unless the sample and standard sample are of similar sulphide mineral

composition (koni et al. 1982). When measured on the fusion preparate, the detection

limit of sulphur is about 120 ppm (Potts 1993).

In many analytical methods, sulphur is first separated by heating the sample under

oxidizing conditions. Sulphur oxidized into sulphur dioxide in pyrolysis can be

determined by IR spectrometry (Terashima 1988), ion chromatography (Hall et al.

1986) and iodometric (Bouvier et al. L972) or colorimetric titration (Atkin &Somerfield L994). Hall and Vaive (1989) have compared the zulphur determination

methods used by the Geological Survey of Canada, that is, pyrohydrolyse-ion

chromatography, pyrolyse-infra-red spectrometry and pyrolyse-titration.

Determination of loss on ignition

The reduction in the mass of the sample on ignition is reported as loss on ignition

(LOD. On ignition (usually for i h at 1000"C), water together with carbon in itsvarious forms is expelled from the weighed sample as are, either totally or partially,

sulphur, fluorine, chlorine and such rare elements as mercury and selenium. However,

the mass also increases during ignition, as ferrous oxide is oxidized into ferric oxide.

The mass increment can be calculated if the concentration of ferrous iron is known. Ifit is not, then total iron must be reported as FqOr; the plus error due to the expression

34

solution and the sulphur oxides determined spectrophotometrically, gravimetrically or

titrimetrically (Johnson & Maxwell 1981) .

The sulphur concentration of rocks and minerals is usually measured with more or less

automated analysers. An X-ray fluorescence spectrometer is useful for the rapid

determination of several elements simultaneously . The powdered sampie to be analysed

is compressed into a briquette or converted into a glass-like fusion preparate. For the

briquette, the detection limit of sulphur in routine determinations is about 20 ppm

(Potts 1993). The disadvantage of this preparate is that correct sulphur data cannot be

obtained unless the sampie and standard sampie are of similar sulphide mineral

composition (Leoni et al. 1982). When measured on the fusion preparate, the detection

limit of sulphur is about 120 ppm (Potts 1993).

In many analytical methods, sulphur is first separated by heating the sampie under

oxidizing conditions . Sulphur oxidized into sulphur dioxide in pyrolysis can be

determined by IR spectrometry (Terashima 1988), ion chromatography (Hall et al.

1986) and iodometrie (Bouvier et al. 1972) or colorimetric titration (Atkin &

Somerfield 1994). Hall and Vaive (1989) have compared the sulphur determination

methods used by the Geological Survey of Canada, that is , pyrohydrolyse-ion

chromatography, pyrolyse-infra-red spectrometry and pyrolyse-titration.

Determination of loss on ignition

The reduction in the mass of the sampie on ignition is reported as loss on ignition

(LOI) . On ignition (usually for 1 h at 1000°C), water together with carbon in its

various forms is expelled from the weighed sampie as are, either totally or partially,

sulphur, fluorine, chlorine and such rare elements as mercury and selenium. However,

the mass also increases during ignition, as ferrous oxide is oxidized into ferric oxide .

The mass increment can be calculated if the concentration of ferrous iron is known. If

it is not, then total iron must be reported as Fe:z03; the plus error due to the expression

l

35

of ferrous iron as ferric iron is then of the same magnitude as the minus error in the

weighed LOI. Thus the errors compensate for each other and do not affect the sum of

the oxides in total analysis. The determination of LOI complements the total rock

analysis. Measurement of the concentrations of volatile components expelled from the

sample on ignition can be used to test the accuracy of rock analyses by XRF and

plasma spectrometry if it is neither possible nor necessary to determine these

concentrations independently (kchler & Desilets 1987, King & Vivit 1988, Huka &

Rubeska 1993, Kane & Skeen 1993).

SI,]MMARY

This study investigated and developed chemical analytical methods for rocks, minerals

and other geological samples such as meteorites. With the aid of Finnish and

international geological reference samples the methods were compared with other

methods in use. Numerous rock, mineral, meteorite and other geological samples were

analysed with modified and classical wet-chemical and instrumental methods. The

results are presented in papers I-VIII.

The analytical method comprising modified old and new determination methods used

for this work is one of the most accurate available for the total analysis of many

geological samples. Normally the following major and minor components are

determined in total analysis: silica, titanium oxide, aluminium oxide, manganese oxide,

ferric iron oxide, ferrous iron oxide, calcium oxide, magnesium oxide, constitutional

water (HrO.) and moisture water (HrO) and often also fluorine, chlorine, sulphur and

native carbon. In the main-portion analysis of the method, silica, calcium oxide and

magnesium oxide as well as the oxide-group precipitate of all the elements that

precipitate with ammonia are determined gravimetrically. Titanium oxide and total

iron(Ill)oxide are measured from the oxide group precipitate spectrophotometrically'

Aluminium oxide is obtained by subtracting the weight of the other oxides from the

total weight of the oxide group precipitate. The main-portion analysis was tested and

investigated in Publication II.

35

of ferrous iron as ferric iron is then of the same magnitude as the minus error in the

weighed LOI. Thus the errors compensate for each other and do not affect the sum of

the oxides in total analysis. The determination of LOI complements the total rock

analysis . Measurement of the concentrations of volatile components expelled from the

sampie on ignition can be used to test the accuracy of rock analyses by XRF and

plasma spectrometry if it is neither possible nor necessary to determine these

concentrations independently (Lechler & Desilets 1987, King & Vivit 1988, Huka &

Rubeska 1993, Kane & Skeen 1993).

