i

THE CARBONATITE-HOSTED APATITE DEPOSIT OF JACUPIRANGA, SE

BRAZIL: STYLES OF MINERALIZATION, ORE CHARACTERIZATION, AND
ASSOCIATION WITH MINERAL PROCESSING

by

PAULA REGINA ALVES

A THESIS

Presented to the Faculty of the Graduate School of the

MISSOURI UNIVERSITY OF SCIENCE AND TECHNOLOGY
In Partial Fulfillment of the Requirements for the Degree

MASTER OF SCIENCE IN GEOLOGY

2008
Approved by

R. D. Hagni, Advisor
J. P. Hogan
F. S. Miller

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iii
ABSTRACT

The carbonatite-hosted apatite deposit of Jacupiranga is located in southeastern

Brazil. The major styles of apatite mineralization are veins or veinlets, small pods or
patches, disseminated apatite, and massive aggregates (locally). The concentration of
apatite involves grinding of the carbonatite, removal of magnetite with a magnet drum,
size classification with cyclones, and flotation to suppress carbonates and collect apatite.
Samples of carbonatite were collected from more recent exposures of the mine
and drill holes. This study utilized a variety of microscopy methods, namely transmitted
and reflected light, cathodoluminescence (CL), and scanning electron microscopy (with
wavelength-dispersive spectrometers for mineral compositions).
Results showed that LREE, Na and Sr are the main elements replacing Ca in the
studied apatite, with relatively low oxide contents (< 0.5%, but up to about 1% for Sr).
LREE and Sr contents consistently increase in the latest intrusions (C4, C5 and SP24).
Chemical and morphological modifications in apatite identified in this work can be
related to detrimental effects on flotation recovery. For instance, the reddish apatite was
fractured, and some grains show no CL, probably as a result of quenching caused by iron
entering the apatite structure, which has also changed its color. In the apatite from the
xenolith-rich area, the elevated presence of fine, platy silicates may be interfering more
with the lower flotation recovery than compositional variations. In the case of the hard
apatite (more difficult to grind), most of the area where it occurs was affected by
hydrothermal activity, as evidenced by the development of a bright, white CL rim in
apatite, and the presence of late veins of carbonates and sulfides filling fractures and
possibly resulting in higher cohesiveness of the grains.

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ACKNOWLEDGMENTS

The completion of this thesis represents the culmination of a trajectory along

which many people have contributed at different times and in different ways, but all very
important. It started back in 2000, when Dr. Richard Dick Hagni, during a field trip to the
Cajati mine, as part of the International Geological Congress, approached the mine
geologist, who was showing the site to the visitors, about joining the group of graduate
students of the University of Missouri-Rolla. The writer thanks Dick Hagni for all his
great support along the road, for his dedication in recruiting students around the world,
and for his lovely wife, who walked an extra mile to help the writer settle in Rolla upon
her arrival.
The initial adaptation in a foreign country, and many other circumstances, became
much easier to overcome due to the constant support of the writers family, Ira, Michele,
Priscila and Junior, many miles away but always present, as well as very special friends
who have been always available during the difficult moments that are part of life.
The development of this thesis also received the invaluable support from the
Society of Economic Geologists, through the Hugh E. McKinstry research grant, from the
colleagues with Bunge Brazil, allowing access to the mine and facilitating the field work,
and from Dr. Maria Cristina Toledo Motta, a carbonatites enthusiast and professor at the
Universidade de So Paulo, through fruitful discussions and access to the thin section
preparation laboratory.
The writer is also very thankful for the motivation received from the committee
members, Dr. John Hogan and Dr. Scott Miller, from the Geology and Geophysics staff,
and from Imerys Pigments, in the figure of Dr. Robert Pruett, for his support during the
writing of this thesis.
Finally, the writer would like to thank the fundamental assistance provided by the
Josephine Husbands Radcliffe fund, through the granted teaching assistant scholarship.

v
TABLE OF CONTENTS

Page
ABSTRACT .................................................................................................................. iii
ACKNOWLEDGMENTS............................................................................................. iv
LIST OF ILLUSTRATIONS ....................................................................................... vii
LIST OF TABLES ........................................................................................................ ix
LIST OF PLATES.......................................................................................................... x
SECTION
1. INTRODUCTION...................................................................................................... 1
1.1. OBJECTIVE AND RELEVANCE OF THE RESEARCH ................................ 1
1.2. BRIEF HISTORY OF THE JACUPIRANGA IGNEOUS COMPLEX (JIC) ... 2
1.2.1. Discovery and Mapping of the Complex ................................................. 2
1.2.2. Mining Activities...................................................................................... 3
2. PETROLOGIC AND TECTONIC CONTEXT OF THE CARBONATITE............. 6
2.1. REGIONAL GEOLOGY AND TECTONIC SETTING.................................... 6
2.2. LITHOLOGIES OF THE JACUPIRANGA IGNEOUS COMPLEX (JIC)..... 10
3. METHODS............................................................................................................... 14
3.1. FIELD WORK .................................................................................................. 14
3.2. ANALYTICAL METHODS ............................................................................ 16
3.2.1. Petrography ............................................................................................ 17
3.2.2. Cathodoluminescence Microscopy......................................................... 17
3.2.3. Scanning Electron Microscopy and Electron Probe Micro-Analysis..... 20
4. RESULTS................................................................................................................. 22
4.1. THE APATITE ORE ........................................................................................ 22
4.1.1. Geochemical and Microscopic Aspects of the Apatite .......................... 25
4.1.2. Characteristics of the Apatite Mineralization......................................... 45

vi
4.2. THE GANGUE MINERALS ........................................................................... 47
4.2.1. Carbonates: Calcite and Dolomite.......................................................... 47
4.2.2. Oxides: Magnetite and Ilmenite ............................................................. 54
4.2.3. Silicates: Olivine and Phlogopite ........................................................... 62
4.2.4. Sulfides: Pyrrhotite, Pyrite, Chalcopyrite, Valleriite ............................. 72
4.2.5. Other Minerals........................................................................................ 77
5. DISCUSSIONS ........................................................................................................ 81
5.1. APATITE PROCESSING IN CAJATI ............................................................ 81
5.2. APATITE CHARACTERISTICS RELATED TO PROCESSING ISSUES ... 82
5.3. DEVELOPMENT OF THE MINERALIZATION: CONTRIBUTIONS
FROM THE GANGUE MINERALS............................................................... 84
5.4. PETROGENETIC ASSOCIATION OF THE DOLOMITIC
CARBONATITE SP 24 ................................................................................... 85
6. CONCLUSIONS ...................................................................................................... 87
6.1. STYLES OF MINERALIZATION .................................................................. 87
6.2. ORE CHARACTERIZATION ......................................................................... 87
6.3. ASSOCIATION WITH MINERAL PROCESSING........................................ 88
APPENDICES
A. PLATE SHOWING SELECTED DRILL CORES ................................................. 90
B. PLATES SHOWING SELECTED MICROGRAPHS ............................................ 92
C. ESTIMATED MODAL COMPOSITIONS FOR SELECTED THIN
SECTIONS ............................................................................................................ 104
D. DATA FROM MICROPROBE ANALYSES....................................................... 106
E. STANDARDLESS QUANTITATIVE ANALYSES (SEM-EDS) OF
PYROCHLORE..................................................................................................... 118
F. TABLES WITH MINERALOGICAL DESCRIPTIONS PER AREA OF
STUDY .................................................................................................................. 121
BIBLIOGRAPHY ...................................................................................................... 131
VITA .......................................................................................................................... 140

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LIST OF ILLUSTRATIONS

Figure

Page

1.1. Photographs of the Cajati Mine ................................................................................. 4

2.1. Tectonic Setting of the Paran Sedimentary Basin, and Related Main Occurrences
of Alkaline Complexes With Carbonatites Along the Margins of the Basin............. 8
2.2. Simplified Regional Geology and Tectonic Domains in the Region of the
Jacupiranga Igneous Complex ................................................................................... 9
2.3. Zone of Jacupirangite Xenoliths in the Northern Portion of the Cajati Mine.......... 11
2.4. Schematic Map of the Jacupiranga Igneous Complex............................................. 13
3.1. Map Showing Areas Selected for Sample Collection in the Carbonatite Mine....... 15
4.1. Graphs Showing Chemical Composition Variations in Apatite From Five
Different Areas in the Jacupiranga Carbonatite....................................................... 28
4.2. Triangular Plot Showing the Level of Substitution of Ca by LREE and Na in
Apatite From Jacupiranga........................................................................................ 32
4.3. Comparison Between New Data of SrO Levels in Apatite From Jacupiranga
and From Other Brazilian Carbonatites Along the Margins of the Paran Basin.... 33
4.4. Diagram Plotting Total LREE Oxides Against Sr Oxide ........................................ 35
4.5. CL Image Showing Zoned Apatite with Euhedral Cores, Evidence of Spiral
Growth, and Concentration of Fluid Inclusions ..................................................... 38
4.6. Microprobe Profile for Oxides of Ce, Sr and Na Along Two Apatite Grains ......... 39
4.7. CL/SEM Image of Apatite Showing Chemical Zoning and Concentration of
Fluid Inclusions in the Core of the Grain ................................................................ 40
4.8. BSE/SEM Image of Calcite With Dolomite Exsolution.......................................... 49
4.9. Dolomite Exsolution as Observed in TL Image, Un-Crossed Nicols...................... 49
4.10. Proportional Content of MgO, SrO and FeO Total in Calcite Versus Dolomite
for a Small Set of Samples From the Jacupiranga Carbonatites.............................. 50
4.11. Triangular Plot Showing level of Substitution of Fe by Mg and Mn in
Magnetite From Jacupiranga.................................................................................... 56
4.12. Variation of % TiO2 in Magnetite From Five Distinct Areas of the Jacupiranga
Carbonatites ............................................................................................................. 58
4.13. RL Image of Ilmenite Inclusions in Magnetite ........................................................ 61
4.14. BSE/SEM Image of Magnetite Showing Ilmenite as Small Inclusions and
Exsolution Laths ...................................................................................................... 61

viii
4.15. Highly Fractured and Partly Altered Olivine Observed Under TL Image With
Crossed Nicols ......................................................................................................... 65
4.16. BSE/SEM Image Showing Detail of Highly Fractured and Partly Altered
Olivine...................................................................................................................... 65
4.17. BSE/SEM Image of Complex Zoning Developed in Subhedral Phlogopite ........... 68
4.18. BSE/SEM Image of Another Zoned Phlogopite Crystal, Cut in a Different
Orientation ............................................................................................................... 69
4.19. RL Image of Pyrrhotite Being Replaced by Colloform Pyrite and Minor
Magnetite ................................................................................................................. 74
4.20. RL Image of Pyrrhotite Being Replaced by Pyrite, Chalcopyrite, Minor
Magnetite, and Valleriite ......................................................................................... 74
4.21. BSE/SEM Image of Pyrrhotite Being Replaced by Pyrite....................................... 74
4.22. BSE/SEM Image of Zoning in Pyrochlore .............................................................. 80
4.23. BSE/SEM Image Showing Close-Up of Twinned Baddeleyite in Contact
With Magnetite ........................................................................................................ 80
E.1. Standardless Quantitative Analysis (SEM-EDS) of Core Zone of Pyrochlore
Crystal .................................................................................................................... 119
E.2. Standardless Quantitative Analysis (SEM-EDS) of Rim Zone of Pyrochlore
Crystal .................................................................................................................... 120

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LIST OF TABLES

Table

Page

2.1. Rock Types Occurring in the Jacupiranga Igneous Complex.................................. 12

3.1. Comparison Between Cathodoluminescence Methods............................................ 19
4.1. Comparison Between the Jacupiranga Primary Apatite Ores and the Secondary
Ores From Other Active Carbonatitic Phosphate Mines in Brazil .......................... 24
4.2. Comparison Between Igneous and Sedimentary Apatite Ores ................................ 26
C.1. Estimated Modal Compositions for Selected Thin Sections................................. 105
D.1. Microprobe Analyses of Apatite ........................................................................... 107
D.2. Microprobe Analyses of Calcite and Dolomite..................................................... 111
D.3. Microprobe Analyses of Magnetite....................................................................... 113
D.4. Microprobe Analyses of Ilmenite ......................................................................... 114
D.5. Microprobe Analyses of Olivine........................................................................... 115
D.6. Microprobe Analyses of Phlogopite ..................................................................... 116
D.7. List and Range of Results of the Applied Sets of Standards ................................ 117
F.1. Microscopic Characteristics of the Apatite............................................................ 122
F.2. Microscopic Characteristics of the Carbonates ..................................................... 124
F.3. Microscopic Characteristics of the Oxides ............................................................ 126
F.4. Microscopic Characteristics of the Silicates.......................................................... 127
F.5. Microscopic Characteristics of the Sulfides .......................................................... 129
F.6. Microscopic Characteristics of the Other Minerals ............................................... 130

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LIST OF PLATES

Plate

Page

A.1. Drill Cores Showing Various Aspects of the Apatite Mineralization..................... 91

B.1. Microscopic Images of Apatite From the Jacupiranga Carbonatite........................ 93
B.2. Microscopic Images of Calcite and Dolomite From the Jacupiranga Carbonatite 97
B.3. Microscopic Images of Magnetite From the Jacupiranga Carbonatite ................... 99
B.4. Microscopic Images of Olivine From the Jacupiranga Carbonatite...................... 100
B.5. Microscopic Images of Phlogopite From the Jacupiranga Carbonatite ................ 101
B.6. Microscopic Images of Various Sulfides From the Jacupiranga Carbonatite....... 102
B.7. Microscopic Images of Other Minerals From the Jacupiranga Carbonatite ......... 103

1
1. INTRODUCTION

Carbonatites are very unique rocks from the Earths mantle. There are over 300
known carbonatite localities in the world (Kogarko et al., 1995). Because of the growing
interest of a number of researchers, the understanding of the carbonatite genesis and
evolution has significantly increased since the 1960's, when its magmatic origin was
experimentally demonstrated by Wyllie and Tuttle (1960). In 1958, eruption of very
fluid, alkaline carbonatite lava from the Oldoinyo Lengai volcano in Tanzania was
observed and subsequently studied by Dawson (1966).
The object of this study is the carbonatite from a world-class igneous complex
located in Cajati (formerly a district of Jacupiranga), southeastern Brazil. Because the
complex is better know as Jacupiranga, this will be the name adopted for the carbonatite
from this region, although the mine will be referred as the Cajati mine.
The Jacupiranga carbonatite forms an apparently continuous orebody of economic
importance with respect to phosphate mining. Despite the fact that they have been known
for many years, no previous work had emphasized the apatite mineralization and its
association with process mineralogy. The idea for this research project arose from the
author's daily experience with apatite beneficiation at the mine, together with the
scientific interest to investigate the possible correlation of the effect of the character of
phosphate ore variations upon the beneficiation process.

1.1. OBJECTIVE AND RELEVANCE OF THE RESEARCH

The objective of this research project was to describe and study the apatite
mineralization in microscopic detail, in order to analyze possible relationships between
these microscopic characteristics and observed mineral processing behavior. Since an
investigation of the mineralization cannot be adequately conducted apart from the other
minerals present in the rock, to which apatite is related, the work consequently provides
additional information on geochemical and petrologic aspects of the Jacupiranga
carbonatite.

2
The utilization of the cathodoluminescence technique was emphasized in the
detailed study of apatite, carbonates and minor minerals of the carbonatite. Updated field
data, mainly based on the writer's mapping and exploration activities, were included in
this study. A variety of samples was collected from several rock exposures not accessible
to authors of works published before 2002.
The relevance of this study relies on its contribution for a better understanding of
the character of the apatite mineralization. This type of work is conducted by mining
companies, but data commonly remains available only as internal information. Thus, this
research project combined industry experience with scientific investigation. From a
scientific standpoint, the use of Jacupiranga's data for comparison with other deposits
may support new insights on the petrogenesis and economic potential of many other
carbonatites.
The importance of carbonatites has continually grown as better knowledge of this
type of rock has evolved. Carbonatites have very unusual compositions, and they
typically hold world class deposits of Nb, REE, and exceptionally Cu. The most recent
studies in the field of economic geology include the possible association of carbonatites
with IOCG (Iron Oxides Copper Gold) deposits (Groves and Vielreicher, 2001).
Carbonatites provide vast opportunities for scientific and geo-economic studies.