4 SUMMARY

This study investigated and developed chemical analytical methods for rocks , minerals

and other geological sampies such as meteorites. With the aid of Finnish and

international geological reference sampies the methods were compared with other

methods in use . Numerous rock, mineral, meteorite and other geological sampies were

analysed with modified and classical wet-chemical and instrumental methods . The

results are presented in papers I-VIII.

The analytical method comprising modified old and new determination methods used

for this work is one of the most accurate available for the total analysis of many

geological sampies. Normally the following major and minor components are

determined in total analysis: silica, titanium oxide , aluminium oxide, manganese oxide,

ferric iron oxide , ferrous iron oxide, calcium oxide, magnesium oxide, constitutional

water (H20 +) and moisture water (H20 ") and often also fluorine, chlorine , sulphur and

native carbon. In the main-portion analysis of the method, silica, calcium oxide and

magnesium oxide as well as the oxide-group precipitate of all the elements that

precipitate with ammonia are determined gravimetrically. Titanium oxide and total

iron(III)oxide are measured from the oxide group precipitate spectrophotometrically .

Aluminium oxide is obtained by subtracting the weight of the other oxides from the

total weight of the oxide group precipitate. The main-portion analysis was tested and

investigated in publication II .

36

The second subsample in the total analysis method is dissolved with hydrofluoric, nitric

and perchloric acids. Sodium and potassium are determined from the solute thus

obtained by flame photometry or flame AAs. Manganese and phosphorus

concentrations are measured colorimetrically as pennanganate and molybdo-vanado

phosphoric acid complex (Fig..1). Water, ferrous iron and carbon dioxide, and often

also native carbon, fluorine, chlorine and sulphur, are analysed as individual

determinations. The concentrations of total and constitutional waters in the sample are

determined with IR spectrometry. The water of crystallization in the sample can also

be obtained by subtracting the concentration of moisture water from that of total water.

The concentration of ferric iron is calculated by subtracting that of ferrous iron from

total iron (Fig. 1).

The above package of methods is suitable for analysing single samples requiring an

individual approach and analysis, e.g. rock and mineral reference samples, certain

mineral samples and meteorite samples. It cannot be used for analysing samples en

masse. Instruments suitable for this purpose are the X-ray fluorescence spectrometer,

atomic absorption spectrophotometer and plasma spectrometer. The precision and

accuracy of the analyses of many of the elements determined with XRF, that is, Si, Ti,Al, Fe,o,, Mn, Mg, ca, Na, K and P, are of the same order of magnitude as those

determined in total analysis as described above. The accuracies of flame AAS and ICp-AES analyses are equal to those of XRF for some elements. Many trace elements can

also be determined with XRF, AAS and ICP-AES instruments. But, as pointed out

above, in the total analysis of rocks and minerals by these instruments cannot analyse

all of the components (Table 2). For individual determinations a new subsample must

be taken from the sample powder, which then requires separate chemical pretreatment

(dissolution, separation, etc.) and measurement of concentration.

The objectives of the present work were to develop new and more rapid individual

determination methods that would be appropriate in other respects, too (e.g. accuracy,

precision and detection limit) for analysing rocks, minerals and other related geological

samples, and to improve existing methods for individual determination.

The method for determining water with IR absorption was investigated and refined inthe course of the work. It has several advantages. Operation with the RMC-100

36

The second subsampie in the total analysis method is dissolved with hydrofluoric, nitric

and perchloric acids. Sodium and potassium are determined from the solute thus

obtained by flame photometry or flame AAS. Manganese and phosphorus

concentrations are measured colorimetrically as permanganate and molybdo-vanado

phosphoric acid complex (Fig. ). Water, ferrous iron and carbon dioxide, and often

also native carbon, fluorine, chlorine and sulphur, are analysed as individual

determinations . The concentrations of total and constitutional waters in the sampie are

determined with IR spectrometry. The water of crystallization in the sampie can also

be obtained by subtracting the concentration of moisture water from that of total water.

The concentration of ferric iron is calculated by subtracting that of ferrous iron from

total iron (Fig . 1).

The above package of methods is suitable for analysing single sampies requiring an

individual approach and analysis, e.g. rock and mineral reference sampies, certain

mineral sampies and meteorite sampies. It cannot be used for analysing sampies en

masse. Instruments suitable for this purpose are the X-ray fluorescence spectrometer,

atomic absorption spectrophotometer and plasma spectrometer. The precision and

accuracy of the analyses of many of the elements determined with XRF, that is, Si , Ti,

Al, Felol , Mn, Mg, Ca, Na, K and P, are of the same order of magnitude as those

determined in total analysis as described above. The accuracies of flame AAS and ICP

AES analyses are equal to those of XRF for some elements. Many trace elements can

also be determined with XRF, AAS and ICP-AES instruments. But, as pointed out

above, in the total analysis of rocks and minerals by these instruments cannot analyse

all of the components (Table 2). For individual determinations a new subsampie must

be taken from the sampie powder, which then requires separate chemical pretreatment

(dissolution, separation, etc .) and measurement of concentration.

The objectives of the present work were to develop new and more rapid individual

determination methods that would be appropriate in other respects, too (e. g. accuracy,

precision and detection limit) for analysing rocks, minerals and other related geological

sampies, and to improve existing methods for individual determination.

The method for determining water with IR absorption was investigated and refined in

the course of the work. It has several advantages. Operation 'with the RMC-lOO

37

instrument is simple and unvarying. The total and crystallization waters of rocks and

minerals can clearly be determined more rapidly with this method than with the

gravimetric Penfield method and with equally good accuracy. This method is in use at

the chemical laboratory of GSF (Paper VI, Saikkonen 1990).