1.2. BRIEF HISTORY OF THE JACUPIRANGA IGNEOUS COMPLEX (JIC)

1.2.1. Discovery and Mapping of the Complex. The Jacupiranga Igneous
Complex (JIC) was discovered in 1877 by H. E. Bauer. In 1891, Derby described the area
of carbonatite outcrop as an iron ore occurrence, due to its high magnetite content. In
1954, Melcher provided the first detailed mapping and petrographic descriptions of the
rocks in the complex, recognized the carbonatites, and proposed they had been intruded
in two distinct events. The weathered carbonatites, on the top of a smoothed hill, were
already being mined at the time.
Continuous development of open pit mining exposed the carbonatite and its host
rock, clinopyroxenite. This provided important outcrops for more detailed study of these
rocks. The first geological map of the complex at a scale of 1:25,000 was completed in

3
1989 by Gaspar, and he subsequently prepared a second map of the mine area at a scale
of 1:10,000. Based upon petrological and structural data, he concluded that the
carbonatite body was composed of five successive intrusions. Study of the JIC conducted
by Germann et al. (1987) better outlined the contacts of the large dunite body in the
northern portion of the complex.
In 1999, the regional geological map of the Jacupiranga Igneous Complex was
updated (scale 1:50,000) and expanded by the Brazilian geological survey (CPRM),
aiming to identify mineral opportunities related to the JIC and country rocks. The main
change in the map of the ultramafic complex was the inclusion of an adjacent satellite
body that was detected by processing airborne (magnetic and gamma-spectrometric)
geophysical data. The description of the composition of the satellite body was
preliminary, since it was based only on the petrographic study of a sample collected at a
single reported outcrop. The sample consisted of a biotite-olivine gabbro with
hornblende.
Because most rock types that make up the complex occur in a limited number of
outcrops, some lithological contacts remain inferred. In contrast, the carbonatites are well
exposed on the mine walls, and they have been continuously mapped in detailed scale
(1:500) for deposit modeling, grade control and other mining-related purposes. That
detailed mapping, initiated in 2000, has resulted in better delineation of the carbonatite
intrusions, marginal dikes, and zones of xenoliths.
1.2.2. Mining Activities. Phosphate mining activities began in 1943, and apatite
concentrate has been continuously produced since then. The mine is located at the town
of Cajati, which was a district of the town of Jacupiranga in the 1990's. Initially the ore
was mined from the weathered rock accumulated on top of an oblate hill called Morro
da Mina (Mine Hill). The hill was comprised mainly of the carbonatite body, and
surrounded by clinopyroxenite (jacupirangite). In the 1960s, phosphate-rich
concentrations were also found and mined in the northern foothill area. Recent
gravimetric and borehole surveys have confirmed the extension of the carbonatite body
into the low lands north of the hill.

4
The weathered ore had characteristically high grade (>20%) P2O5, but it was
virtually exhausted in the early 1970s. In order to concentrate phosphate from the
underlying bedrock, an appropriate mineral processing based on flotation was developed
to recover lower grade ore (average of 5 % P2O5). Diverse applications of the resulting
tailings were subsequently developed, as they are economically useful for the cement
industry (both carbonate and magnetite concentrates). The carbonate tailings with high
magnesium are utilized as soil additive. Part of the fragmented (blasted) clinopyroxenite
is further crushed and sold as construction aggregate.
Currently, Cajati is producing apatite from one of the worlds lowest phosphate
average grade deposit. In 2002, the ore was being mined from as low as 70 m below the
sea level, to as high as 120 m above sea level. The hill originally reached 225 m at its
highest topographic level. Figure 1.1 below depicts the changes undergone at the mining
site along the years, from residual to bedrock apatite ore.

Figure 1.1: Photographs of the Cajati Mine. Left: Residual Ore as Mined in the 1970's
(Menezes and Martins, 1984). Right: Bedrock Mining in 2002 (photo by the author).

5
The Cajati mine was the only relevant source of phosphate in Brazil before the
1970s, when additional carbonatite-related, weathered apatite deposits were developed.
In 2003 there were four significant phosphate mines in Brazil, and Cajati ranked fourth,
representing approximately 10% of the national production (DNPM, 2003).
Approximately 590,000 t of phosphate concentrate were produced in Cajati in
2003, out of a total rock removal of 5,400,000 t/yr of carbonatite plus 6,600,000 t/yr of
clinopyroxenite (waste). Ore reserve modeling and long term mine planning have
demonstrated that at such production rates, the estimated remaining open pit mine life
was 17 years.
The apatite concentrate is obtained after a process involving grinding, magnetic
separation, size classification, and finally, flotation stages. The concentrate is used to
produce phosphoric acid, which in turn is applied to manufacture animal feed, fertilizers,
and food grade phosphoric acid. Igneous apatite is clean and yields concentrates with
high P2O5 content. However, as fertilizer, phosphate of igneous origin is released to the
soil at slower rate, as compared to that from a sedimentary source.
Apatite occurs as small, elongated crystals resembling grains of rice, generally
arranged in continuous, parallel veinlets forming magmatic foliation. Larger crystals
usually exhibit the prismatic, hexagonal shape, and they formed at an earlier time in the
paragenetic sequence. The average content of apatite is about 12 % in the carbonatites,
which corresponds to 5 % P2O5. The mine cut off grade is 3 % of P2O5.
The average modal concentration of the gangue minerals, in relation to the whole
rock, is approximately: 54% calcite, 20% dolomite, 8% magnetite, 2% olivine, 2%
phlogopite, 1% sulfides, and less than 1% of other minerals.

6
2. PETROLOGIC AND TECTONIC CONTEXT OF THE CARBONATITE

2.1. REGIONAL GEOLOGY AND TECTONIC SETTING

The tectonic setting provides the fundamental platform for petrogenetic studies of
carbonatite complexes. The majority of carbonatite occurrences are located in stable
continental intraplate settings, in some cases in continental margins, and more rarely in
intraplate oceanic basins (Winter, 2001). Carbonatites have been emplaced since the Late
Archean to the present day. However, they show a geological time relationship which is
not very well understood, because the main episodes of carbonatite activity appear to
have occurred only in the Proterozoic to Early Cambrian, during the Cretaceous, and in
the Cenozoic (Bell, 1989).
The Jacupiranga Igneous Complex was intruded in the Early Cretaceous,
approximately 130+/- 4 M.a. ago. The age has been determined through isotopic studies
of the carbonatites (Roden et al., 1985), and other rocks of the complex, confirming the
data primarily obtained by Amaral (1978), with the K-Ar method for phlogopite and
other minerals. This age is corresponds well with that of the Paran (Brazil) and Etendeka
(Namibia) Flood Basalts, marking the fragmentation of the Gondwana supercontinent
with the opening of the Atlantic Ocean.
Alkaline magmatism commonly occurs in areas associated with continental
rifting. A common origin related to a mantle plume has been proposed for the large
tholeiitc basalts floods and alkaline igneous complexes. Basu et al. (1993) concluded that
the occurrence of alkaline igneous complexes within or in the proximity of major
lineaments and grabens is evidence for structural controls and mode of interaction
between a mantle plume head and the continental lithosphere.
Other carbonatitic and non-carbonatitic alkaline complexes in Brazil, with ages
that correlate with that of the JIC, are present in the same region, and are associated with
magmatic arches within the context of the volcanic passive margin, such as the Ponta
Grossa Magmatic Arch, in the case of the JIC (Gomes et al., 1990). The alkaline rock
complexes that occur along the border of the Parana Intracratonic Basin have been
systematically studied, and the work of Gomes et al. (1990) provides a good review. A

7
map showing the localization of these carbonatite complexes and their intercontinental
tectonic context is shown in Figure 2.1.
On a more local scale, two tectonic domains can be recognized in the area of the
JIC, namely the Ribeira Belt and the Coastal Domain (Vasconcelos et al., 1999). These
tectonic units are separated by the Lancinha-Cubatao shear zone, and are illustrated in
Figure 2.2.
According to the geology compiled by Vasconcelos et al. (1999), the Ribeira Belt,
situated north of the shear zone, shows evident NE-SW lineament and comprises a
complex association of metavolcanic-sedimentary rocks of low metamorphic grade (with
estimated metamorphic peak dates around 580 Ma and 530 Ma), intruded by large calcalkaline granite bodies. The Ribeira Belt is analogous to the Damara Belt in southern
Africa, and both structures represent ancient suture zones of Precambrian amalgamation
of microcontinents.
The Coastal Domain, south of the Lancinha-Cubatao shear zone, corresponds to a
set of supracrustal rocks exhibiting variable degrees of metamorphism, and it forms the
Paleoproterozoic basement whose mica-schists and gneisses were later intruded by the
JIC (Vasconcelos et al., 1999).
Other alkaline-ultramafic igneous complexes that are present in the region of
Jacupiranga, such as Juqui, Itapirapu and Mato Preto, occur as discordant intrusions in
rocks of either (or even both) tectonic areas, i.e. Ribeira Belt and Coastal Domain.

Figure 2.1: Tectonic Setting of the Paran Sedimentary Basin, and Related Main Occurrences of Alkaline Complexes With
Carbonatites Along the Margins of the Basin (After Gomes et al., 1990).
8

Figure 2.2: Simplified Regional Geology and Tectonic Domains in the Region of the
Jacupiranga Igneous Complex (After Vasconcelos et al., 1999).

10
2.2. LITHOLOGIES OF THE JACUPIRANGA IGNEOUS COMPLEX (JIC)
The Jacupiranga Igneous Complex is located in southeastern Brazil,
approximately at latitude 24o 42 S and longitude 48o 08 W, close to the border line
separating the states of So Paulo and Paran, and not far from the Atlantic coast. The
area, in the Ribeira River Valley, can be reached by driving 240 km along the highway
BR116, southwest from the city of So Paulo.
The Jacupiranga Igneous Complex is an intrusive body with a described
outcropping area of approximately 65 km2 (Ruberti et al., 2000). It has an elongated
ellipsoidal shape in plan view, with its longest dimension oriented in a NNW direction.
The JIC is largely formed by two ultramafic intrusions: dunites in the north, and
clinopyroxenites (jacupirangite) in the south. Subordinate alkaline rocks and other
lithologies are present in the complex in smaller volumes.
The carbonatites exclusively intrude the clinopyroxenite and outcrop in an area of
approximately 0.7 km2. They largely correspond to a sequence of pipe-like intrusions
with sub-circular cross sections, and related dikes. Numerous rounded, large xenoliths of
the clinopyroxenite (from few centimeters up to about four or five meters) occur in the
carbonatite, especially in the area of contact between the more magnesium-rich
intrusions, in the northern portion of the deposit (Figure 2.3), and in the southern, earlier
intrusions.
Drilling has demonstrated that the carbonatites extend in depth to at least 400m
below the sea level, with a general dip angle of 80 degrees. Structures in the carbonatites
are mainly represented by a fault zone oriented NNW, sets of joints, and fractures.
Magma flow structures, such as magmatic foliation, are also present and are described in
more detail in the section 4.2.2.
Gaspar (1989, 1991) grouped the JIC rocks into three categories: 1) ultramafic, 2)
nepheline-bearing, and 3) plagioclase-bearing. These rocks are summarized in Table 2.1,
and their general distributions within the complex are schematically shown in Figure 2.4,
based on mapping by Gaspar (1989), together with additional information from
Vasconcelos et al. (1999).

11

Figure 2.3: Zone of Jacupirangite Xenoliths in the Northern Portion of the Cajati Mine.

The rocks of the JIC are generally poorly exposed and covered by a thick mantle
of lateritic soil. The current local climatic conditions are favorable for deep weathering of
rocks: humidity usually over 80 %, and subtropical temperatures ranging from 3oC to
39oC throughout the year, with an average of 22oC (Vasconcelos et al., 1999). The area
comprises several hills, usually oblate at the top, and covered by the Atlantic Forest.
Contrasting to the hills there are low lands and river flood terrains, locally forming
swamps. One of these hills, northwest to the mine and called Morro Grande, reflects
the ijolite intrusion, whereas apparently most of the carbonatite body is constrained by
the Morro da Mina hill area.

12

Table 2.1: Rocks Types Occurring in the Jacupiranga Igneous Complex. Mapping and Classification by Gaspar (1989), With
Additional Information From Vasconcelos et al. (1999).

Rock Types
Dunites

Rock Names
Dunite, Wehrlite (Clinopyroxenite Dunites)

Associated Mineralogy
Olivine (Fo90), Spinel (Fe, Cr), Clinopyroxene,
Fe-hydroxides, rare carbonates

Ultramafic

Pyroxenites

Rocks

Mgt-Clinopyroxenites, Phlog-Clinopyroxenites,

Clinopyroxene*, Magnetite, Phlogopite, Perovskite, Kaersutite,

Melteigites (Clinopyroxenite with >10% Neph)

Neph, Apatite, Andesine

Carbonatites Carbonatites (sovite, rauhagite, beforsite)

*mostly diopside, some Ti-Augite

Calcite, Dolomite, Apatite, Magnetite, Phlogopite, Forsterite, Pyrrhotite,

Pyrite, Chalcopyrite, Serpentine, Pyrochlore, Clinohumite, Perovskite

Lamprophyres Lamprophyres

Olivine, Augite, Biotite, Sanidine, Plagioclase, Sphene, Apatite,

Epidote, Sericite, Quartz, Opaques, Hornblende, Serpentine

Nepheline-

Ijolites

Ijolite (30-70% Nepheline), Melilite-Ijolite

and rare Kalsilite and Apatite

Bearing
Rocks

Clinopyroxene, Nepheline, Magnetite, Perovskite, Biotite, Melilite,

Syenites

Syenite, Nepheline Syenite, Quartz Syenite

Orthoclase, Nepheline or Quartz, Clinopyroxene, Biotite, Sphene,

Amphibole, Magnetite, occasionally Melanite, Cancrinite

Gabbros

Gabbro, Amphibole-Gabbro

Clinopyroxene, Amphibole (mostly kaersutite), Labradorite, Biotite,

Magnetite, Sphene, Apatite

Plagioclasebearing

Diorites

Rocks

Monzonites

Diorite

Clinopyroxene, Andesine, Biotite, Magnetite, Apatite, Zircon

Monzonites, Olivine-Monzonite, Quartz-Monzonite Clinopyroxene, Andesine, K-Feldspar, Biotite, Olivine (Fo55-45),

Magnetite, locally Amphibole, Quartz, Apatite, Zircon

Mgt= magnetite, Phlog = phlogopite, and Neph = nepheline.

12

13

Figure 2.4: Schematic Map of the Jacupiranga Igneous Complex (After Gaspar, 1989 and Vasconcelos et al., 1990). Localization and
13

Access to the Area Are Also Shown.

14
3. METHODS

Field mapping, systematic sampling, and analytical microscopy methods

(transmitted and reflected light, cathodoluminescence, and scanning electron microscopy)
were employed to study the apatite mineralization from the Cajati mine. A description of
the work procedure is presented in this section. The analytical methodology was selected
to provide information regarding the relationship between apatite characteristics and the
efficiency in recovery during the ore beneficiation at the processing plant.

3.1. FIELD WORK

Field work at the carbonatite mine site in Cajati, Brazil, was completed in 10
days, and involved both mapping and sampling activities.
The field work conducted for this research included only the carbonatites of the
Jacupiranga Igneous Complex. The writers previous experience in the detailed mapping
(1:500) of the Cajati phosphate mine formed the foundation for planning the field portion
of the research project. The geological interpretation in the detailed map was supported
by a database comprised of over 3500 structural measurements acquired by the company
staff, which included the writer. The main goal in the field was to sample and describe
variations in the apatite mineralization. The key locations targeted were those where the
apatite ores more difficult to process occur (mainly areas C, D and E in Figure 3.1.), as
well as representative samples of the apatite mineralization from each of the five
intrusions.
The illustration presented by Figure 3.1, despite being a very simplified version of
the detailed mapping done in the more recent years, is considerably updated with respect
to the map by Gaspar (1991), which was based on the mine walls as exposed in 1985.
The simplified map of Figure 3.1 was drawn by the author based on the available
information that was released by the company.

15

15

Figure 3.1: Map Showing Areas Selected for Sample Collection in the Carbonatite Mine.

16
Samples were collected from selected locations in 6 distinct areas throughout the
mine (A to F), and from one selected drill hole (SP24). These areas are shown on the
sampling map (Figure 3.1), and correspond, approximately, to the following intrusions
(C1 to C5), as defined by Gaspar (1989): A and B = C1; C = C1, C2; D = C2, C3; E and
F = C4, C5. The drill hole SP24 does not correlate with any of the referred intrusions.
The majority of the selected samples were collected from areas C, D, E and F.
The scope of this project did not include obtaining representative specimens from
all mapped units. Still, the large quantity and volume of collected material had to be preselected and sawed prior to being shipped overseas for thin section preparation. The hand
samples were described, photographed and used to make more than 150 thin sections, 38
of which were chosen for fine polishing and detailed study. The samples were named
according to the area from where they were obtained (A to F). They were collected either
directly from the fragmented rock already available at the toe of the mine wall, or by
locally breaking the mine face with a hydraulic hammer. Most collection points were
topographically surveyed, otherwise they were only approximately located on the map
(Figure 3.1). Table C.1 (Appendix C) lists the samples whose images are shown in this
thesis, indicates their location in the mine, and describes the modal composition of each
respective thin section.

3.2. ANALYTICAL METHODS

The analytical methods utilized in this research were selected according to their
applicability to the objective of the project, and their availability at the Missouri
University of Science and Technology (formerly University of Missouri-Rolla). The
work was based strongly on the interpretation of petrographic (transmitted and reflected
light) and cathodoluminescence (CL) data. Certain thin sections were selected for
quantitative electron microprobe analyses (EPMA) of the constituent minerals. The
respective procedures and analytical conditions are described in this section. Also, due to
its relevance in this study, a description of the CL method is emphasized.

17
3.2.1. Petrography. Petrographic observations were intensively applied to study
the large variety of samples collected from the carbonatite at the Cajati mine. The mineral
assemblage includes carbonates (calcite, magnesian calcite, dolomite, and rarely
strontianite), fluorapatite, magnetite (primary and secondary), ilmenite, olivine
(forsterite), phlogopite, sulfides (pyrrhotite, pyrite, chalcopyrite, valleriite), and minor or
secondary phases (baddeleyite, perovskite, goethite, serpentine, and the pyrochloregroup). Reflected light (brightfield and darkfield), RL, was used complementary to
transmitted light, TL, to provide detailed observations of opaque and translucent
minerals. Mineralogical and textural aspects were carefully described and interpreted for
each sample, and a total of 1254 microphotographs were obtained from petrographic
observations of the thin sections. Images of the most relevant petrographic features were
selected to illustrate the interpretations drawn from their analysis.
Determination of modal compositions (shown in Appendix C, Table C.1), was
entirely based on visual estimation of the amount of minerals in each thin section. All TL
and RL microscopy descriptions were organized in a notebook. The proportions of calcite
and dolomite were distinguished with cathodoluminescence (CL) microscopy. The CL
characteristics were described in a separate form for each sample.
3.2.2. Cathodoluminescence Microscopy. The use of cathodoluminescence
microscopy is extremely advantageous to the study of mineral assemblages such as those
present in the Jacupiranga carbonatite. Calcite, dolomite and apatite, which in most cases
represent more than 70% of the composition of the samples, emit distinct CL radiation
when excited by an electron beam.
The cathodoluminescence phenomenon is characterized by photons with long
wavelength, ranging from UV, through visible light, to IR spectra. Therefore, in most
cases the CL emission of a mineral will display specific visible colors and shades. For
instance, calcite from carbonatites is usually yellow to yellowish orange, but a
composition more towards dolomite will produce a reddish orange color. Dolomite is
generally red or brownish red. Baddeleyite, present in small amounts in the carbonatite of
Jacupiranga, also emits CL radiation. Finally, apatite is one of the minerals most
extensively studied by means of cathodoluminescence (Waychunas, 2002).

18
Apatite constitutes a ubiquitous phase in a large variety of rock types, and its
crystal structure favors this mineral to act as a trace element repository, providing a
geochemical record of geological processes (Toledo and Pereira, 2001). The CL emission
spectrum of a mineral is strongly dependant on the trace element concentrations, resulted
from variations in the environment in which the crystal was formed. Thus, apatite
represents an excellent target for CL studies. The apatite from Jacupiranga exhibits colors
with several variations around blue: light blue, bluish grey, greenish blue, reddish blue,
lilac (such as in Figure 4.5), and also white. Luminescence in apatite is known to be
caused by Mn and REE replacing Ca (Marshall, 1988).
The variations in CL colors allow the distinction of zoning in crystals that may
not be observed by means of optical microscopy or even backscattered electron
microscopy images. However, crystallographic control causes the CL spectrum to vary
according to the orientation of the crystal, and this factor should be analyzed carefully to
avoid misinterpretations, for instance, as an evidence of multiple episodes of
mineralization (Murray and Oreskes, 1997).
Intensity of the observed colors is not very stable over time, and irreversible
fading may occur as an exponential decrease of luminescence intensity. This effect was
noted for calcite, dolomite and apatite from Jacupiranga, especially for the latter. The
intensity of the luminescent color is visibly affected by temperature, especially because
of the heating caused by electron bombardment. According to Murray and Oreskes
(1997), self-activated peaks corresponding to bound defects or oxygen vacancy will result
in increase of number of defects under the exposure to the beam with time.
The equipment used for the current research was a Technosyn CL instrument
mounted on a Nikon microscope, operating with an acceleration voltage from 10 to 15
kV (usually 11 to 12 kV). A minimum energy is necessary to activate the CL for various
minerals. Shorter wavelengths require more energy to excite their emission. Pagel et al.
(2000) note that the maximum of excitation for a given crystal is not always the highest
acceleration voltage. The applied beam current used in this research was the lowest
possible to avoid damaging the sample. However, due to instability of the vacuum, the
applied beam current was actually quite variable, from 76 to 299 A, but usually within
190-225 A.

19
The CL technique described here is referred in technical literature as the cold
cathode, whereas a CL detector coupled to an SEM has been described as hot cathode.
A comparison between both methods is provided in the Table 3.1.

Table 3.1: Comparison Between Cathodoluminescence Methods. Source: Pagel et al.

(2000), and Personal Observations.

Cold Cathode (Technosyn)

PROS

Small price of stage, adaptable to an

Hot Cathode (Oxford PANA-CL)

Good spatial resolution due to low

optical microscope; easy to use due to size of the electron beam; capable of
low vacuum requirement; large field

high magnification; possibility of

of observation; no coating necessary

imaging at a given wavelength; when

to neutralize charge effects.

attached to SEM, allows BSEI and xray mapping; can be coupled to

EPMA.

CONS Offers low spatial resolution; low

Sample coating required; high

magnification; instability due to

vacuum is necessary; images are

variation of the gas pressure;

always black and white (recording in

damaging of the surface from electron false color is possible); method may
bombardment; it requires a CL

be limited by phosphorescent

spectrometer for qualitative activator

phenomena in some materials (e.g.

determinations.

calcite).

An Oxford PANA-CL detector with multiple removable wavelength-band filters

coupled to the SEM-WDS system of the University of Oklahoma was used in one apatite
crystal of the current study. The objective was to characterize the bright, white CL outer
zone of this large crystal. The conditions for SEM-CL imaging of the apatite were 20 kV

20
for acceleration voltage, and 1 nA for beam current. The image was acquired at 79x
magnification (1000 x 1000 m area) into a 1024 x 1024 pixel array. The image area was
swept two times, and each pixel was read 60 times, with 20 microseconds delay to allow
decay of CL emission between pixels. If the material being scanned has a long CL decay
time, i.e. still emits intensity after the beam is removed, thus applying pixel delay keeps
the intensity of the previous pixel from being read by the detector at the current pixel.
Carbonates have a very long decay time (100-200 microseconds), thus use of a CL
detector is not recommended.
There are several applications for CL in geological sciences. The hot cathode
technique, for instance, has seen increasing application in studies of provenance of
sedimentary rocks, based on observations on quartz, feldspar, zircon, apatite and clay
minerals (e.g. Reed and Milliken, 2003; Boggs and Krinsley, 2006). The properties most
commonly studied by CL have been cited by Pagel et al. (2000) as the following:
distribution of trace elements in minerals and zoning patterns, healed microfractured,
brecciated or recrystallized areas of minerals, quantitative separation of mineral phases,
mineral growth and evidence of different mineral generations to recognize paragenetic
evolution, as a complement to other methods by the location of trace elements, and
textural relationships between minerals (e.g. dissolution and recrystallization, grainboundary alteration). All these characteristics were investigated in the present work on
carbonatitic apatite ores from Jacupiranga.
3.2.3. Scanning Electron Microscopy and Electron Probe Micro-Analysis.
Mineral compositions were determined by electron probe micro-analysis (EPMA) at the
University of Oklahoma, using a Cameca SX50 equipped with 5 wavelength-dispersive
spectrometers (WDS). Phase identification was accomplished by backscattered electron
imaging (BSEI), coupled with energy-dispersive (EDS) x-ray analysis. Composition was
determined by WDS, with matrix correction utilizing the PAP algorithm (Pouchou and
Pichoir, 1991).
Apatite was analyzed using two beam conditions, in order to minimize halogen
volatilization and provide acceptable detection limits. According to Stormer et al. (1993),
most of the previously published microprobe data for apatite have not applied this
required correction. Analysis of F, Na, Mg, Al, Si, P, S, Cl, Mn and Fe utilized a 20 kV,

21
10 nA beam with 5 m spot size; counting times on peak were 20 to 30 seconds for all
elements, except S that was counted for 60 seconds. Fluorine and chlorine were counted
first (and concurrently) for 20 seconds. Subsequent to the prior group, Si, K, Sr, Y, Ba,
La, Ce, Nd, Sm, and Gd were analyzed with a 20 kV, 20 nA beam with 5 m spot size;
counting times were either 60 seconds (Si, Sr, Ce, Nd) or 120 seconds (K, Y, Ba, La, Sm,
Gd). Natural crystalline solids were used as the standard materials for all elements except
the REE, for which the REE-bearing glasses of Drake and Weill (1972) were used.
Durango apatite was used both as the primary standard for P, and as a secondary standard
for REE analysis.
All other mineral phases were analyzed using a 20 kV, 20 nA beam with 2 m
spot size. All standard materials were either natural or synthetic crystals. The counting
times on peak for mica and olivine were 30 seconds for all elements analyzed. For the
oxides, all elements were counted for 60 seconds, except Fe (20 s), Ti (40 s), and Mn (30
s). The overlap of Ti K on V K was handled within the analytical software, by
subtracting Ti K counts (as a function of Ti content) from V K prior to the matrix
correction. Ilmenite (V-absent) was used as the standard for correcting V K intensity by
subtraction of the Ti K component. Fe3+ was calculated by stoichiometry as per the
method given in Deer et al. (1992), using a 4 oxygens basis.
Counting times, especially for the more exotic elements, were balanced with
minimum detection limits (MDL) for elements concentrations. High counting results in
low MDL, but increasing counting times (slow scans) will not proportionally improve
MDL. The range of MDL at 3 sigma above mean background was 0.01 to 0.05 wt% for
most elements in all minerals, except VK (0.07%), BaL (0.09%), FK (0.13% in
mica), and NbL (0.07% in oxides).
All EPMA data for the selected set of samples analyzed from the Jacupiranga
carbonatite have been attached in the Appendix D (Tables D.1 to D.6). The list of
standards utilized to obtain the EPMA results presented in this work is provided by Table
D.7 (Appendix D), as well as the measurement ranges obtained for each set of standards.

22
4. RESULTS

The following sections present the results obtained through the methods
previously described for the apatite ore and the gangue minerals, with emphasis upon the
former. The results are simultaneously compared or associated with information from
literature review. This review also provides a variety of background information
concerning carbonatite minerals.

4.1. THE APATITE ORE

Apatite is among the most common non-silicate minerals that occur in nature, and
it can be found in a variety of geochemical environments that will ultimately form
sedimentary, igneous and metamorphic rocks. Apatite can also have biochemical origin,
such as that forming bones and teeth, and therefore it represents an important object of
study in the health sciences (Hughes and Rakovan, 2002).
Apatite has been extracted from the carbonatites of the Jacupiranga Igneous
Complex for several decades. The final apatite concentrate is submitted to the chemical
plant, where it is converted to phosphoric acid via the sulfuric acid process route. Then,
phosphoric acid is used to manufacture fertilizers, but most of the production from the
plant at Cajati has been actually destined to animal feed.
Originally, apatite was mined from high phosphorus grade, weathered product
accumulated on top of the Jacupiranga Igneous Complex carbonatite orebody, and
flotation was not required to obtain the desired concentrate grade. Later, the addition of
this process required emphasis on the surface characteristics and composition of the
apatite ore, in order to optimize or increase its recovery. It should be expected that the
higher the variability of the apatite ores in a deposit, the more difficult it will be to
develop and establish a processing flowsheet that will be flexible enough to
accommodate these variations without noticeable negative effects in the mineral
recovery.
In comparison to the other carbonatite-hosted phosphate ores being mined in
Brazil, the exposed apatite ores from Cajati might, at first, be considered more

23
homogeneous, since they have not been affected by laterization processes. Still, distinct
beneficiation responses are noticed in the daily production. For instance, the apatite from
areas marginal to fault zone, especially those described by the companys staff as
reddish, yields lower flotation recovery. A similar effect also occurs with apatite
associated with silicates from the xenolith-rich zones. The ore in a northwestern area of
the pit may not grind as efficiently because of greater hardness, possibly related to
modification of apatite in association with hydrothermal fluids.
Table 4.1 highlights the major differences observed between the carbonatitehosted types of apatite ores mined around the globe, i.e. primary (bedrock) and secondary
(either residual or supergene) ores, using examples of active phosphate mines that occur
along the margins of the Paran Sedimentary Basin in SE Brazil. In general, a deposit
that predominantly contains primary apatite, which has been the case of Jacupiranga
since the exhaustion of the residual ore, tends to show lower phosphate average grade,
prevalence of prismatic apatite crystals, and a less significant variation of the CaO/P2O5
ratio, since this variation will typically extend beyond the stoichiometric value only if
apatite was significantly affected by post-magmatic fluids.

24
Table 4.1: Comparison Between the Jacupiranga Primary Apatite Ores and the Secondary
Ores From Other Active Carbonatitic Phosphate Mines in Brazil. Sources: Personal
Observations (Jacupiranga), Torres, 1996 (Arax), and Toledo and Pereira, 2001 (Tapira
and Catalo).

CHARACTERISTIC
Origin of apatite

JACUPIRANGA
Primary.

ARAX, TAPIRA, CATALO

Mostly supergene, some residual
and preserved primary.

Crystal habit and

Prismatic, less

Radial, fibrous aggregates,

morphology

heterogeneous morphology.

globular, locally prismatic.

Typical P2O5 content

Usually < 15%. In most

Commonly reaches 30% or higher.

of the deposit

cases, < 10%, but there are

economic deposits with
content as low as 4%.

Chemistry

CaO/P2O5 ratio

Heterogeneous, reflecting

Very heterogeneous, affecting

magmatic and post-

density, solubility and optical

magmatic processes that

properties of several distinct

affected each intrusion.

generations of apatite.

Approximately 1.3

> 1.3, wider variation range

25
4.1.1. Geochemical and Microscopic Aspects of the Apatite. The complex
chemical and physical characteristics of apatite have been studied for many distinct
scientific purposes, including several with commercial applications. For instance, the
flexible apatite structure has applications in synthetic phosphor for industrial and
consumer products, as laser matrix material (Waychunas, 2002), as potential nuclear
waste form (due to its ability to incorporate REE and actinides), and as a host phase for
toxic metals (Ewing and Wang, 2002), among others. In terms of non-commercial
scientific applications, as the composition of a mineral is a result of the environment in
which it has crystallized and grown, and because a wide range of elements can be
accommodated in the apatite structure, its composition can be particularly useful for
fractionation and isotopic analysis, interpretation of growth rate and conditions, etc.
In carbonatites, the study of apatite can provide important petrogenetic
information, based on the distinct chemical and physical characteristics it can show
according to the composition of the evolving carbonatite magma, the effect of
hydrothermal fluids, and redox conditions, for example. (Waychunas, 2002).
Piccoli and Candela (2002) demonstrated, based on data compiled from the
literature in their triangular plots of fluorapatite, cloroapatite and hydroxylapatite for
different groups of igneous rocks, that in general, igneous apatites are fluorapatites. A
few exceptions have been described for carbonatites, such as the hydroxylapatite from
Kaiserstuhl, Germany (Toledo and Pereira, 2001), and igneous carbonato-fluorapatite
from Barra do Itapirapu, Brazil (Lenharo, 1994). Carbonate-fluorapatite is more typical
of sedimentary environments, and biogenic apatite will probably have a carbonatehidroxylapatite composition. Table 4.2, put together by the writer, describes the major
differences expected from igneous and sedimentary phosphate (apatite) ores.
The chemical formula Ca10(PO4)6F2 corresponds to the ideal composition of
fluorapatite, but this type alone can show a broad range of geochemical variations.
According to Deer et al. (1992), the typical fluorapatite structure is represented by a
hexagonal prism, formed by two symmetric planes parallel to (001), with tetrahedrons of
PO4 linked to Ca-O columns, in addition to F atoms connected to three Ca atoms. Ca
occupies two different sites perpendicular to the (001) plane. The site Ca1 has a diameter
of 2, and is coordinated to 9 oxygen atoms. The site Ca2 is larger (3 to 3.5 ), and the

26
cations are coordinated to 7 oxygen. One fluorapatite structural unit will contain four ions
Ca1, six ions Ca2, six P, two F and 24 oxygens.

Table 4.2: Comparison Between Igneous and Sedimentary Apatite Ores.

CHARACTERISTIC

IGNEOUS

SEDIMENTARY

Trace Element Marker

U, Th

Cd

Solubility

Relatively low

Good

Chemical Composition

Typically, fluorapatite. Typically, carbonatofluorapatite (francolite)

Crystal Structure

Hexagonal, tending to

Usually triclinic or

monoclinic

monoclinic

Na2O %

Typically < 0.5

Typically > 0.5

SrO %

Typically > 0.2

Typically < 0.2

Phosphate Content in

High

Lower than igneous

Concentrate
Deposit Aspects

apatite
Bedrock: smaller,

Larger deposits, soft

deeper mines, higher

rocks (lower mining

mining cost if blasting

costs).

is required;
Supergene: shallower
mines, usually shows
more complex
mineralogy.