The analytical methods for ferrous iron were assessed by comparing ttree titrimetric

methods: the Pratt method, the Wilson method and the Amonette & Scott method. It

was concluded that the modified Pratt method is the most useful for determining of

ferrous iron in unknown samples. The Wilson method and the Amonette & Scott

method can be applied to samples of known mineral composition. The modified Pratt

method is in use at the chemical laboratory of GSF (Paper VII).

The method based on IR absorption and used for determining total carbon in geological

samples was studied and an IR method was developed for determining the

concentration of non-carbonate carbon, which is either graphite or other forms of

element carbon deriving from organic matter. The concentration of carbonate carbon

is obtained by subtracting the concentration of non-carbonate carbon from that of total

carbon. The methods described above are in use at the chemical laboratory of GSF

(Paper VItr).

Methods for determining halogens, sulphur and LOI were reviewed on the basis of the

literature and in the light of practical experience.

37

instrument is simple and unvarying. The total and crystallization waters of rocks and

minerals can clearly be determined more rapidly with this method than with the

gravimetrie Penfield method and with equally good accuracy. This method is in use at

the chemicallaboratory of GSF (Paper VI, Saikkonen 1990).

The analytical methods for ferrous iron were assessed by comparing three titrimetrie

methods: the Pratt method, the Wilson method and the Amonette & Scott method. It

was concluded that the modified Pratt method is the most useful for determining of

ferrous iron in unknown sampies. The Wilson method and the Amonette & Scott

method can be applied to sampies of known mineral composition. The modified Pratt

method is in use at the chemical laboratory of GSF (Paper VII).

The method based on IR absorption and used for determining total carbon in geological

sampies was studied and an IR method was developed for determining the

concentration of non-carbonate carbon, which is either graphite or other forms of

element carbon deriving from organie matter. The concentration of carbonate carbon

is obtained by subtracting the concentration of non-carbonate carbon from that of total

carbon. The methods described above are in use at the chemical laboratory of GSF

(Paper VIII).

Methods for determining halogens, sulphur and LOI were reviewed on the basis of the

literature and in the light of practical experience.

38

ACKNOWLEDGEMENTS

The work discussed in this thesis was carried out at the Geological Survey of Finland.

I would like to thank Professor Veikko Lappalainen, Director of the Geological

Survey, professor Marklu Mäkelä and professor Lauri Eskola for giving me the

opportunity to carry out this pröject, and for approving publication of this paper as an

issue of the GSF, Miscellaneous publications. GSF's chemical laboratory has provided

me with modern laboratories, instruments and equipment and also a good working

atrnosphere. I also express my gratitude to the former heads of the chemical laboratory:

Professor Birger Wiik and Pentti Noras, and to HarrJ'Sandström, the laboratory's

present head, and to Gustaf Wansen, the head of the Espoo laboratory and to all my

coworkers at the chemical laboratorv.

I am greatly indebted to my colleagues, Ringa Danielsson, Dr Kari Kinnunen,

Professor Kauko Laajoki, Dr Seppo Lahti and Irja Rautiainen for good co-operation.

Useful cotnments on many versions of the manuscript and papers were received fromDr Juha Karhu, Esko Kontas, Maija llmasti, Riitta Juvonen and Pentti Noras - thank

you! In addition, I want to acknowledge the assistance I received from Christer

Ahlsved, Juhani oinonen, Ari Puisto and Mervi wiik in the laboratorv.

The manuscript was reviewed by Dr. Tapio Koljonen and Dr. Esko Saari and I thank

them for their corrections and suggestions. I am particularly indebted to my supervisor,

Professor Markku I-eskelä, of Helsinki University, whose advice and critical reading

helped me to improve the manuscript.

This summary was translated into English by Gillian Häkli. The library staff and the

staff in the publications section gave their kind help. I am very grateful to all these

people, and to the many others who helped me at various stages of the work.

Last, but not least, I thank my wife Tuire and my children for their patience and

sympathy during this work.

38

ACKNOWLEDGEMENTS

The work discussed in this thesis was carried out at the Geological Survey of Finland.

I would like to thank Professor Veikko Lappalainen, Director of the Geological

Survey , professor Markku Mäkelä and professor Lauri Eskola for giving me the

opportunity to carry out this project, and for approving publication of this paper as an

issue of the GSF, Miscellaneous publications. GSF ' s chemicallaboratory has provided

me with modem laboratories , instruments and equipment and also a good working

atmosphere . I also express my gratitude to the former heads of the chemicallaboratory:

Professor Birger Wiik and Pentti Noras, and to Harry Sand ström , the laboratory ' s

present head , and to Gustaf Wansen, the head of the Espoo laboratory and to all my

coworkers at the chemical laboratory .

I am greatly indebted to my colleagues, Ringa Danielsson, Dr Kari Kinnunen,

Professor Kauko Laajoki, Dr Seppo Lahti and Irja Rautiainen for good co-operation.

Useful comments on many versions of the manuscript and papers were received from

Dr Juha Karhu , Esko Kontas , Maija Ilmasti , Riitta Juvonen and Pentti Noras - thank

you! In addition, I want 10 acknowledge the assistance I received from Christer

Ahlsved, Juhani o inonen , Ari Puisto and Mervi Wiik in the laboratory.

The manuscript was reviewed by Dr. Tapio Koljonen and Dr. Esko Saari and I thank

them for their corrections and suggestions. I am particularly indebted to my supervisor,

Professor Markku Leskelä , of Helsinki University , whose advice and critical reading

helped me to improve the manuscript.

This summary was translated into English by Gillian Häkli. The library staff and the

staff in the publications section gave their kind help . I am very grateful to all these

people, and to the many others who helped me at various stages of the work.

Last, but not least, I thank my wife Tuire and my children for their patience and

sympathy during this work.

39

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Talanta 32,224-226.

Adler, I. 1986. The analysis of extraterrestrial materials. New York: John Wiley & Johns. 346 p.

Akaiwa, H., Kawamoto, H. & Hasegava, K. 1980. Determination of a trace amount of bromine in rocks by

ion exchange chromatography and direct potentiometry with an ion-selective electrode. Talanta 27,9O9-9IO.

Amonette, J.E. & Scon, A.D. 1991. Determination of ferrous iron in non-refractory silicate minerals. l. An

improved semi-micro oxidimetric method. Chemical Geology. 92, 329 -338.

Angino, E.E. & Bitling, G.K. 1967. Atomic absorption spectrometry in geology. Amsterdam: Elsevier

Scientific Publishing Co. 2O2 p.

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Geologiska Undersökning, Serie C 616, Arsbok 6l (L). 77 p.

Atkin, B. P. & Somerfield, C. 1994. The determination of total sulphur in geological materials by

coulometric tiuation. Chemical Geology 111, 131-134.

Bancroft, G. M., Sham, T.K., Riddle, C., Smith, T.E. & Turek, A. 1977.Fercic/ferrous-iron ratios in bulk

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39

REFERENCES

Adelantado, J. v. G., Martinez, v. P. , Moreno, A. C. & Reig, F. B. 1985 . Spectrophotometric determination of fluoride in fluoride-bearing minerals after decomposition by fusion with sodium hydroxide . Talanta 32, 224-226.

Adler, I. 1986. The analysis of extraterrestrial materials. New York: John Wiley & Johns. 346 p.

Akaiwa, H., Kawamoto , H. & Hasegava, K. 1980. Determination of a trace amount ofbromine in rocks by ion exchange chromatography and direct potentiometry with an ion-selective electrode . Talanta 27, 909-910.

Amonette , J.E. & Scott, A.D. 1991. Determination offerrous iron in non-refractory silicate minerals . 1. An improved semi-micro oxidimetric method. Chemical Geology. 92, 329-338 .

Angino , E.E. & Billing, G.K. 1967. Atomic absorption spectrometry in geology. Amsterdam: Elsevier Scientific Publishing Co. 202 p.

Asklund, M.A., Grundulis, V & Rönnholm B. 1966. Vätkemisk analys av silikatbergarter. Sveriges Geologiska Undersökning, Serie C 616, Ärsbok 61 (1). 77 p.

Atkin, B. P. & Somerfield, C. 1994. The determination of total sulphur 10 geological materials by coulometric titration. Chemical Geology 111, 131-134.

Bancroft, G. M., Sham, T.K., Riddle , C., Smith, T.E. & Turek, A. 1977. Ferric/ferrous-iron ratios in bulk rock sampies by Mössbauer spectroscopy - The determination of standard rock sampies G-2, GA, W-l and Mica-Fe . Chemical Geology 19, 277-284.

Baur, W.H. 1978. Hydrogen, 1 A. In: Wedepohl , K.H. (ed.) Handbook of geochemistry lI-I. Berlin: Springer-Verlag. p. l-A-1.

Berry, H., & Rudowski , R. 1965 . The preparation of chondritic meteorites for chemical analysis . Geochimica et Cosmochimica Acta , 29 , 1367-1369.

Beyer, M. E., Bond, A. M. & McLaughlin, R. J. W. 1975. Simultaneous polarographic determination of ferrous, ferric and total iron in standard rocks . Analytical Chemistry 47, 479-482.

Bock, R.A. 1979. Handbook of decomposition methods in analytical chemistry. New York: John Wiley & Sons. 444 p.

Bouvier, J ., Sen Cupta, 1. G. & Abbey, S. 1972. Use of an "automatic sulphur titrator" in rock and mineral analysis: determination of sulphur, total carbon, carbonate and ferrous iron. Geological Survey of Canada, Paper 72-31. 23 p.

Bruce, C. B. & Bower, N.W. 1987. Spectrophotometric determination of ferrous iron in eighteen United States geochemical reference standards. Geostandards Newsletter 11,41-42.

Canfield, D. E., Raiswell, R., Westrich, J. T., Reaves, C. M. & Berner, R. A. 1986. The use ofchromium reduction in the analysis ofreduced inorganic sulfur in sediments and shales. Chemical Geology 54, 149-155.

Chao, T .T. & Sandszolone , R.F. 1992. Decomposition techniques. Journal of Geochemical Exploration, Special Issue 44, 65-106 .

Charles, M. J. & Simmons, M. S. 1986. Methods for determination of carbon in soils and sediments. A review. Analyst 3, 385-390.

Conrad, V. B. & Brownlee, W. D. 1988. Hydropyrolytic-ion chromatographic determination of fluoride in coal and geological materials. Analytical Chemistry 60, 365-369.

40

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40

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45

Volborth, A. 1969. Elernental analysis in geochemistry. Amsterdam: Elsevier Scientific Publication Co.373 p.

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45

Volborth , A. 1969. Elemental analysis in geochemistry. Amsterdam: Elsevier Scientific Publication Co . 373 p.

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Westrieh, H.R. 1987. Determination of water in volcanic glasses by Karl-Fisher titration. Chemical Geology 63, 335-340.

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WhippIe, E.R. , Speer, I .A . & Russel, C.W. 1984. Errors in FeO determinations caused by tungsten carbide grinding apparatus. American Mineralogist 69 , 987-988 .

Wiik , H.B. 1956. The chemical composition of some stony meteorites . Geochimica et Cosmochimica Acta 9,279-289 .

Wiik, H.B. 1972. The chemical composition of the Haverö meteorite and the composition of the other five ureilites . Meteoritics 7, 553-557 .