27
There are many elements that can enter the apatite structure and significantly
affect the hexagonal arrangement, resulting in some cases in a monoclinic
(pseudohexagonal) symmetry. Substitutions reportedly occur at both Ca2+ sites, as well as
at the PO43- and F- anion positions. Among the most common cationic replacements are
Na+, Mg2+, Sr2+, Fe2+, Fe3+, Mn2+, REE3+, REE2+, Ba2+ and Al3+. The phosphate anion
(PO43-) can be replaced by CO32-, SiO44-, SO42-, and others. Substitution of F- by Cland/or OH- is common, although there are other compounds that can also occupy this
position (Toledo and Pereira, 2001).
In most cases, these substitutions occur in trace concentrations. Complete solidsolution is possible, but occurs more rarely. Toledo and Pereira (2001) provide a
comprehensive compilation of chemical variability and several possible substitutions in
apatite described in the literature, with emphasis on those related to carbonatite deposits.
The data provided by the selected set of samples that was submitted to
microprobe (WDS) analysis (results in Table D.1, Appendix D), combined with the
information obtained from the detailed microscopic (optical) study of the entire sample
collection, demonstrated distinctive geochemical trends and textural characteristics
among the Jacupiranga carbonatite intrusions.
Figure 4.1 shows the variations of the percentage of oxides of REE, Na, Sr, and
the ratio CaO/P2O5 for apatite from southern (early) to northern (later) Jacupiranga
carbonatite intrusions, including the extension of the northern bodies, represented by
sample SP24-53.

28

REE2O3 %

NaO %

0.50

0.50

0.45

0.45

0.40

0.40

0.35

0.35

0.30

0.30

0.25

0.25

0.20

0.20

0.15

0.15

0.10

0.10

0.05

0.05
0.00

0.00
0

10
J151A R-30S

20 B-60S
J137C

30 B30N
J179E

40
J106F B70N

50SP24-53 N

60

1
J151A
R-30S

2
J137C
B-60S

from south to north

J179E B30N

J106F B70N

SP24-53 N

from south to north

CaO/P2O5

SrO %
1.10

1.30

1.00

1.29

0.90

1.28

0.80

1.27

0.70

1.26

0.60

1.25

0.50

1.24

0.40

1.23

1.22

0.30
0

10
J151A R-30S

20
J137C B-60S

30
J179E B30N
from south to north

40
J106F B70N

50
SP24-53 N

60

10
J151A R-30S

20
J137C B-60S

30
J179E B30N

40
J106F B70N

50
SP24-53 N

60

from south to north

28

Figure 4.1: Graphs Showing Chemical Composition Variations in Apatite From Five Different Areas in the Jacupiranga Carbonatite.

29
The ratio CaO/P2O5 is particularly useful to distinguish the primary phase from
those affected by interaction with meteoric (weathering) and magmatic (hydrothermal)
fluids, or to track distinctive patterns of substitution within the same deposit that can
correlate with petrogenetic events.
Pure, ideal (stoichiometric) fluorapatite has CaO/P2O5 = 1.318 (McClellan, 1980).
In nature, most primary apatites show values below (but close to), 1.318. As shown by
Figure 4.1, the calculated ratio for fluorapatite from the carbonatites of the JIC ranges
from 1.232 to 1.292 (n = 88). As comparison, Toledo (personal communication, 2002), in
her work about igneous apatite from other Brazilian carbonatite deposits currently being
mined, has found CaO/P2O5 ratios from 1.28 to 1.51, for example, for seven distinct
generations of mineralization from the Catalo I carbonatite. The ores from Catalo I, as
well as those from the carbonatites of Tapira, Arax and Juqui, correspond to the
residual apatite accumulated on top of the carbonatites after prolonged humid weather
exposure. The range of CaO/P2O5 variation of apatite from the carbonatites of the JIC is
significantly narrower than Catalo I due to the fact that the Jacupiranga ore is being
mined from the bedrock, and also has not been significantly affected by post-magmatic
fluids.
Apatite can strongly influence the trace element evolution of a magma, and in
igneous rocks in general, the REE trends are particularly affected. The REE distribution
in apatite can be very useful to determine the mineral provenance (Fleischer and
Altschuler, 1986). High LREE and low yttrium concentrations are typical in mafic and
ultramafic rocks, whereas high HREE and higher levels of yttrium are more typical of
granites, most pegmatites, and also sedimentary rocks.
Apatite that has grown in an alkaline environment has been reported as showing
strong LREE enrichment (Piccoli and Candela, 2002). The most common LREEs in
fluorapatite from carbonatites are especially Ce3+, then Nd3+and La3+. They have been
detected by SEM-WDS in this study, but most medium to heavy REEs are affected by
high bremsstrahlung background produced by the electron flux, not allowing their
detection as they are present in trace concentration levels, below the detection limit.
Therefore, this method alone does not allow the interpretation concerning the complete
REEs partitioning into apatite.

30
It has been suggested, by many authors (Roeder et al., 1987; Hoggarth, 1989;
Hughes et al., 1991; Fleet and Pan, 1995), that a common substitution of Ca2+ in apatite is
associated with REE3+. According to Hughes et al. (1991), this substitution usually is
accompanied by Na+ that results in a charge balance, as given by:
2 Ca2+ REE3+ + Na+

(1)

Thus, the more REE3+ and Na+ enter the apatite structure, the lower the ratio
CaO/P2O5 should be. Figure 4.1 shows that in the carbonatites from Jacupiranga, as the
total LREE content of apatite increases or decreases, it is not necessarily followed by Na,
but there is a slightly better correlation with the CaO/P2O5 ratio, indicating that calcium is
being replaced, but in a more complicated manner than that suggested by the formula
above.
The sodium content in apatite from carbonatites is usually lower than in
sedimentary apatite, typically less than 0.5% Na2O (or 1.35% Na) for the former. In
Jacupiranga, the Na2O content ranges from 0.07 to 0.37% in apatite. Figure 4.1 shows
that most values are lower than 0.25% Na2O, and that there is no clear correlation
between the content variation in apatite and the carbonatite intrusions.
The triangular plot from Figure 4.2 shows the level of replacement of Ca,
considering only LREE and Na. It is small for sample J179-E, whereas it is quite variable
for sample J151-A7, more expressive for sample J106-F, and much more important for
sample SP24-53.
In general, total REE oxides level in apatites from carbonatites can vary from less
than 1%, to more than 8%, in some cases. In Jacupiranga, apatite shows low level of total
REE oxides, ranging only from 0.04 to 0.49%. Early stage carbonatites (i.e., the least
evolved carbonatites in a regional context), are typically somewhat enriched in REE and
have the sum of La2O3 and Ce2O3 in apatites ranging from 0.17 to 1.21%, with the level
of Ce2O3 usually higher than that of La2O3 (Liu and Comodi, 1993). This description fits
Jacupiranga, which has been classified as an early stage carbonatite, and the referred sum
ranges from 0.01 to 0.35%.

31
LREE3+ replaces Ca2+ along the magmatic evolution, but the pattern of REE
increase may not be consistent in carbonatite deposits, mainly due to the complex
combination of magma mixing and local disequilibrium. Other substitutions can
simultaneously occur, due to the ability of apatite to accept many incompatible elements
in its structure. According to Pan and Fleet (2002), the uptake of REEs in apatite is
complex, with incorporation of elements occurring by site preference, determined by
intrinsic (substitution mechanisms, spatial accommodation, equalization of bond
valence), and external (pressure, temperature) factors.
In the areas of samples J179-E, J106-F, and SP24-53, there is a consistent REE
enrichment in apatite, as seen in Figure 4.1, with an increase of the incompatible
elements concentration as the magma differentiated, pointing to a possible association
with fractional crystallization, at least for intrusions C4, C5, and the dolomitic carbonatite
(SP24). However, the level of enrichment of sample SP24 is much higher than those for
the other two samples, probably being a result of a temporal and compositional gap in
relation to the carbonatites C4 and C5.

32

CaO/100

J151A R-30S
J137C B-60S
J179E B30N
J106F B70N
SP24-53

Na2O

LREE

Figure 4.2: Triangular Plot Showing the Level of Substitution of Ca by LREE and Na in
Apatite From Jacupiranga. Samples in the Legend are Arranged From South (Top) to
North (Bottom). All Vertices Represent Oxides.

Apart from REE3+ and Na+, another important cation replacing Ca2+ in the apatite
structure is Sr2+. The presence of this element in apatite from different carbonatites
around the world is very common, and its concentration varies widely.
Strontium can represent an important geochemical marker. For example, Liu and
Comodi (1993), based on analyses of apatite specimens from different geological
environments, found the highest SrO levels in hydrothermal apatite (> 1%), and the
lowest levels in sedimentary apatite (usually < 0.2%).
In a study of apatite from several Brazilian carbonatites, Lenharo (1994) obtained
the following concentrations of SrO % for two occurrences contemporaneous (127 to 131

33
Ma) to the Jacupiranga Igneous Complex, and located in the same region: 0.5 to 1.0% for
Juqui, and 1.4 to 1.5% for Itapirapu. In the same study, she obtained SrO values from
0.4 to 0.6 % for apatite of the carbonatites from Jacupiranga, but the current study has
found a wider content, ranging from 0.40 to 1.02 %. These SrO variations are illustrated
in Figure 4.3.

SrO% in Apatite from Selected Carbonatite Complexes

12.0
11.0
10.0
9.0
8.0

Jacupiranga

7.0

Itapirapua

6.0

Juquia

5.0

Tapira

4.0

Catalao

3.0

Araxa

2.0
1.0
0.0
MIN %

MAX %

Figure 4.3: Comparison Between New Data of SrO Levels in Apatite From Jacupiranga
and From Other Brazilian Carbonatites Along the Margins of the Paran Basin. Sources:
this Thesis Research (for Jacupiranga) and Lenharo (1994).

According to Hoggarth (1989), strontium tends to increase towards the later

phases of the carbonatite intrusions. In fact, for Jacupiranga, SrO > 0.6 % is apparently
exclusive to the youngest intrusions of the northern portion of the deposit: up to 0.90 %

34
in sample J106F, and from 0.86 to 1.02 % in sample SP24-53. The rather elevated degree
of substitution of Ca2+ in the latter, by mechanisms involving Sr2+ and REE3+, becomes
clearly distinctive when strontium is plotted against REE (Figure 4.4). Such
characteristic leads to the proposition of two hypotheses: that sample SP24-53 may
represent an individual carbonatite dike or intrusion, instead of an extension of the
supposedly youngest northern body, or that it is an evidence of strong hydrothermal
overprint that affected part of the latest intrusion (sample J106F).
However, optical microscopy analysis (Table F.1, Appendix F) supports the
hypothesis of an individual intrusion, showing that sample SP24-53 has distinct texture
and mineralogy, with as much as 5 % modal pyrochlore, approximately only 3 % finegrained magnetite (< 0.7 mm), moderately high content (16 %) of fine-grained apatite (<
0.6 mm), and carbonates represented almost exclusively by dolomite (< 2 mm). The
actual size of the body related to sample SP24-53 is not known, and it may be a minable
intrusion, or just a late beforsite (medium to fine grained dolomite carbonatite) dike.
Figure 4.4 shows that REE enrichment, compared to strontium, is much higher for
samples J151-A7, J137-C, and J179-E. For sample J106-F, strontium variability is wider
than REE. Finally, as previously mentioned, enrichment is high for strontium and REEs
in sample SP24-53, which appears to represent the latest carbonatite intrusion within the
Jacupiranga Igneous Complex. When analyzing the variability of only strontium among
samples from the different intrusions, as depicted in Figure 3.1, the resulting graph seems
to show the most regular pattern, with a more pronounced sequential increase in
concentration in the northern intrusions, than that shown by the graph for the REEs.
Other minor elements present in apatite do not seem to be of great relevance for
geochemical analysis of the apatites from Jacupiranga. For example, Al2O3 measured less
than 0.03%, close to the detection limit for the method, and quite below the supposed 2%
maximum admitted in the apatite structure. According to Hoggarth (1989), the typical
content of SO3 in apatites from carbonatites is low, which is in agreement to the
measurements obtained for Jacupiranga, which were below 0.07%. MnO presented very
low levels too, but trace concentrations of manganese can affect CL color in apatite. The
dull grey to white cathodoluminescence in apatite from Jacupiranga was found, by

35
Anthony Mariano (personal communication, 2002), to be activated by a broad Mn2+ peak,
which superimposes peaks of Sm3+, Dy3+ and Tb3+.

0.50

0.45

0.40

0.35

LREE2O3%

0.30

J151A R-30S
J137C B-60S
J179E B30N

0.25

J106F B70N
SP24-53 N

0.20

0.15

0.10

0.05

0.00
0.00

0.20

0.40

0.60

0.80

1.00

1.20

SrO%

Figure 4.4: Diagram Plotting Total LREE Oxides Against Sr Oxide. Note the Higher
Level of Substitution in Apatite for Sample SP24-53.

The main activators for cathodoluminescence in apatite are Mn2+, Sm3+, Dy3+,
Tb3+, Eu3+ and Eu2+(Mariano, 1978). Activation occurs even if the concerned elements
are present in concentrations < 100 ppm. The blue colors of cathodoluminescence in
apatites from carbonatites are often related to the emission from Eu2+ in the 410-430 m

36
range (Mariano and Ring, 1975, and Mariano, 1978). In the apatites from the Jacupiranga
carbonatites, Eu3+ is a dominant activator (Mariano and Ring, 1975, and Roeder et al.,
1987), reflecting the typical anomalous abundance of the cerium subgroup (LREE) in the
carbonatites. In relation to Fe2+, since it is an effective quencher of cathodoluminescence
(Mariano, 1978), its content in the apatite from Jacupiranga must be limited, and indeed
that is indicated by the EPMA data (Appendix D, Table D.1).
In the current study, cathodoluminescence was very important to demonstrate
chemical zoning in apatite crystals (such as in Figure 4.5, and in the Appendix B, Plate
B.1, images b, p, q and r) and their distinct growth stages, as well as to show the
relationship with calcite and dolomite occurring in the different carbonatite intrusions of
the Jacupiranga Igneous Complex , as illustrated in Plate B.1, images a, c, d, and g
(Appendix B).
In relation to growth conditions, in order for apatite to nucleate and grow, the
carbonatite magma must have been originally enriched in phosphate. If the magma is
super saturated, an important condition for nucleation is satisfied, allowing the crystal
nucleus to overcome the high surface free energy barrier, and reach its critical size
(Winter, 2001). The transition to the growth of a stable mineral, and the characteristics of
such growth, will depend on the environment conditions. Chemical elements must be
available and move to the growing crystal surface, followed by surface diffusion, binding
at surface sites of incorporation, and dissociation from complexing ions from solution
(Rakovan, 2002).
The type of growth mechanism will be determined by the free energy of the
surface and edges (steps) of crystal faces, the characteristic and density of defects within
the crystal, and the degree of super saturation of the solution. Most apatite growth occurs
by a layering mechanism, where the addition of growth units results in the development
of crystal faces. Under very high saturation conditions, the crystal formed will likely be
anhedral (Rakovan, 2002).
Layering growth can occur through different mechanisms. A common layering
mechanism is the spiral growth, which occurs when a screw dislocation or other relevant
defect in the crystal intersects a crystal face (Rakovan, 2002). Many dislocations
originate from errors during growth, which can be induced, for example, by the

37
incorporation of foreign ions or particles, or by misfits at impinging growth fronts (Wenk
et al., 1983). The displacement of the structure around the dislocation creates a step on
the crystal face. Because incorporation of atoms and growth units tend to occur
preferably at steps, and at kink sites in the steps, the step spreads laterally, terminating in
the dislocation, resulting in spiral growth. (Rakovan, 2002). Evidence of this mechanism
can sometimes be seen under the microscope as a surface micro-topographic spiral. In the
case of the apatite crystals illustrated by Figure 4.5, development of spiral growth was
suggested by CL microscopy. A possible spiral reflecting the continuous growth of the
euhedral core of a large apatite crystal can be observed through the variation in the CL
colors, within the core zone, from violet to light blue.
Conversely, the presence of impurities has also been suggested to inhibit apatite
growth in certain situations, through the obstruction of the spreading of growth steps,
interfering with active growth sites. The higher level of LREE and particularly Sr in
apatite from sample SP24-53 can then possibly be a significant factor on the small grain
size of apatite. Based on the relatively high amount of this mineral found in the area of
SP24-53, it is reasonable to affirm that the magma was still enriched in phosphate.
According to Rakovan (2002), it has been found that strontium can inhibit rates of
dissolution and growth of hydroxylapatite.
As apatite grains have grown in conditions of non-equilibrium, compositional
zoning has developed. In general, zoned crystals are formed by incomplete chemical
reactions during fractional crystallization. The complicated zoning in some apatite
crystals from Jacupiranga, and their related heterogeneous chemical composition pattern,
is an evidence of the changing environment conditions during growth. The characteristics
of growth can vary for different faces of the same crystal. The partition coefficient for a
given mineral-fluid system can differ for structurally distinct regions of a crystal surface
(Rakovan, 2002). Incorporation of trace elements can be face or step specific.
In Figure 4.5, the CL image displays a more regular zoning, with the typical CL
color variation seen in many grains of apatite from Jacupiranga. Conversely, Plate B.1,
image r (Appendix B) shows a CL image of apatite with complex, heterogeneous zoning
developed in the crystal.