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Wiik, H.B . 1986. Geometrie regularity in the ratios of the stable isotopes. Commentationes PhysicoMathematicae 77 . 16 p.

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Yuchi , A., Yanai , N. , Wada, H. & Nakagawa, G. 1988. Tiron as a masking reagent for aluminium in the determination of fluoride with an ion-selective electrode : equilibrium studies and application. Analyst 113, 1405-1408.

Appendix.choieIMp6itb!oldtni@|!rnpbm|y$dbyRir.s.irbß'AIr!yti5lfIId'nodifEdc|s5k'maio6gmiM.l!rinÜic'.dorimÜic)'mic'üdpthnd.nf!Fliicdn!.

SlOr TIO, ALOr FerOr FeO MnO MgO CaO NarO KrO pro, CO, HrO* HrO. F CI Li:O RbrO CsrO B€O SrO BaO CrrO, NiO BrO,

0.680.680.760.71

0.r3 0.t90.19 0.160.07 0.7114.07 0.100.10 0.340.1 I 0.960.04 L t00.10 0.9236.18 0.0411.02 t.700.03 0.040.0? 0. r00.lE 0.060.13 0.040.07 0.590.19 0.380.540.060.05I1.28 1.250.00 0.450.16 0.294.350.64 0.010.10 0.020.10 0.030.09 0.01

0.t20.140,120.23

9.42 0.008.44 0.079.66 0.030.16 0.00o.zt 0.010. t 8 0.000.06 0.030.23 0.030.0s 0.0s1.25 0.000.05 0.002.52 0.071.63 0.14t.46 0.130.13 0.000.26

0.03 0.0010.64 0.038.97 0.00

0.01 0.010.02 0.000.0t 0.130.02 0.02

2.04,1.59,

1.49,

l 3E,

0.00 1.650.00 3.28

3.64s.33

0.00 t.2t0.00 1.59

0.00 7.060.00 2.t20.00 0.160.00 r.26

0.00 I 1.550.00 t2.300.00 t2.440.00 0.08

0.00 4.063.91

0.00 2.50

t.57 5.271.90 4.823.13 4.893.27 4.800.87 4.881.48 4.911.83 5.04o.99 5.150.88 5.160.5t 4.940.77 5.200.54 5.ZO

0.I I 4.360.16 t.290.10 2.000.41 0.390.330.33 0.000. l50.100.000.08

0.06 0.00 0.020.ol 0.00 0.020.06 0.00 0.030.07 0.00 0.02t.l9 0.900.31 0.310.03 0.o22.32

0.30 0.00 0.020.15 0.01 0.00

7.49 0.00 0.00

0.01 0.00 0.000.0E 0.071.33 0.28 0.I I

t2.7913. l812.79

12.79

0.00 0.00.00 0.0

7.21

0.33

0.72

0.01

0.00

Silicates

l. Beryl2. Beryl3. Beryl4. Beryl5. Biotite6. Biotite7. Biothe8. Biryite9. Cordierite10. Cordieritell. Cordierite12. Cordierite13. Grossularite14. Hornblende

15. Kaolinile16. Kaolinite17. KaolinirelE. Kaolinite19. Kunzite

20. Kyanite2l. Kyanite22. Kyanite

23. Kyanite24. Margarite25. Muskovite26. Phengite

27. Pyrcpe28. Talc29. Talc

30. Talc

31. Talc32. Talc33. Talc

34. Talc

35. Talc36. Talc

37. Talc38. Talc

39. Talc

LOI Total

38.57

32.61

39.74

33.35

47.92

44.81

45.91

45.99

40.43

42.66

45.69

47.t246.4946.46

63.85

46.48

52.r435.43

38.47

30.464E.8546.4041.5658. l057.25

56.U56.17

5E.24

57.81

58.2959.6259.76

59.63

59.17

60.02

0.18t.7 |1.09

0.000.03

o.t70.060.05

0.322.68

|.280.050.100.13

0.01

0.540.280.03

0.03

0.05l.5l0.91

0.620.010.020.02

0.4

18.90 5.82t8.n 7.6tt7.40 0.3234.61

34.34 1.2033.1I |.5031.53 2.3731.52 2.t221.95 0.15,11.40 2.97

37.08 1.86,

36.64 0.8337.6 0.7738.01 0.6227.72 0.16,48.3 1.50,

4t .2 1.00,

62.20 0.40,59.16 0.4q5l.l? 0.t530.51 0.4026.73 t.2623.s9 L.sr0.69 0.061.00 0.430.7t 0.ll0.73 0.220.36 2.15,0.47 2.3410.49 2.39,0.51 1.41,

0.59 1.46,

0.57 t.42,0.76 r.44,0.64 1.38,

19.53 0.60 0.o224.53 0.34 0.22o.l2 0.00 26.t4|.23, 0.00 1.846.92 0.23 8.4115.72 t.Oz 0.89t0.45 1.91 3.5710.73 0.90 3.96

0.25 0.5616.04 0.20 9.03

0.00 0.05o.42 0.02 0.220.13 0.01 o.2r0.14 0.01 0.16

0.16 0.05

0.200.43

0.01 0.160.01 0.30

0.18 0.00 0.650.0t 3.07

5.63 0.16 2.706.81 O.32 20.ss2.26 0.01 30.972.26 0.01 3t.522.62 0.01 3t.392.4r 0.0t 31.40

30.39

30.88

31.33

3t.633l.6331.70

31.83

3t.33

0.000.29 0.440.l3 3.62

0.03

0.20 0.0

0.00 0.1E

0.00 0.03

0.0s 0.00

r.39

0.15 0.180.26 0.200.23 0.19

99.85

99.6810{J.24

t00.86l0t.3lr00.3999.59

100.51

100. l4100.29

t3.72 99.8099.65

99.68

99.73

100.34

98.29

98.42

9.49100.3E

99,79

100.70

99.64

99.68

100.05(8.09) 99.575.706.366.8r

0.000.000.02

Appendix. Chemieal eomposition of 63 mineral sam pies analysed by Risto Saikkonen. Analytieal methods: modified c1assical methods (gravimetrie, titrimetrie, colorimetrie), atOll1ie absorption and emission speetrometrie methods and other mcthods .

Silicates

I. Beryl 2. Beryl 3. Beryl 4 . Beryl 5. Biotite 6. Biolite 7. Biotite 8. Bityite 9. Cordierite 10. Cordierite 11. Cordierite 12. Cordierite 13 . Grossularitc 14 . Hornblende 15. Kaolinite 16. Kaolinite 17. Kaoli nite 18. Kaolinite 19. Kunzite 20. Kyanite 21. Kyanite 22 . Kyanite 23. Kyanite 24 . Margarite 25. Muskovite 26 . Phengite 27. Pyrope 28. Tale 29. Tale 30. Tale 31. Tale 32. Tale 33 . Tale 34. Tale 35. Tale 36. Tale 37 . Tale 38 . Tale 39 . Tale

510, TiO, AI,O, Fe,O, FeO MnO MgO CaO Na,O K,O P,O, CO, ",0' ",0- F

38.57 0. 18 18.90 5 .82 32.61 1.71 18.90 7.67 39.74 1.09 17.40 0 .32 33 .35 0.00 34 .61 47 .92 0 .03 34 .34 1.20 44 .81 0.17 33 . 11 1.50 45 .91 0.06 31.53 2.37 45 .99 0.05 31 .52 2.12 40.43 0.32 21.95 0.15, 42 .66 2.68 11 .40 2 .97 45 .69 1.28 37.08 1.86, 47 .12 0.05 36.64 0.83 46.49 0 .10 37.66 0.77 46.46 0.13 38.01 0 .62 63.85 0.01 27.72 0.16, 46.48 0.54 48 .3 1.50, 52.14 0.28 41.2 1.00, 35.43 0.03 62.20 0.40, 38.47 0.03 59.16 0.40, 30.46 0.05 51.17 0.15 48.85 1.51 30.51 0.40, 46.40 0.91 26.73 1.26 41.56 0 .62 23.59 1.51 58. 10 0.01 0.69 0.06 57 .25 0.02 1.00 0.43 56.44 0.02 0.71 0.11 56.17 0.02 0.73 0.22 58.24 0.36 2.15, 57.81 0.47 2 .34, 58.29 0.49 2.39, 59.62 0.51 1.41, 59.76 0.59 1.46, 59 .63 0.57 1.42, 59.17 0.76 1.44, 60.02 0.64 1.38,

19.53 0.60 0.02 24 .53 0 .34 0.22 0 .12 0.00 26.14 1.23, 0.00 1.84 6.92 0.23 8.41

15 .72 1.02 0 .89 10.45 1.91 3.57 10.73 0.90 3.96

0.25 0.56 16.04 0.20 9.03

0 .00 0 .05 0.42 0.02 0.22 0.13 0.01 0.21 0.14 0.01 0.16

0.16 0.05 0.20 0.43

0.01 0 .16 0.01 0.30

0.18 0.00 0.65 0.01 3.07

5.63 0.16 2.70 6.81 0.32 20.55 2.26 0.01 30.97 2.26 0.01 31.52 2.62 0.01 31.39 2.41 0 .01 31.40

30.39 30.88 31.33 31.63 31.63 31.70 31.83 31.33

0 .68 0 .68 0 .76 0 .71

0. 13 0 . 19 0 .19 0 .16 0.07 0 .71

14 .07 0 .10 0.10 0 .34 0 .11 0 .96 0.04 1.10 0 .10 0 .92

36.18 0.04 11.02 1.70 0.03 0 .04 0.07 0 .10 0.18 0.06 0.13 0.04 0 .07 0 .59 0.19 0.38 0 .54 0 .06 0 .05 11.28 1.25 0.00 0.45 0 .16 0.29 4.35 0.64 0.01 0 .10 0 .02 0.10 0 .03 0.09 0.01

0.12 0.14 0. 12 0.23 9.42 0 .00 8.44 0.07 9.66 0.03 0 .16 0.00 0 .21 0.01 0 .18 0.00 0.06 0.03 0.23 0.03 0.05 0.05 1.25 0.00 0 .05 0 .00 2.52 0.07 1.63 0.14 1.46 0.13 0 .13 0 .00 0 .26