38

Figure 4.5: CL Image Showing Zoned Apatite With Euhedral Cores, Evidence of Spiral
Growth (Lower Right Side), and Concentration of Fluid Inclusions (White Spots).
Apatite Occurs With Calcite (Yellow), Dolomite (Red), and Baddeleyite (Small, Bright
Blue Spot). Sample J128-C. FOV: 1.5 mm.

Figure 4.6 shows an electron microprobe compositional profile along two zoned
apatite grains from sample J179-E. The sequence of spot areas analyzed can be seen in
Figure 4.7. Except for a certain correlation between cerium and sodium for apatite grain 1
(apt1), there seems to be no evident distribution pattern in the profiles. Although zoning
in this sample apparently shows clear distinction between rims and core, the
compositional variability pattern within the grains contributes to demonstrate the
complex uptake of Sr, Ce and Na in apatite.

39

Apatite microprobe profile: sample J179-E

% (oxides)
0.50

0.40

Sr-apt1
Sr-apt2
Na-apt1
Na-apt2
Ce-apt1
Ce-apt2

0.30

0.20

0.10

0.00

distance (m)
0

50

rim

100
core

150

200
rim apt1

250

300
rim apt2

Figure 4.6: Microprobe Profile for Oxides of Ce, Sr and Na Along Two Apatite Grains.
Spacing: 50 m. Sample J179-E.

40

Figure 4.7: CL/SEM Image of Apatite Showing Chemical Zoning and Concentration of
Fluid Inclusions in the Core of the Grain. Round Spots on Top of the Image are Areas
Subjected to Micro-Analysis. Sample J179-E. Compare With Image m From Plate B.1
(Appendix B), Obtained With Transmitted Light Microscopy for the Same Sample.
Magnification: 79x. Area of the Image: 1000 x 1000 m.

41
The compositional zoning in apatite from Jacupiranga is evidenced by changes in
the CL color, from the core to the face of the crystal, such as in the Figure 4.5, and in the
Appendix B, Plate B.1, images b and p, for example. In many cases, these color changes
agree with the following sequence, from core to rim (Alves and Hagni, 2006):
1) pinkish blue/violet core, commonly euhedral with hexagonal shape, indicating that
nucleation and initial growth occurred while much of the melt was still in the liquidus
phase, allowing small euhedral crystals to remain temporarily suspended in the melt. In
the core of coarse apatite grains, it is possible to observe two or more crystals clustered,
forming one grain (Plate B.1, image q, Appendix B).
2) blue CL zone, locally absent.
3) light blue/greenish blue zone, more persistent color, more persistent along
crystallization.
4) blue CL, very similar to zone 2.
5) bright, white CL developed along the borders of a few apatite crystals (Plate B.1,
image r, Appendix B). Most of the crystals with white CL occur in the northern, later
intrusions, especially where they were affected by local hydrothermal fluids, as
evidenced by fracturing caused by dolomite and sulfide veins, and later calcitic
microveins (Plate B.1, image d, Appendix B).
Additionally, some highly fractured apatite grains show no CL (dull). This case is
illustrated by image c in Plate B.1 (Appendix B).
The habit and texture of apatite are also important to understand the development
of the mineralization. The study of the variability of the apatite habit in the Oka
carbonatite, Canada, according to Piccoli and Candela (2002), led to the interpretation
that the carbonatite crystallized from a medium that was at least partially fluid. This
interpretation also applies to the carbonatite of Jacupiranga, with evidence from the
current study of interstitial apatite and the carbonates phases (Plate B.1, image a,
Appendix B) of calcite and apatite crystallizing by accommodation on older crystals,
especially on calcite and magnetite (Plate B.1, images e, h, i, l, and z, Appendix B), and
of rapidly grown apatite embaying calcite (Plate B.1, image v, Appendix B).
Wyllie et al.(1962), performed experiments to study the habit of apatite in a
compositionally simple melt (synthetic system), and noted that small, equigranular apatite

42
grew in a near-equilibrium condition with the presence of a liquid or vapor, whereas
acicular apatite was produced in situations of rapid undercooling (quenching), and also
along conditions of increasing cooling rate. Further studies in natural systems, as
mentioned by Piccoli and Candela (2002), demonstrated that needle-like apatite formed
from surface-controlled growth under high super saturation, whereas small, stubby
crystals formed under lower degrees of super saturation, with growth dominated by
diffusion.
In some cases the small, stubby apatite grains are concentrated in the core of an
igneous body, but its margins show acicular apatite, inferring that the margins were much
faster cooled than the core. In the apatite deposit of Jacupiranga, elongated, centimetric
apatite grains occur in the contact zone of the carbonatite with the host pyroxenite,
especially in the southern end of the carbonatite body, representing the earliest intrusion.
Throughout the Cajati mine, there is a fairly limited size variation range of apatite
grains. Typically, finer crystals dominate in veinlets and disseminated mineralization.
Apatite in clusters tends to be slightly coarser, but the coarsest crystals are those that
comprise the less common massive aggregates (usually in the phoscorite rock area), and
grains in the contact region with the jacupirangite. Table F.1 (Appendix F) provides an
overview of the grain size variation among apatite from the six different areas examined
in the current study.
Another useful feature that contributes to a better understanding of the
petrogenetic history of the Jacupiranga carbonatite and its apatite mineralization is the
study of their fluid inclusions (e.g., Constanzo et al., 2006). However, in this work, the
fluid inclusions are mentioned and described only in as much as they are within the scope
of a microscopy study whose emphasis is in fact on the cathodoluminescence
characteristics of the carbonatite minerals.
In carbonatites, studies of fluid inclusions commonly indicate a wide range of
temperature and compositions, as a result of the many processes involved in their
crystallization (Roedder, 1984). Also, it is noteworthy that data of temperature of
trapping, as well as data of pressure, obtained from fluid inclusions still carry serious
questions concerning the accuracy of such determinations.

43
According to Roedder (1984), the composition of fluid inclusions in carbonatites,
as revealed by different studies, includes various silicates, carbonates and chloride
daughter phases in a water solution, dense CO2, or simple gas-liquid water inclusions.
Inclusions of CO2 are more commonly found in carbonatites, alkaline magmas,
and diamonds. The presence of volatiles indicates that such phases reached saturation at a
certain period of time during the magma evolution. The accurate analysis of the
composition of the volatiles in inclusions is difficult, and quite often produces data with
limited reliability.
Generally, most of the fluid inclusions studied in carbonatites occur in apatite. In
the Jacupiranga carbonatite, the presence of numerous fluid inclusions in apatite is
relatively common and evident, whereas in calcite and dolomite they can be seen more
rarely, are much smaller, and occur in much lower amounts. The same was observed, for
example, by Nesbitt and Kelly (1977) for fluid inclusions in samples from the Magnet
Cove carbonatite, Arkansas. They also described for that deposit that water solution plus
a small bubble made up more than half of the volume of most inclusions. In the apatites
from Jacupiranga, it is possible to notice liquid, gas and solid phases, although solids are
less prevalent. The trapped solid phases from fluid inclusions of some samples of apatite
from Jacupiranga were identified by Constanzo et al. (2006) as sylvite, burbankite,
apatite, pyrite, chalcopyrite, and ilmenite.
Fluid inclusions in the apatite from Jacupiranga constitute additional evidence of
a complex history involving fluids of varied compositions, and it is very difficult to
establish the temporal sequence of these various fluids. The complex chemical
interactions during the growth history of the apatite from Jacupiranga have been revealed
by many characteristics of its internal structure. The observed presence of primary fluid
inclusions, oriented parallel to the apatite c-axis, is common but mostly restricted to the
core (Plate B.1, images m, n and o, Appendix B). These inclusions are generally small
(<10 m), but their width can exceptionally reach as much as 110 m as measured in a
sample from the hydrothermally affected carbonatite area. Fluid inclusions are usually
oblong, but very irregular shapes can also be observed (Plate B.1, images s and u,
Appendix B). Most inclusions carry a liquid (L) and a vapor (V) phase, and quite often L
< V. Solid phases (including an opaque mineral) may be present (Plate B.1, image t,

44
Appendix B). The white spots present in the cores of apatite crystals in CL images, such
as in Figures 4.5, 4.7, and in images d and p from Plate B.1 (Appendix B), are fluid
inclusions.
Observation of the fluid inclusions in the apatite from Jacupiranga also suggests
that an important stage of volatiles release, or possibly boiling (represented by fluid
inclusions with vapor and liquid phases in grain cores) ceased, but apatite continued to
grow under different magma conditions, as evidenced by its chemical zoning.
Any process that interferes with growth of a crystal may cause trapping of
primary fluid inclusions. Many of them form as a result of the non-uniform availability of
ions and chemical compounds in time and space (Roedder, 1984). A common mechanism
for the development of fluid inclusions in apatite from Jacupiranga appears to have been
derived from trapping of inclusions between individual growth layers, such as in the
center (beginning) of growth spirals, for example.
The following characteristics of the fluid inclusions in apatite and carbonates
from Jacupiranga attest to their primary origin, according to the list of criteria defined by
Roedder (1984):
1) inclusions follow the direction of growth and zoning, and are oriented along the c-axis.
2) inclusions are randomly distributed in three-dimensions throughout the crystal.
3) inclusions occur along a twin plane (in calcite).
4) relatively large, flat inclusions occur parallel to an external crystal face, and near its
center.
5) inclusions occur in the core of a tabular crystal.
According to Constanzo et al. (2006), secondary fluid inclusions are also present
in apatite, and were trapped during a hydrothermal event that precipitated a strontium and
REE-rich mineral assemblage, including strontianite, which had also been described by
Raposo (2002) forming inclusions in calcite.

45
4.1.2. Characteristics of the Apatite Mineralization. The styles of apatite
mineralization present in the carbonatites from the Cajati mine are typical of magmatic
phosphate ores, and have been described and listed by this writer (Alves and Hagni,
2004) as the following:
1) veins or veinlets, usually strongly oriented, forming magmatic foliation (for instance,
in the Appendix B, images e, f, h and j from Plate B.1).
2) small pods or patches, either associated with veins, or formed by individual clusters of
short, acicular crystals (for example, in the Appendix B, images b, i, p and x from Plate
B.1).
3) disseminated, discrete grains (less common), as in the Plate B.1, images c and d
(Appendix B).
4) massive aggregates of medium to coarse apatite grains, formed in the phoscorite
(apatite + magnetite + olivine) rock, in the oldest carbonatite intrusion.
Some aspects of the apatite mineralization are illustrated by a few photographs of
drill cores in Plate A.1 (Appendix A), such as the veins and small pods in images a and d,
various veinlets in image b, and coarse apatite crystals in image c.
Bhn et al. (2001), through their study of the systematic of REE distribution
between fluorapatite and carbonatite melt, based on data collected from five African
carbonatite complexes, proposed an episodic phosphate saturation and crystallization
model for fluorapatite, resulting in layers and stringers formed during all stages of the
carbonatite evolution. In this model, the fluorapatite crystallization increments are treated
as individual melt systems, hence taking each residual melt composition as parental melt
for successive fractionation increments. Then, the crystallization of the near-liquidus
phases, fluorapatite and calcite, drives the melt towards a composition that is no longer
saturated in these phases, especially in fluorapatite. At further cooling, the evolved melt
will only precipitate fluorapatite when phosphate saturation is achieved again.
Consequently, the melt behaves as an independent melt system at each step of the
sequential fluorapatite precipitation, and does not follow liquid lines of descent in a
closed system.
In the sequential crystallization mode (Bhn et al., 2001), fluorapatite saturation
occurs with instantaneous precipitation of fluorapatites in layers, pods and stringers (e.g.

46
veins and veinlets). Closed system conditions represent fluorapatite crystallization
following a liquid line of descent, yielding disseminated fluorapatite, which is also
observed in many carbonatites. Based on the field relationships of the mineralization in
the Cajati mine, the model of episodic crystallization appears to show good correlation
with the apatite ore. However, other modes of development of the mineralization must
also have taken place, as indicated by the chemical characteristics of apatite and its
different forms of occurrence. One evidence in Cajati for the crystallization mode
proposed by Bhn et al. (2001), may be the fact that in those areas where the
concentration of apatite through veins or veinlets and small pods is dominant, it appears
that a certain periodicity of apatite-rich magma influx has occurred, represented by
repeated areas or layers with high concentration of apatite, followed by sugary, white,
virtually apatite-free areas of carbonatite.

47
4.2. THE GANGUE MINERALS
The minerals with no economic value, from a mining and processing standpoint,
constitute the gangue assemblage. However, the study of these minerals, in particular
magnetite, phlogopite, and ilmenite, in the case of Jacupiranga, has provided fundamental
information for a better understanding of the petrogenesis of the carbonatite.
The characteristics of these and other gangue minerals from Jacupiranga are
briefly reviewed in the following sections, and supplemented with information obtained
through the current study. The modal abundance of the gangue in each studied thin
section is presented in Table C.1 (Appendix C).
4.2.1. Carbonates: Calcite and Dolomite. Per definition, carbonatites are
igneous rocks with more than 50% modal carbonate minerals, which in most cases are
represented by calcite and/or dolomite, but significant amounts of ankerite and siderite
have also been described. These carbonates originated from melts of the upper mantle.
The carbonate phase relations at high pressures and temperatures are complicated,
and remain not fully understood (Goldsmith, 1983). Melting and decarbonation reactions
add to the complexity in the definition of these relations. Despite such difficulty, one of
the first strong evidence for the magmatic origin of carbonatites, either as a primary
magma or by liquid immiscibility between carbonate-rich and silicate-rich melts, was
demonstrated experimentally by the pioneering work of Wyllie and Tuttle (1960), in the
system CaCO3-H2O, showing that the high melting temperature of calcite is markedly
lowered in the presence of CO2 and H2O volatiles under pressure. Goldsmith (1983)
referred to important carbonate phases investigations in the subsolidus and melting
relations of the CaCO3-MgCO3 join performed by Byrnes and Wyllie (1981) at 10kbar. In
addition, Goldsmith (1983) also revised and modified the pre-determined phase relations
of the CaCO3-MgCO3 join at 27 kbar, and deduced these relations for other pressures. At
27 kbar, a milestone is reached where no decarbonation occurs, and the referred join
becomes binary.
In the carbonatites from Jacupiranga, calcite, magnesian calcite and dolomite
phases show a variety of textures that can be related to those predicted in the
experimental phase diagrams of the CaCO3-MgCO3 join. For instance, dolomite
commonly occurs as small exsolution blebs in calcite (Figures 4.8, 4.9, and Plate B.2,

48
images a and b, Appendix B), or interstitial among earlier calcite grains. Calcite
commonly is interstitial too, forming rounded, anhedral shapes among earlier calcite and
apatite grains (Appendix B, Plate B.2, images e, g, j and l). Grain boundaries may be
interlocking, serrated, sutured, or distinctly angular (Appendix B, Plate B.2, images d, f,
g and i). Calcite twinning is very common (Appendix B, Plate B.2, images a, d, f and l).
Table F.2 (Appendix F) provides a petrographic description of calcite and dolomite for
each studied area.
In the carbonatite intrusions where dolomite is (or tends to be) dominant, i.e. in
the northern area of the deposit, CL color zoning (red core and brown rim) can be
commonly observed in dolomite (Plate B.2, image h, Appendix B). Exsolved brown blebs
and spindles can also be seen in red CL dolomite grains. In calcite, CL zoning is usually
formed by the successive intercalation of yellow and brown colors, and constitutes an
evidence of late recrystallization (Plate B.2, image c, Appendix B).
In relation to the chemical composition, the incorporation of trace elements into
carbonates can occur through the following methods (according to Veizer, 1983):
1) substitution of Ca2+ in the structure,
2) interstitial substitution between planes,
3) substitutions at lattice positions that are vacant due to defects in the structure,
4) adsorption due to remnant ionic changes.
Analysis of REE in carbonates by EPMA was not included in the current study
because this method would not be adequate for the expected low content levels.
In dolomites, small amounts of Fe2+ replacing Mg commonly occur (Deer et al.
1992). Based on the total iron analysis data for dolomite samples from Jacupiranga
(Table D.2, Appendix D), apparently these amounts are very small. The results also show
an interesting increase in total FeO in dolomite toward the later intrusions, with 0.28%
average for sample J179-E, 0.72% for J106-F, and 0.91% for SP24-53. This increasing
trend can be inferred through the triangular plot from Figure 4.10.