0.03 0.00 10.64 0.03 8.97 0.00

0.01 0.01 0 .02 0.00 0.01 0.13 0.02 0.02

0.00 0.00

0 .00 0 .00 0.00 0 .00 0.00 0.00

0.00 0.00 0.00 0 .00

0.00

0.00

1.57 1.90 3.13 3.27 0.87 1.48 1.83 0.99 0.88 0.51 0.77 0 .54

2.04, 1.58, 1.48, 1.38, 1.65 3.28 3.64 5.33 1.27 1.59 2.06 2.12 0.16 1.26

11.55 12.30 12.44 0 .08

4.06 3.91 2.50

5.27 4 .82 4 .89 4.80 4.88 4.91 5.04 5.15 5. 16 4.94 5.20 5.20

0. 11 0. 16 0. 10 0.41 0.33 0.33 0 .15 0 .10 0 .00 0.08

0.00 0.00 0.02

0.00 0.29 0 .13

0 .03

4 .36 1.29 2.00 0 .39

0.00

0.44 3.62

Cl S Li,O Rb,O Cs,O BeO SrO BaO Cr,O, NiO B,O, LOI Total

0.06 0.04 0.06 0 .07 1.19 0.31 0.03 2.32

0 .30 0 .15

7.49

0.01 0.08 1.33

0 .00 0.02 0.00 0.02 0.00 0.03 0.00 0 .02 0.90 0 .31 0 .02

0.00 0.02 0 .01 0.00

0.00 0.00

0.00 0.00 0.07 0.28 0.11

12.79 13.18 12.79 12.79

7.21

0.33 0 .72

0.00

0.00 0.0 0 .00 0 .0

0.01

0 .20 0.0

0.00 0 .18

0.00

0.05

1.39

0 .15 0.26 0.23

0.03

0 .00

0 .18 0.20 0.19

99.85 99.68 100.24 100.86 101.31 100.39 99.59 100.51 100. 14 100.29

13 .72 99.80 99.65 99.68 99.73

100.34

98.29 98.42 99.49 100.38 99 .79 100.70 99.64 99.68 100.05

(8.09) 99.57 5.70 6.36 6.81

Appendix

Silicates40. Turmalin41. Turmalin42. Turmalirt43. Turnralin44. Turmalin45. Turmalin46. Turrnalin47. Vermiculite48. Zoisite

(Tanzanite)

Oxides49. Brokite50. Rutile

Phosphates

51. Antplygonile52. Apatite

53. Apatite54. Apatite

55. Apatite56. Apatile57. Apatite58. Apathe

59. Eosphorite

60. Herderile

61. Trifylite-litiofilite

62. Triplile

Sulfat€s63. Selestine

Nui|h.r sr{ in tü. drd* or OSF (GltritlM & S.ldom lta) (h Fioiitn):

Ahd|lmmimlg.Dl6'iIshi.h|.5dfd3o.@liMhrwb6le|'cdb,th.pE'aü.r'e,|bit6''l|Iit6''dlrpiB'a!{ik'bhtl6'b'ü'gkjB,dii6'itMiEr, trolinitd. l.oilolit6. merlta, miceliG, pkg@ldd, pyriB, queÄ, .idcd6, $.d'i|l1ß, Elc!, t !.u {d 6liB

sior Tio,

36.19 0.27

35.25 0.27

35.26 0.2235.13 0.1036.E2 0.m36.85 0.0238.38 0.03

38. 14 l.s3

39.99 0.05

Alro, Fero,

36.7't 8.96,35.28 13.26.37.99 10.94,

38.83 7.15,

f2.27 2.59,41.21 0.23,41.91 0.40,

16.59 0.30

34.24 0.06,

0.32 0.63,0.32 r.52,

34.70 0.001.11,

0.43,0.53,

0.36,0.66,

1.56,

0.23 1.05,

24.s0 0.220.19 0.17,

0.22 t.u0.09 1.66

0.10 L960.19 2.26l.5l t.740.38 |.740.14 | .76

1.41 0.33

24.40 0.09

K,o &q

0.06 0.000.06 0.000.06 0.000.06 0.000.06 0.m0.18 0.000.45 0.000.15 0.03

0.06 0.07

FeO MnO MgO CaO NerO

0.14 4.690.20 2s20.25 0.621.08 0.37

0. 14 I 1.03

r.26 0.12

0.41 0.43

0.11 0.01 23.09

0.04 0.04

0.01 0. t00.03 0.07

0.00 0.00 0.000.04 0.77

0.02 0.500.03 0.570.01 0.03

0.02 0.340.07 0.190.69

1.98 24.30 0.00o.29

29.37 t3.39 0.68t5.47 44.55 0.10

cq Hro'

0.00 2.590.00 2.6r0.00 2.840.00 2.740.00 z.ffi0.00 3.060.00 3.22

0.00 10.41

0.00 l.l5

HrO F Cl

0.03 0.150.l I 0.35

0.04 0.97

0.04 l.l80.04 0.53

0.08 1.04

0.09 0.93

7 .56 1.60

0.01 0.02

LitO RbrO CsrO BeO SrO BaO

0.01

0.05

0.59I .18

0.05

t.82L86 0.03 0.040.14 0.00

0.00

9.70

0.4Eo.4z0.550.720.700.550.32

t4.81

CrrO, NiO BrQ LOI

8.78

9. 16

8.m9.03

8.22

10. l29.77

0.00 0.00

0.11

0.01

0.000.000.000.000.000.00

Y2Ot:9.24n 1*.0,

2t2.

Total

100.44

lw.72100.33

99.54

98.3099.67

99.39100.65

9E.83

99.26

99.29

0,14 0.00

1.43

0.16 0.000.40

0.01 0.29 0.02 48.5 2.80 0.00 7.24

54.0 0.17 0.03 42.9 0.68

53.8 0.13 0.02 42.3 0.41

s3.t o.22 0.07 42.7 0.73

55.2 0.t4 0.03 42.9 1.00

s4.3 0. t6 0.03 42.3 0.76

53.7 0.17 0.01 41.2 0.7951.96 0.76 0.06 3E.71 0.19 l.& 0.18 2.43

0.06 0.t5 0.02 32.95 14.26 0.02 0.41

36.24 0.77 0.08 43.21 3.28 0.00 4.21

0.06 0.07 0.03 45.99 0.00 0.02 0.02

o.37 0.00 0.02 32.39 0.00 0.88 0.00 8.00

0.83

0.00

0.30

100.32

100.2

98.699.1

100.4

99.398.2

Tl,O = 0.53% 98.5

99.82

t00.85

0.12 0.01 0.08 0.48

0.00 0.12 0.t6 0.43

0.00 0.020.960.05

9.08

SO, = 43'55 54.69 0.22

t-

Appendix SiO, TiO, Alp, Fe,O, FeO MnO MgO CaO Na,O K,o pp, CO,

Silicates 40. Turmalin 41. Turmalin 42. Turmalin 43 . Turmalin 44 . Turmalin 45 . Turm31in 46. Turmalin 47. Vermiculite 48 . Zoisite