49

Figure 4.8: BSE/SEM Image of Calcite (Light Grey) With Dolomite Exsolution (Dark
Grey). Sample J137-C. Magnification: 200x. Area of the Image: 395 x 395 m.

Figure 4.9: Dolomite Exsolution as Observed in TL Image, Un-Crossed Nicols.

Sample J137-C. FOV: 1.0 mm.

50

Figure 4.10: Proportional Content of MgO, SrO and FeO Total in Calcite Versus
Dolomite for a Small Set of Samples From the Jacupiranga Carbonatites.

In addition, dolomite from carbonatites typically contains appreciable strontium

and LREE. Results for SrO in dolomite from Jacupiranga (Table D.2, Appendix D) have
ranged from 0.11 to 0.63%, averaging 0.34%, which is much lower than the 0.81% SrO
average obtained for the calcite set of grains. Figure 4.10 demonstrates the clear
preference of strontium for calcite, in comparison to dolomite, in analyses of samples
from Jacupiranga.

51
The experimental field of stability for dolomite under moderated temperatures and
high CO2 pressures demonstrates small deviation from the ideal 1:1 Ca:Mg ratio, moving
into the direction of excess calcium for conditions of equilibrium with magnesium calcite
at high temperature (Deer et al., 1992). The calculated Ca:Mg ratio from EPMA analysis
of dolomites from Jacupiranga varies from 1.00 to 1.06 (average 1.03), which supports
the above statement.
Well crystallized dolomite has been described to occur in hydrothermal veins,
commonly associated with ores. The thermal dissociation of dolomite, in which the
MgCO3 component breaks down first, has been suggested as a possible source of
hydrothermal solutions rich in Mg and CO2, which under certain conditions can lead to
dolomitization (Deer et al., 1992). In limestones, secondary dolomitization with
magnesian solutions entering through fractures and faults has been described as a very
selective process, usually replacing only the matrix, especially if recrystallization has
taken place (Deer et al., 1992). However, the mechanism of magnesium uptake into the
carbonate structure is not clear. Magnesium partitioning supposedly will prefer pyroxene
(in early assimilations), olivine and phlogopite, over dolomite.
There has been some evidence that dolomitization can only occur with dissolved,
reduced low sulfate concentrations. Chemical conditions conducive to dolomitization
include alkaline environments, temperature above 50oC, and salinity of saturation with
respect to dolomite (Deer et al., 1992). In Jacupiranga, CL microscopy shows that
dolomite, probably secondary, commonly occurs around large magnetite and olivine
crystals, embedded in veins of apatite, and especially following sulfides in veinlets. It
also occurs as a later phase penetrating micro-fractures, evidencing local hydrothermal
activity in the Jacupiranga carbonatites.
There had been some speculation about the hypothesis that the area with high
concentration of dolomite in the northern intrusions, which partially encompasses
intrusions C4 and C5 (Gaspar, 1989), is a result of dolomitization, rather than primary
dolomite crystallized from the carbonatite melt. The dolomitic carbonatite body can
hardly be distinguished in the field from its neighboring calcitic carbonatite, thus it can
be interpreted that although the field relations do not prove that dolomitization has
occurred, they also do not provide clear evidence in favor of a separate intrusion. This is

52
not the case, for example, for the dolomitic carbonatite from the area of SP24, whose
characteristics are clearly distinct from all other carbonatites.
In addition, there is much evidence for local hydrothermalism in thin section, with
sulfide (pyrite) microveins penetrating and fracturing crystals (Appendix B, Plate B.6,
image e), as well as recrystallized magnesian calcite penetrating and fragmenting several
apatite crystals (Appendix B, Plate B.1, image d). The well developed zoning seen in
dolomite is also a common featured observed in secondary grains along veins of apatite.
In summary, all these characteristics offer some extent of support to a metasomatic event
like dolomitization, but this may have occurred only very locally, and the bulk of
dolomitic carbonatite may likely be a result of complex injections of high magnesiumbearing dikes into the crystallizing calcitic carbonatite.
Strontianite, a carbonate which has been mentioned by many investigators to be
present in the Jacupiranga carbonatites, certainly in trace concentrations, is known to
occur most commonly in limestones, although it is also found as a post-magmatic,
secondary phase in alkaline rocks (including kimberlites and carbonatites, possibly being
a primary phase in the latter), and it is typically associated with hydrothermal sulfide
veins. In fact, Constanzo et al. (2006) refer to the presence of strontianite in the
Jacupiranga carbonatites, and a number of other uncommon phases carrying incompatible
elements, as associated with a hydrothermal event that also caused trapping of fluid
inclusions (Appendix B, Plate B.2, image m). Indeed, as indicated above, the current
study demonstrates evidence for hydrothermal activity.
Speer (1983) affirms that most strontianite are solid solutions along the CaCO3SrCO3 join, with Ca substituting for Sr up to about 27 %, but the system requires further
study for a better understanding of the calcium strontianite-calcite relation. In the
SEM/EDS data obtained by Raposo (2002), strontianite, and in particular a Sr-LREE-Ba
rich carbonate, clearly represent late, secondary phases present as small inclusions, filling
cracks, or edging calcite grains found among the flotation rejects from apatite processing
at Cajati.
Overall, strontium is strongly partitioned into calcite, but the presence of apatite
adds an important competitor in the uptake of this element. Carbonate minerals in general
are strongly affected by the presence of dissolved ions. Phosphates, for example, have

53
been found to be an extremely strong inhibitor of carbonate reaction kinetics, even at
very small concentrations (Morse, 1983). The adsorbed ions can actually control the
phase that precipitates by blocking the growth of the sub-critical size nuclei. Dissolved
ions will also influence reaction rates if they are extraneous to the system, then enter it,
and affect the saturation state (Morse, 1983). Thus, the influx of magma saturated in
phosphate may have led not only to the emplacement and crystallization of apatite, but
also it may have slowed or temporarily halted the growth of the carbonates. In summary,
the crystal growth is a result of the balance between adsorption and dissolution, since
both are preferred at high energy sites on crystal surfaces.
The non-equilibrium conditions under which the carbonatites originated favor a
high concentration of structural defects. Different types of lattice defects, such as
dislocations, stacking faults, sequential stacking disorder, twins, and point defects, can
develop in a crystal structure as it grows from a solution. Defects can also be formed as a
result of deformation, and phase transformation (Wenk et al., 1983). All natural crystals
contain defects, which affect their structure at least locally, and consequently their
stability.
In the carbonates from the Jacupiranga carbonatites, twinning can be easily
recognized in thin sections. It is a common structure in carbonates, resulting not only
from growth, but also from deformation. Basically, primary twins are formed by
nucleation error during growth. In the twin boundary, two separated domains are brought
to coincidence by a lattice rotation. In relation to deformation twins, it appears to occur
readily in calcite at low temperatures, up to approximately 500oC. It can cause cracks,
increase the biaxial angle of the grain (only structurally perfect calcite is uniaxial), and
form sub-grain boundaries in certain cases (Wenk et al., 1983).
There are several known twin laws for calcite and dolomite. Although it may be
difficult, in some cases, to distinguish growth twins from deformation twins, as a rule
most of the twin laws apply to the former. In Jacupiranga, deformational twinning was
recognized in thin section in an area of recrystallized calcite (Table F.2, Appendix F).

54
4.2.2. Oxides: Magnetite and Ilmenite. Magnetite is one of the most abundant
and ubiquitous oxides in igneous and metamorphic rocks. It generally occurs as an
accessory mineral, but it may become concentrated by magmatic processes such as
crystal settling and accumulation.
Magnetite is common in carbonatites, and according to Kasputin (1966), it occurs
disseminated in the natrocarbonatite lavas of the Oldonyo Lengai volcano in Tanzania. It
is commonly euhedral to subhedral, but significant amounts of magnetite in carbonatites
may be present as resorbed, anhedral relics in calcite. It may also develop along the
contact rims of individual veins, such as in the Okorusu carbonatites, Namibia.
In the Jacupiranga carbonatites, magnetite is almost as abundant as apatite. Many
crystals may appear to have perfect euhedral shape at a glance (chiefly octahedral), but
under the microscope, most of them are actually partly resorbed.
Petrography of thin sections from Jacupiranga demonstrates that coarse and
medium-grained magnetite, typically euhedral to subhedral, had its crystallization
initiated early in the development of the carbonatite rock, coexisting with the bulk of
liquidus phases. Magnetite continued to grow over an extensive period of time during the
carbonatite crystallization, as evidenced by the textures developed and by its conspicuous
crystal zoning, which were studied in detail by Gaspar and Wyllie (1983a). Still, apatite
growth was even more extensive than that of magnetite, as demonstrated by some grains
that formed earlier (such as inclusions in magnetite core), and many more (in particular
apatite veins) that formed later than magnetite. In the final stages of the magnetite growth
history, many crystals were affected by resorption, as previously mentioned (petrographic
description in Table F.3, Appendix F), resulting in the irregular grain boundaries
(sometimes appearing ragged, fringed) observed in thin section (Plate B.3, images a, b, d
and f, Appendix B), or even in hand samples.
Magmatic flow structures can be seen throughout the Jacupiranga carbonatite
deposit. Flow banding is particularly marked by magnetite phenocrysts segregation.
These segregations may exhibit some crystal size ordering. Magnetite crystals are much
denser than the carbonatite melt, which is a favorable factor for the occurrence of crystal
settling inside the magma chamber, but this factor alone cannot explain all flow structure
characteristics observed in the field. The carbonatite magma chamber was very dynamic,

55
and involved many mechanisms of ascending magma and flow differentiation, including
several episodes of influx of magma with distinct compositions, the development of
nearly vertical magnetite-rich flow bands (near chilled margins), laminar flow forming
mineralized lineations (as seen on the drill core photograph, Plate A.1, image b,
Appendix A), slump structures (also marked by magnetite), and other evidences of local
currents associated with density and/or temperature that can be noticed on hand sample
scale. Nevertheless, the segregation of magnetite phenocrysts is evidence that fractional
crystallization is part of the history of the carbonatite magma evolution.
The movement of apatite-rich magma flow, with associated calcite, led these
minerals to accumulate around (and sometimes mold on) earlier magnetite phenocrysts,
calcite, phlogopite and olivine. As magnetite crystals continued to grow, a poikilitic
texture was developed mainly by the inclusion of apatite, calcite and dolomite, as seen on
images a, b and c from Plate B.3 (Appendix B). Through this relationship, it is possible to
infer that under certain conditions, magnetite growth may have been faster than that of
apatite and carbonates. In fact, in some cases, the resorption appearance of magnetite is
probably a result of its rapid growth enveloping melt, rather than a result of re-melting. A
good example of this situation is given by magnetite embaying calcite in Plate B.3, image
e (Appendix B).
According to Deer et al. (1992), the magnetite general formula is: Fe2+ (Ca, Mn,
Mg, Ni, Co, Zn) Fe3+ (Al, Cr, V) O4. Chromium has been reported to be present only in
trace amounts in magnetite from Jacupiranga, as expected for carbonatites. The content of
zinc is similarly not significant. Calcium content can also be considered marginal, but
manganese, aluminum and vanadium are important minor elements. A detailed analysis
of microprobe data set presented by Gaspar and Wyllie (1983a) demonstrated that 95% of
their results were represented by the magnesioferrite-magnetite series, and confirmed that
the composition of spinel from Jacupiranga is nearly pure magnetite.
Magnetite crystals from Jacupiranga apparently contain more magnesium and less
titanium than those from other carbonatites (Gaspar and Wyllie, 1983a). In the set of
analyses of magnetite for the current study (Table D.3, Appendix D), results obtained for
MgO were as high as 7.42% (sample J179-E), whereas TiO2 was, in most cases, < 1%.
MgO, MnO, and to a lower extent ZnO, correlate very well with the replacement of FeO.

56
The degree of substitution of Fe2+ by Mg and Mn may increase either towards the
core or the rim of magnetite, depending on the sample location. A continuous increase or
decrease of the MgO and MnO contents with the carbonatite intrusion sequence could not
be demonstrated by the current EPMA results (Table D.3, Appendix D). Figure 4.11
illustrates that sample J179-E (northern carbonatite) shows a distinctly higher level of
substitution, more to Mg than Mn. Sample J151-A (earliest carbonatite intrusion) also
shows significant level of replacement, whereas the other three samples represented purer
magnetite composition.

Figure 4.11: Triangular Plot Showing Level of Substitution of Fe by Mg and Mn in

Magnetite From Jacupiranga. Elements are p.f.u.

57
Figure 4.11 also indicates that magnetite from sample SP24-53 (Mag1) can be the
purest of all, with very little MgO and MnO replacing Fe2+O, or Al2O3 and V2O3
replacing Fe3+2O3, as demonstrated by the analytical data (Table D.3, Appendix D).
Another grain of magnetite (Mag2) from sample SP24-53 is not as pure as Mag1, but
except for TiO2 and V2O3, the chemical contents of the impurities were much lower or
similar to those found for magnetite samples analyzed from other areas in the carbonatite.
The chemical characteristics of magnetite grains from sample SP24-53 indicate that the
area SP24 indeed represents a late-emplacement carbonatite that crystallized when the
magma was depleted of most impurities.
Another interesting feature observed in the analysis of the two magnetite crystals
from sample SP24-53 is the striking difference of the titanium content between the
grains, being almost zero for one grain, and showing the highest values found in the
complete set of samples in the other grain. The EPMA data obtained in this study (Table
D.3, Appendix D) shows that the range of titanium content in magnetite is quite variable
among the carbonatite intrusions. This is illustrated by Figure 4.12. Magnetite from the
recently discovered, youngest carbonatite intrusion (area SP24) also shows very distinct
size (fine to medium grained) and content (scarce) in relation to the characteristic
magnetite occurrence from all other carbonatite intrusions in Jacupiranga (description per
area in Table F.3, Appendix F). This carbonatite possibly forms a dike or a small plug,
given the fact that the vertical drill hole was continuously positive for a depth of 180 m.
Secondary magnetite is also present in Jacupiranga, mainly replacing pyrrhotite,
and some pyrite (Plate B.6, image f, Appendix B). Gaspar and Wyllie (1983a), in their
description of the composition of secondary magnetite from Jacupiranga, emphasized that
TiO2 and Al2O3 are extremely low, MgO is very low, and the Fe3O4 content is very high,
therefore being chemically distinct from primary magnetite. Therefore, both primary and
secondary magnetite may have been developed in sample SP24-53, but they could not be
distinguished in the single thin section analyzed.

58

2.2
2.0
1.8

% TiO2

1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0

R-30S

B-60S

B30N

B70N

SP24

Figure 4.12: Variation of % TiO2 in Magnetite From Five Distinct Areas of the
Jacupiranga Carbonatites.

Ilmenite is another oxide mineral present in the Jacupiranga carbonatites. It is a

common accessory in many igneous and metamorphic rocks, and it may be one of the
earlier constituents of the magma to crystallize (Deer et al., 1992). It is ubiquitous in
detrital sediments, in some cases forming economic concentrations in beach sands that
can be mined and processed to yield a TiO2 product.
According to Deer et al. (1992), the majority of ilmenites contain only minor
amounts of MgO and MnO. Exceptionally, major amounts of magnesium are prominent
in ilmenites from kimberlites and related ultrabasic xenoliths, and in lunar basalts and
soils. In relation to manganese, higher than usual concentrations can be found in
carbonatites and some acid rocks. Trace amounts of trivalent ions, such as Al, Cr and V,
if present in ilmenite, appear to substitute for Fe3+. In addition, ilmenite from carbonatites
commonly contains niobium. Fractionation of Nb, Mn and Mg is preferably assimilated

59
by ilmenite instead of magnetite, regardless of the former being primary or the result of
oxidation exsolution.
Indeed, ilmenite from Jacupiranga shows high Mg, Mn and Nb, and this has been
reconfirmed by the EPMA data collected in the current study. The high and variable
MgO content has been described by Mitchell (1978) as an outstanding feature of the
ilmenite from Jacupiranga, whose range (he reported 15 to 24%) is beyond that found in
other carbonatites.
Ilmenite occurs as exsolution laths or small granules (or both) in magnetite of
some of the Jacupiranga carbonatite intrusions. Gaspar and Wyllie (1983b) affirm that the
irregular distribution of MnO between magnetite and ilmenite indicate that these minerals
did not result from simple exsolution, under equilibrium conditions. In relation to the
granular intergrowths, they may be a result of a tendency of ilmenite lamella to coalesce
into irregular or rounded grains, or less often, it may represent enclosed primary ilmenite.
However, very few, discrete grains are not included in magnetite, and they apparently
contain higher Nb than the exsolved laths (Gaspar and Wyllie, 1983b).
Some ilmenite crystals in Jacupiranga do not exhibit the typical strong
anisotropism character under reflected light, in particular when associated with the higher
Nb content. In previous investigations (Gaspar and Wyllie, 1983b; Mitchell, 1978),
ilmenite from Jacupiranga was extensively investigated, and the compositions of
coexisting ilmenite and magnetite were used as a geothermometer, based on the data of
selected samples with lower MgO and MnO content from the banded reaction rock,
formed in the contact between carbonatite and the host jacupirangite. The calculated
temperatures were 570oC and 595oC.
The EPMA data for ilmenite obtained for the current study (Table D.4, Appendix
D) shows that vanadium was strongly partitioned into magnetite, as it was not detected in
ilmenite. Also, the content of Nb2O5 of one ilmenite grain exterior to magnetite was
within the range of the other analyses, included or exsolved in magnetite. However,
additional chemical data would be required to contradict the presumed higher Nb for
grains outside magnetite.
Ilmenite is not present in magnetite from all carbonatite intrusions at Jacupiranga
(description per studied area in Table F.3, Appendix F), and despite its small modal

60
content, it is commonly observed under the microscope. In very general terms, it is
thought that the intergrowth of ilmenite with magnetite develops under slow cooling
conditions, whereas rapid cooling would lead available titanium to enter the magnetite
structure. This may partially explain the variable TiO2 content in magnetite.
Ilmenite inclusions and exsolution laths are conspicuous in magnetite, with its
light to dark brown color contrasting with the whitish grey of magnetite. The exsolution
lamellae of ilmenite develop parallel to octahedral planes of magnetite, forming a
triangular pattern. The petrographic relation between ilmenite and magnetite is illustrated
by Figures 4.13 and 4.14, through reflected light and SEM images, respectively.