(Tan7.anite)

Oxides 49. Brokite 50. Rutile

Phosphates 51. Amplygonite 52. Apatite 53. Apatite 54. Apat ite 55 . Apatite 56. Apatite 57 . Apatite 58. Apatite 59. Eosphorite 60. Herderite 61 . Trifylitc

litiofilite 62. Triplite

Sulfates 63 . Selestine

1 = lotal

36.19 0.27 36.77 8.96, 35 .25 0.27 35 .28 13 .26, 35 .26 0.22 37 .99 10.94, 35 .73 0.10 38.83 7.15, 36.82 0.92 32.27 2.59, 36.85 0.02 43 .21 0.23, 38.38 0.03 41.91 0.40, 38.14 1.53 16.59 0.30

39.99 0.05 34.24 0.06,

0.32 0.63, 0.32 1.52,

0.14 0.00 34 .70 0.00 1.11, 0.43, 0.53, 0.36, 0.66, 1.56,

1.43 0.23 1.05, 0.16 0.00 24.50 0.22 0.40 0.19 0.17,

0.12 0.01 0.08 0.48 0.00 0.12 0.16 0.43

0.11

0 .14 4.69 0.20 2.52 0.25 0.62 1.08 0.37 0.14 11.03 1.26 0.12 0.41 0.43 0.01 23.09

0.04 0.04

0.01 0.10 0.03 0.07

0.00 0.00 0.00 0.04 0.77 0.02 0.50 0.03 0.57 0.01 0.03 0.02 0.34 0.07 0.19 0.69

1.98 24.30 0.00 0.29

29.37 13.39 0.68 15.47 44 .55 0.10

0.22 1.64 0.09 1.66 0.10 1.96 0.19 2.26 1.51 1.74 0.38 1.74 0.14 1.76 1.47 0.33

24.40 0.09

0.01 0.29 54.0 0.17 53.8 0.13 53.7 0.22 55.2 0.14 54 .3 0.16 53 .7 0.17 51.96 0.76 0.06 0.15

36.24 0.77

0.06 0.07 0.37 0.00

0.83

Numbers stored in the dalabase of GSF (Gustafsson & Saikkonen 1994) (in Finnish):

0.06 0.06 0.06 0.06 0.06 0.18 0.45 0.15

0.06

0.00 0.00 0.00 0.00 0.00 0 .00 0.00 0.03

0.07

0.02 48 .5 0.03 42.9 0.02 42.3 0.07 42.7 0.03 42.9 0.03 42 .3 0.01 41.2 0.06 38.71 0.02 32.95 0.08 43 .21

0.03 45.99 0.02 32 .39

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.00

0.19

0.00 0.00

H,O· Hp' F

2.59 2.61 2 .84 2.74 2.60 3.06 3.22 10.41

1.15

2.80

1.04 14 .26 3.28

0.02 0.88

0.03 0.11 0.04 0.04 0.04 0.08 0.09 7.56

0.01

0.15 0.35 0.97 1.18 0.53 1.04 0.93 1.60

0.02

0.00 7.24 0.68 0.41 0.73 1.00 0.76 0.79

0.18 2.43 0.02 0.41 0.00 4.21

0.02 0.00 8.00

2/2. CI S Li,O Rb,o Cs,O DeO SrO BaO Cr,o, NiO D,O, 1-01 Total

0.00 0.02

0.01 0.05 0.59 1.18 0.05 1.82 1.86 0.14

9.70

0.96 0.05

9.08

so, = 43 .55

0.03 0.00

0.00

0.04

0.48 0.42 0.55 0.72 0.70 0.55 0.32 0.00

14.81 0.30

54.69 0.22

0.00

0.11 0 .01

8.78 100.44 9.16 100.72 8.90 100.33 9.03 99.54 8.22 98.30

10. 12 99.67 9.77 99.39

100.65

0.00 V,O, = 0.24 % 100.49

100.32 0.00 100.2 0.00 98.6 0.00 99.1 0.00 100.4 0 .00 99.3 0.00 98 .2

TI,o = 0.53 % 98 .5 99.82

100.85

98 .83 99.26

99.29

1. 71001,2. 71002, 3. 71003.4.71004.5.72101.6. 72102 . 7.840003.8.79030. 9. 72089.10. 72090.11.74126.12.74127. 13 . 840005.14. 67039. 19.81021.20.71022. 21. 71023 . 22 . 71076. 23.71077. 24. 77383.25.840004.26. 78187. 27 . 72088. 40. 73005.41. 73006. 42. 73007. 43 . 73008.44. 73009.45 . 73010.46. 73011.47 . 840001 . 48.840002. 49.71051.50. 71050,51 . 76152.52. 80025, 53.80026,54 . 80027 . 55 . 80028,56. 80029, 57 . 80030, 58. 81020, 59. 76112, 60.81022,61. 75124, 62 . 76098, 63 . 69132 .

About 100 mineral sampies, in which 1-5 elements or constituents have been analysed by the present author, are albites, allanites, antigorites, apatites, biotites, britolites, calsites, chromites , chrysotiles, cordierites. cryolites, hematites, hornblendes , kornerubines , kyanites , ilmenites, kaolinites, lepidolites, margarites, microclines , plagioclases, pyrites, quartzes , siderites, spodumenes, tales, topases, and zeoliles .

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CHEMICAL ANALYSIS OF ROCKS AND MINERALS Geological ...

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