61

Figure 4.13: RL Image of Ilmenite Inclusions in Magnetite. No Exsolution Laths of

Ilmenite Were Observed. Sample J103-F. FOV: 0.18 mm.

Dol

Ap

Mgt

Ilm

Figure 4.14: BSE/SEM Image of Magnetite Showing Ilmenite as Small Inclusions and
Exsolution Laths. Inclusions of Dolomite and Apatite Are Also Present. Sample J106-F.
Magnification: 50x. Area of the Image: 1580 x 1580 m.

62
4.2.3. Silicates: Olivine and Phlogopite. Silicates typically comprise less than
20% of the carbonatites composition, represented by mica, pyroxene, olivine, and
amphibole (richterite). At Jacupiranga, the main silicate phases in the carbonatites are
olivine and phlogopite, and together they comprise only about 3% of the entire rock
content.
Olivine is a major constituent of rocks from the mantle. The Mg-Fe olivines form
a complete solid solution series. The melting temperature has a strong effect on the
replacement of Mg by Fe. The oxygen bonds are weaker for ferrous iron, a cation with
the same charge but larger radius than Mg. Thus, as more Fe2+ enters the olivine
structure, more the melting points of intermediate compositions are reduced. The
expected result is that the first olivines to separate from a liquid of a given composition
should be richer in Mg than those of later crystallization, and in consequence the larger
Fe2+ ions are concentrated in the residual liquids. For instance, as described by Deer et al.
(1992), olivine from dunites and peridotites has typical forsterite (Mg2SiO4) composition
varying between Fo96 and Fo87. Ultramafic nodules in basalts and kimberlites show
olivine compositions between Fo91 and Fo86. A variety of volcanic rocks also contain
olivine, both as phenocrysts or in the groundmass. The most magnesium-rich
composition, Fo94-Fo85, occur in the ultrabasic komatiite lavas. Olivines in the
compositional range Fo80-Fo50 are more common in gabbroic rocks.
Calculations of forsterite content in the current study complied with the
recommendation from Gaspar (1989) to apply the following formula:

Fo# = 100*Mg/(Mg+Fe+Mn)

(2)

Results were Fo98.5 in a sample from the northern calcitic carbonatite intrusion,
collected at topographic level 30 m, and Fo95.8 from the largest southern intrusion,
collected at level -60 m. The latter number agrees very well with the results obtained by
Gaspar (1989) through measurements in olivine from equivalent samples (intrusion C1).
However, the number for the northern calcitic carbonatite is higher than that determined
by Gaspar (1989) for the equivalent intrusion C4 (Fo96.3). This may be due to the fact that
the data for sample J179-E in the current study was compromised by the total weight

63
percent of oxides being below a statistically acceptable level, summing up in the range of
96%. Nevertheless, it is possible to affirm that the olivine crystals present in the
Jacupiranga carbonatites have a high forsterite component.
Olivine is not present in all carbonatite intrusions at Jacupiranga, as described in
Table F.4 (Appendix F). The consistently lower forsterite content in the southernmost
(oldest) intrusion emphasizes the compositional difference in relation to olivine from the
other intrusions. This fact can be, at the best, only inferred from the small number of
analysis in the current study, but it has been more thoroughly described, based on a larger
EPMA data set, by Gaspar (1989). The forsterite content does not support the hypothesis
that the proposed five intrusions (C1 to C5) were all emplaced in a time continuum and
represent the successive chemical differentiation of the carbonatite magma. Instead, it
indicates a hiatus between the intrusion of C1 (areas A, B, C) and the others. In addition,
microscopy and field relations associated with olivine are also distinct between the
earliest intrusion C1 and the other carbonatites (areas D, E, F). For instance, in the area C
equivalent to the oldest intrusion (C1), apatite molding on olivine, and calcite in veins
penetrating it, are clear evidence that both minerals formed after olivine.
However, in samples from the other areas, apatite is observed as inclusions in
olivine (for example, Plate B.4, images a and e, Appendix B), as well as carbonates,
magnetite and pyrochlore in large grains from area F, representing a certain overlap
between the crystallization of olivine and the included minerals. Moreover, minute fluid
inclusions were observed in olivine from area E, further distinguishing it from olivine in
intrusion C1. Altogether the evidence points to a temporal emplacement hiatus between
the oldest intrusion and the other carbonatites. The hypothesis of an emplacement hiatus
was originally proposed by Gaspar and Wyllie (1983a) based on his interpretation of
EPMA data for magnetite.
The EPMA data collected for olivine in the current study (Table D.5, Appendix
D) show that the amounts of chromium and nickel are negligible, which is expected since
these compatible elements typically are not present in carbonatites. Ferric iron was not
determined separately from total iron in olivine, but it must comprise a very small
amount, particularly related to an oxidation product formed by alteration, or to small
inclusions of magnetite. In relation to CaO, the data showed that the content in olivine

64
from Jacupiranga is very small too, and although Gaspar and Wyllie (1983a) reported as
much as 0.45%, it is still within the maximum 1% of CaO expected for olivine, regardless
of its origin (Deer et al., 1992).
Some olivine crystals from Jacupiranga, especially those from the southernmost
(older) carbonatite intrusion, show a deep blue, brilliant CL color, which can be seen on
images a and b from Plate B.4 (Appendix B). Similarly, a brilliant blue, as well as red CL
colors were reported by Steele, (1986) in olivine from carbonaceous chondrites with less
than 3% FeO. In theory, only nearly pure magnesian olivine (forsterite) will show CL,
since iron is a quencher for cathodoluminescence in the visual range. The high forsterite
composition is typical of olivine from meteorites, but there are some exceptions in
terrestrial rocks, such as olivine from the Jacupiranga carbonatites, with their forsterite
composition in some cases higher than 96%, as indicated previously.
Olivine is known to be very susceptible to weathering, hydrothermal alteration,
and low grade metamorphism. The products of alteration are varied and overall depend
on physical and chemical conditions. Serpentine, present in the Jacupiranga carbonatite,
is very common. Serpentine is not stable in environments with temperatures above 600oC
(Deer et al., 1992). In the olivines from Jacupiranga, alteration features are evident, in
many cases exhibiting sieve texture. These alteration features can be seen in Figures 4.15
and 4.16, as well as in Plate B.4, images c, d and f (Appendix B).

65

Figure 4.15: Highly Fractured and Partly Altered Olivine Observed Under TL Image
With Crossed Nicols. Sample J137-C. FOV: 2.0 mm.

Calcite with

Apatite

exsolved
dolomite

Olivine

Figure 4.16: BSE/SEM Image Showing Detail of Highly Fractured and Partly Altered
Olivine. Also Note Inclusions of Small Apatite, and Calcite With Exsolved Dolomite.
Sample J137-C. Magnification: 50x. Area of the Image: 1580 x 1580 m.

66
Another mineral that replaces olivine from Jacupiranga is clinohumite. Alteration
of olivine to clinohumite (and phlogopite) has also been reported as a common feature in
the Sokli carbonatites, Finland (Gaspar, 1992). Both clinohumite and serpentine can form
olivine pseudomorphs in the Jacupiranga carbonatites. In some cases, especially in the
oldest intrusion, clinohumite completely replaces olivine, but the former is more
commonly found as reaction rims or patches (Gaspar, 1992).
The replacement of olivine by clinohumite reflects the acceptance of Ti, F and
OH in the olivine structure. Gaspar (1992) calculated Fe-Mg partition coefficients that
demonstrate a loss of Fe and/or a gain of Mg. According to Mitchell (1978), clinohumite
may have been formed by metasomatism and reaction with the fluid rich in CO2, H2O,
CaO, and MgO that later crystallized apatite, carbonates and phlogopite. Clinohumite has
been described as present in environments related to carbonatites, kimberlites, Alpine
peridotites, and Archean ultramafics (as well as in marbles). Although it has been subject
to some studies in detail (Mitchell, 1978; Gaspar, 1992), it is not particularly relevant to
the petrology of the upper mantle.
In any case, the products of alteration of olivine are more dependent on external
factors, such as temperature, pressure and composition of the reaction fluids. The aspects
of the alteration textures (reaction rims, filled fractures) and replacement minerals
indicate that olivine was not in equilibrium with the carbonatite liquid during
crystallization.
Phlogopite is another important silicate present in the carbonatites of Jacupiranga,
and like olivine, occurs in small quantity compared to the whole rock. Phlogopite is
typical of ultrabasic rocks, especially kimberlites, in which it can occur in amounts up to
8%. In carbonatites, phlogopite is very common and by far the most important mica
among those that can be present. In the composition field of natural biotites (Deer et al.,
1992), phlogopite is defined as the Mg-rich end member, but there is no clear
demarcation between phlogopite and other biotites.
The occurrence of different generations of phlogopite in carbonatites is quite
common, and those from the initial stage may form poikilitic crystals, enclosing calcite.
The phlogopite from Jacupiranga can display inclusions of different minerals, depending
on the composition of each carbonatite intrusion, but calcite and apatite are the most

67
common (Plate B.5, images d and e, Appendix B). However, phlogopite rarely forms
poikilitic texture. Petrographic description of phlogopite from different areas is provided
by Table F.4 (Appendix F).
Phlogopite crystals display variable aspects of metasomatic alteration, and in few
cases, they actually have been formed as a result of the alteration of olivine (Plate B.4,
image d, Appendix B). Alteration affects phlogopite preferentially along its rim (Plate
B.5, image c, Appendix B) and cleavage planes (Plate B.5, images a and b, Appendix B).
Some grains may also show undulose extinction and/or evident deformation (Plate B.5,
images a and b, Appendix B). As previously mentioned, a variety of minerals can form
inclusions in phlogopite, and in one identified case of pyrochlore, it caused a pleochroic
halo (Plate B.7, image a, Appendix B). The phlogopite present in samples from the
youngest, dolomitic carbonatite intrusion (collected from borehole SP24), can be
distinguished from the other intrusions, such as seen in Plate A.1, image a (Appendix A),
by its consistently fine grain size. Still, chemical zoning could be observed.
The tetrahedral cations in phlogopite are Si4+ and Al3+, but the latter is commonly
partially replaced by Fe3+, which is relevant in alkaline rocks and carbonatites. Another
possible substitute cation in this position is Ti4+. In the octahedral site, Mg2+, Al3+, Fe2+
and Fe3+ are the most common, but Ti4+, Mn2+ and others can be present. The substitution
of Fe2+ by Mg2+, common in igneous silicate rocks, defines the phlogopite-annite series,
and Fe2+ usually increases with magma evolution (Deer et al., 1992). However, in
carbonatites, the Fe/Mg ratio in phlogopites probably is influenced by the co-precipitation
of magnetite, as discussed by McCormick and LeBas (1996). Finally, the interlayer site is
typically occupied by K+ and Na+, but Ca2+ and Ba2+ can also occur. The latter is found to
be commonly enriched in phlogopites from carbonatites and alkaline rocks (Brod et al.,
2001).
The phlogopite present in the carbonatites from Jacupiranga exhibits complex
zoning, as illustrated by Figures 4.17 and 4.18, which can be readily observed under
transmitted light microscopy (for example, in Plate B.5, images c and f, Appendix B).
However, zoning did not develop in some crystals. The most remarkable variations in the
compositional zoning is determined by the relative contents of Ba and Na in the interlayer
sites, and the Fe and Mg in octahedral sites (Figures 4.17 and 4.18).

68

Figure 4.17: BSE/SEM Image of Complex Zoning Developed in Subhedral Phlogopite.

Sample J179-E. Magnification: 175x. Area of the Image: 451 x 451 m.

69

Figure 4.18: BSE/SEM Image of Another Zoned Phlogopite Crystal, Cut in a Different
Orientation. The Darker Zone Has Very Low K and Very High Mg Contents, Whereas
the Lighter Zone Has a Higher Ba Content. Sample J179-E. Magnification: 200x.
Area of the Image: 395 x 395 m.

70
The range of BaO content in phlogopite from the Jacupiranga carbonatites was
found by Gaspar and Wyllie (1982) to vary from 0.1 to 10.3%, which is higher than the
reported values for the majority of other carbonatites, as well as kimberlites and
peridotites, except for some alkaline (leucite-bearing) lavas. The data for BaO obtained in
the current study (Table D.6, Appendix D) fall within this range. The increase of BaO
towards the rim of phlogopite is more commonly observed, but crystals can also show a
decreasing trend towards the rim. According to Gaspar and Wyllie (1982), as Ba2+
replaces K+, the balance of charge is accomplished by Al3+ replacing Si4+in the
tetrahedral site.
Data from Gaspar and Wyllie (1987) also shows that the values of FeO/ (FeO +
MgO) vary within a narrow range, from 0.06 to 0.12, in phlogopite from the carbonatites
of Jacupiranga. Such variation persists in core and rims of the mineral, characterizing it
with a composition closer to common biotite. The variation of FeO/ (FeO + MgO) is
mostly due to Fe3+ replacing Al3+ in the tetrahedral positions, even though the content of
Fe3+ is not very significant.
The iron content of micas depends markedly on the composition of the
carbonatites and mixed rocks, and is usually higher in the associated alkaline rocks. Some
phlogopites from zones of brecciation and intense metasomatism can be more iron rich.
Reddish brown, iron-rich phlogopite can be found in early carbonatites and phoscorites.
The phlogopites from Jacupiranga in most cases contain less than 3% FeO (total iron).
Brod et al. (2001) summarized the composition of the phlogopites from the
Jacupiranga carbonatites as characterized by very low Fe/(Fe+Mg) ratio (0.065 to 1.2),
very low TiO2 (< 0.44%), high MgO (22.5 to 28.2%), and broadly variable, locally very
high BaO (0.1 to 10.3%). In addition, they reported the presence of Na2O up to 2.77%,
and described that Al is in excess of that necessary to fill the tetrahedral site in
conjunction with Si. The excess of Al3+ represents a distinguishing aspect of the micas
from Jacupiranga in relation to the primary micas from many carbonatites, which in
general tend to be poorer in Al. It is the excess of Al3+ that determines the unusually high
content of Ba2+, rather than late stage enrichment by fractional crystallization. The
availability of Al is a dominant factor controlling the formation of micas, and in the case

71
of Jacupiranga, it may be the result of an elevated Al content in the primitive carbonatite
magma.
Brod et al. (2001) note that the MgO content of mica from the Jacupiranga
carbonatites increases with decreasing age of the intrusions, contrary to the trend
described for the associated silicate rocks that comprise the alkaline complex.
Conversely, BaO was reported to decrease progressively in direction to the most recent
intrusions, thus disagreeing with a fractional crystallization hypothesis. However, the
oldest carbonatite intrusion (C1) does not follow the trends presented above for BaO and
MgO (Gaspar and Wyllie, 1982). In addition, mica from this intrusion exhibits contents
of TiO2 higher than the range for the other intrusions (< 0.12%). Thus, phlogopite
provides additional support for the hypothesis defended by Gaspar (1989) that the more
recent intrusions, C2 to C5, did not originate from progressive differentiation of the same
magma that formed C1.
Despite the fact that the composition of micas in carbonatites varies widely, Brod
et al. (2001) cite that in the case of Jacupiranga, the observed trend (along time of
emplacement for intrusions C2 to C5) of rapid decrease of Al with simultaneous increase
in Mg, and approximately constant Fe content, has been interpreted as a product of
differentiation, either in the parent carbonatite magma, or in an evolving silicate magma
from which successive batches of carbonatite derived. Nevertheless, they demonstrated
that the mica composition and evolution in carbonatites strongly reflect the geochemical
affinity with the magma from which these rocks originated.

72
4.2.4. Sulfides: Pyrrhotite, Pyrite, Chalcopyrite, Valleriite. In the carbonatites
from Jacupiranga, a variety of sulfides occurs in small quantities. Pyrrhotite is the main
sulfide mineral present, and it rarely exceeds 2 % of the whole rock content. Pyrite is the
second sulfide in abundance, mainly formed by the replacement of pyrrhotite, in a
manner similar to chalcopyrite and secondary magnetite. Valleriite is also present and
corresponds to a later replacement phase, possibly developed through some affinity with
chalcopyrite and carbonate microveins that percolated through magnetite. Pyrrhotite may
also exhibit goethite, an oxide, as an alteration product, but this occurrence is not very
common (microscopy description is provided in Table F.5, in the Appendix F).
The sulfides in the Jacupiranga carbonatites, in many cases, are not associated
with primary magnetite. Although most pyrrhotite appears to have been crystallized from
the primary magma, some can be related to later hydrothermal events that affected
portions of the carbonatite intrusions, as explained later in this section.
The mineral pyrrhotite can be defined as a ferrous sulfide that typically shows a
deficiency in iron below that required by its formula. According to Deer et al. (1992), the
non-stoichiometric composition of pyrrhotite is a consequence of missing iron atoms,
rather than replacement of some iron atoms by sulfur, and this is evidenced by the
decreasing character in crystal unit cell dimensions as the Fe/S ratio decreases, and by
specific gravity measurements. The Fe/S ratio of pyrrhotite can be estimated through Xray diffraction.
In temperatures above around 400oC in the Fe-S system (Deer et al., 1992),
pyrrhotite in equilibrium with pyrite shows increasing iron deficiency with increasing
temperature, but the pyrite composition remains constant. The phase relations at lower
temperatures are highly complex due to the many hexagonal and monoclinic structural
variants of pyrrhotite. At 742oC, pyrite will melt incongruently to pyrrhotite and liquid
sulfur.
Pyrrhotite has a relatively short stability range, favoring many replacements.
Pyrite or marcasite replacement of pyrrhotite can lead to colloform and birds-eye
textures. In the carbonatites from Jacupiranga, a few examples of colloform texture could
be observed under the reflected light microscope (Figure 4.19), formed on partially
altered pyrrhotite and developed in situ (i.e., not associated with veins). A fairly common

73
mineral assemblage replacing pyrrhotite involves pyrite, some chalcopyrite followed or
not by a later valleriite phase, and locally secondary magnetite (Figure 4.20). Pyrite,
chalcopyrite and magnetite may form complete pseudomorphous after pyrrhotite.
However, the most typical type of replacement of pyrrhotite at Jacupiranga is that
determined mainly by pyrite only (Figure 4.21).
Figure 4.20, if compared to Figure 4.21, implies that the environment conditions
changed over time (copper not always available, for example), resulting in the
crystallization of different mineral assemblages formed from the alteration of pyrrhotite.
Despite pyrrhotite being more commonly associated with basic igneous rocks, it
can also be significantly present in other environments, such as in hydrothermal, high
temperature veins. According to Deer et al. (1992), the prismatic, pyramidal variety of
magmatic pyrrhotite usually shows an affinity to the high temperature minerals (> 320oC)
of hydrothermal sulfide deposits, and the flattened ones to the low temperature minerals.
In general, twinning in pyrrhotite, which resulted from structural transformations,
is not uncommon, but it may be difficult to recognize with the reflected light microscope.
Intergrowth between different pyrrhotite phases can develop, either lamellar or with
irregular grains shape, and are attributed to exsolution. Pyrrhotite lamellar twinning was
observed under the reflected light microscope in one sample from the Jacupiranga
carbonatites (Plate B.6, image c, Appendix B), indicating there was a transition from the
hexagonal, high disorder structure to the lower temperature, simpler monoclinic structure.
Few euhedral, hexagonal and tabular shaped crystals, probably associated with the high
temperature structure, were also observed in samples of carbonatites from Jacupiranga
(Plate B.6, image a, Appendix B), as well as evidence of crystals with hexagonal
pyrrhotite cores (high temperature), and irregular, later rims (possibly lower
temperature).

74

Py
Po
Val

Cp
Mt

Figure 4.19: RL Image of Pyrrhotite

Figure 4.20: RL Image of Pyrrhotite (Po)

Being Replaced by Colloform Pyrite and

Being Replaced by Pyrite (Py),

Minor Magnetite. Sample J216-D2.

Chalcopyrite (Cp), Minor Magnetite

FOV: 0.76 mm.

(Mt), and Valleriite (Val).

Sample J103-F. FOV: 1.0 mm.

Py

Po

Figure 4.21: BSE/SEM Image of Pyrrhotite (Po) Being Replaced by Pyrite (Py).
Sample J137-C. Magnification: 50x. Area of the Image: 1580 x 1580 m.

75
Pyrrhotite can occur alone, but it is more commonly found with other sulfides. At
Jacupiranga, in most cases the other sulfides are small amounts of secondary pyrite and
some chalcopyrite. In general, pyrrhotite forms granular aggregates or compact masses,
but in the Jacupiranga carbonatites, small aggregates and thin veins are predominant.
Some of the studied pyrrhotite grains from Jacupiranga display inclusions of
apatite and carbonates, but in other cases pyrrhotite occurs interstitial to carbonate grains,
molds on apatite crystal, fills fractures in apatite, or forms microveins that penetrate the
calcite cleavage and magnetite grains. These relationships indicate that pyrrhotite may
have crystallized both from the primary magma and also from remobilization by
metasomatism or a late stage hydrothermal event. For instance, in samples from area C
(Figure 3.1), primary pyrrhotite contains inclusions of calcite and apatite, whereas later,
microveins of pyrrhotite, accompanied by other sulfides, also penetrate these minerals. In
area F, pyrrhotite and especially pyrite, are clearly hydrothermal.
The characteristics of pyrrhotite, observed with reflected light microscope, are
cream color with a faint pinkish brown tint, moderately high reflectance, distinct
bireflectance, creamy brown to reddish brown pleochroism, and very strong anisotropy.
In contrast, pyrite has light yellow color, and shows no bireflectance (Uytenbogaardt and
Burke, 1971).
Pyrite is the most abundant of the sulfide minerals, and its occurrences are very
widespread, especially due to its ability to form under many different geological
environments. Pyrite may form large masses or veins of hydrothermal origin, both as
primary or as secondary mineral, in igneous and sedimentary rocks. In ultramafic and
mafic rocks, although pyrite is generally common, pyrrhotite is typically more abundant
(Deer et al., 1992).
In nature, pyrite crystals can display many different habits, but at Jacupiranga,
they are commonly anhedral and fine grained, forming small clusters, thin veins (Plate
B.6, image e, Appendix B) and, in some cases, colloform zones in pyrrhotite (Figure
4.19).
At Jacupiranga, pyrite occurs most commonly replacing pyrrhotite, but in area F
(Figure 3.1), it is also present as a hydrothermally developed phase that crystallized
around carbonates grain boundaries, and filled microfractures in primary magnetite and

76
apatite. In few cases in the same area, well developed pyrite grains are locally replaced
by secondary magnetite, as illustrated by Plate B.6, image f (Appendix B).
Constanzo et al. (2006) referred to pyrite and chalcopyrite among the solid phases
identified as trapped in primary fluid inclusions in apatite from the Jacupiranga
carbonatites.
Chalcopyrite is the most widely occurring copper-bearing mineral, thus
representing an important ore mineral. In copper deposits, chalcopyrite forms massive
aggregates, which locally are botryoidal or reniform. In rare cases, the content of sulfides
in carbonatites can form economic deposits, such as at the Phalaborwa copper mine, in
South Africa. At Jacupiranga, copper was present in the carbonatite magma, as evidenced
by the crystallization of chalcopyrite and valleriite, but the content was very small.
Phase relations in the system Cu-Fe-S are complex, and involve a wide range of
Cu-Fe solid solutions (Deer et al., 1992). Chalcopyrite breaks down between 547 and
557oC, depending on chemical composition. The breakdown is incongruent, resulting in a
cubic phase with slightly higher copper content, and a small amount of pyrite. At
temperatures not far below 550oC, it exists in a range of intermediate solid solutions near
the chalcopyrite ideal composition. Upon cooling, these solid solutions break down and
form phases with various intergrowth textures. The conditions for the crystallization and
stability of such phases are not well understood. In nature, chalcopyrite develops
intergrowths with magnetite, pyrrhotite, pyrite, marcasite, and valleriite. Chalcopyrite has
an ordered structure, and its composition typically does not deviate much from the ideal
formula, CuFe3+S2, but minor and trace amounts of several elements may be present,
especially in the form of mineral impurities.
In the Jacupiranga carbonatites, chalcopyrite is mostly a secondary phase
replacing pyrrhotite, and it is commonly accompanied by some secondary magnetite and
pyrite. Chalcopyrite at Jacupiranga occurs, in most cases, as very small granular masses
along portions of the perimeter of pyrrhotite grains (Figure 4.20). Exceptionally, in area F
(Figure 3.1), chalcopyrite associated with hydrothermal activity apparently is not related
to pyrrhotite (Plate B.6, image d, Appendix B). Chalcopyrite is weakly anisotropic and
shows a distinctly pronounced yellow color under the reflected light microscope.

77
According to Deer et al. (1992), on exposure to air and water, or with slight
heating, chalcopyrite oxidizes to sulfates of iron and copper. In nature, these are generally
altered further to carbonates, hydroxides, and oxides. In the Jacupiranga carbonatites, the
main secondary mineral resulting from chalcopyrite alteration is valleriite, whose general
formula is [(Fe2+, Cu)4 S4] [(Mg, Al)3 (OH)6]. The alteration is most probably related to
metasomatism.
Valleriite is a low temperature (< 500oC) alteration product of chalcopyrite and
secondary magnetite in dunites and pyroxenites. It may be present in sulfide-rich
ultramafic rocks, especially those that underwent carbonate metasomatism
(Uytenbogaardt and Burke, 1971). It was also found associated with high temperature
hydrothermal activity, such as in tin ores in the Transvaal (South Africa), and in the
Broken Hill Pb-Zn deposit (Australia). In the carbonatite from Phalaborwa, valleriite
replaces magnetite.
Valleriite may form inclusions and exsolution in chalcopyrite and pyrrhotite,
showing varying shapes (Uytenbogaardt and Burke, 1971), but in the Jacupiranga
carbonatites, it forms close to the grain boundaries of pyrrhotite, chalcopyrite, and
magnetite, especially in the contact region of these crystals with calcite, as seen in Figure
4.20, and in Plate B.6, image b (Appendix B). Valleriite developed later than the
associated minerals. The presence of apatite, phlogopite and valleriite indicates a volatilerich environment during carbonatite crystallization.
4.2.5. Other Minerals. Several trace minerals have been described, some for the
first time, in Jacupiranga. The majority are rare and have no significant relevance to
applied mineralogy, or even to petrology studies. The most prominent trace minerals at
Jacupiranga are perovskite, pyrochlore, and baddeleyite, which have been introduced in
the microscopy description in Table F.6 (Appendix F), and they are briefly presented in
the paragraphs below.
Perovskite is an accessory mineral that can be present in many basic and alkaline
rocks, including nepheline syenites, kimberlites and carbonatites. It has a simple, but very
densely packed structure, and it is known to be the main stable phase in the lower mantle,
thus being of interest in the study of high pressure environments (Deer et al., 1992).

78
Perovskite is scarcely present in the carbonatites from Jacupiranga, with a general
content well below 1%. It exhibits very high relief, and occurs as small, discrete,
subhedral grains in the groundmass, locally attached to magnetite, and showing
intergrowth twins. Perovskite may also occur associated with sulfides in the carbonatite
intrusions. Its chemical formula is CaTiO3. Ca2+ may be replaced by Na, REE, Sr and
Fe2+, whereas Nb, Ta and Fe3+ usually substitute for Ti4+.
Pyrochlore has been reported from many localities associated with carbonatites
and alkaline complexes, such as lno (Sweden), Kaiserstuhl (Germany), Oka (Canada),
Kola (Russia), and Panda Hill (Tanzania). It may be scarce at Jacupiranga, but it seems to
be more prevalent in the later carbonatite intrusions, such as in areas E and F, and
particularly in the dolomitic carbonatite of area SP24 (Figure 3.1), where it may comprise
almost as much as 5% of the whole rock. Considering the pyrochlore basic formula, (Ca,
Na)2Nb2O6(OH,F), it is clear that its crystallization is associated with the presence of
volatiles, and its relatively enriched amount in area SP24 further distinguishes this
dolomitic carbonatite from the other intrusions.
The pyrochlore from the Jacupiranga carbonatite forms mostly small, subhedral
(octahedral) crystals in the groundmass (Plate B.7, image b, Appendix B). Its radioactive
character is evidenced by the development of a pleochroic halo around a metamict grain
included in phlogopite (Plate B.7, image a, Appendix B). The pyrochlore rim tends to be
colorless in thin section, and the core is always dark to reddish brown. Some pyrochlore
crystals from sample SP24-53 display resorption features. Chemical zoning is ubiquitous
(Figure 4.22), and marked mainly by the substitution of Nb (decreasing towards the rim)
by Th and Ti (both increasing towards rim), as indicated by the standardless quantitative
analyses shown by Figures E.1 and E.2 (Appendix E). It is important to note that the
quantitative data shown in these pictures is merely indicative, as there were not enough
countings on peak for most elements (such as Na, Ti, Th), thus compromising the
accuracy of the data.
Baddeleyite (ZrO2) has been described to be present in carbonatites, phoscorites
(apatite-magnetite-forsterite rocks), kimberlites, syenites, diabases, gabbros, anorthosites,
lunar basalts and meteorites. In carbonatites, it is well known for its occurrence at
Phalaborwa, South Africa.

79
In Jacupiranga, baddeleyite is easily identified by its ubiquitous cross intergrowth
twinning (images c, d and e from Plate B.7, Appendix B, and Figure 4.23), as well as
parallel striae in some crystals, which define polysynthetic twinning. Baddeleyite is
present in very small amounts in the carbonatites, and it is apparently more common in
the oldest intrusions, encompassing part of areas C and D (probably also including areas
A and B), and to some extent in area E. In most cases, baddeleyite from Jacupiranga is
associated with or in contact with magnetite crystals, especially in areas of magmatic
lenses containing many large magnetite grains (Plate B.7, image e, Appendix B).
However, baddeleyite occurrence also is related to high concentrations of apatite, and the
presence of phlogopite, in some cases forming inclusions in the latter (Plate B.7, image d,
Appendix B). In the paragenetic sequence, most baddeleyite crystallized before apatite
and phlogopite.
A distinguishing characteristic of baddeleyite is the greenish blue CL color it
emits upon excitation by the electron beam. The CL was evident even in small grains in
samples from Jacupiranga (Plate B.7, image f, Appendix B), and its color is rather similar
to that exhibited by CL of olivine.

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Figure 4.22: BSE/SEM Image of Zoning in Pyrochlore. Grain Core Has Higher Nb and
Lower Th and Ti Than its Rim. Sample SP24-53. Magnification: 350x.
Area of the Image: 226 x 226 m.

Figure 4.23: BSE/SEM Image Showing Close-Up of Twinned Baddeleyite in Contact

With Magnetite. Sample J179-E. Magnification: 450x. Area of the Image: 176 x 176 m.

81
5. DISCUSSIONS

5.1. APATITE PROCESSING IN CAJATI

In order to better correlate the apatite characteristics described in this study with
beneficiation results, it is necessary to briefly review the process flowsheet.
Cajati has been planned to be an open pit mine until its exhaustion, but this is
periodically re-evaluated as cost conditions change, and geological knowledge of the
deposit advances. At the present time, Cajati is an open pit whose carbonatite (ore) and
jacupirangite (waste) are mined in blocks and benches extracted by employing
explosives. The fragmented rock is hauled to the crushing station, where its size is
reduced to below 1.75 inches, which is then distributed on to a long, homogenized pile
using a stacker. This size and phosphate grade classified pile feeds the beneficiation
plant.
At the beneficiation plant, the first process step is bar milling to further
comminute the ore and allow apatite separation from the gangue, and to increase the
surface area of the particles, a feature that is very important in the flotation step. The bar
mills operate in closed circuit with cyclones, so particles larger than 0.5 mm return to the
mill. This creates a re-circulating load representing about 10 to 20% of the total wet
weight inside the mill.
Next, the ore undergoes removal of magnetite using wet magnetic drums. The
magnet reject contains mostly magnetite with ilmenite, as expected, but also contains
some apatite that forms inclusions in the magnetite. Those apatite inclusions, as
illustrated in this thesis, are very difficult to liberate. However, the amount of nonrecovered apatite in the magnet reject is typically very small.
After magnetic separation, another set of cyclones is used to deslime (i.e., remove
the fines from the ore slip). Although these fines still contain apatite, they are detrimental
to the mechanical flotation cells, so they are scavenged in air flotation columns.
The next process step is flotation, to separate apatite from the remaining gangue.
Flotation is a technique that relies upon differences in the surface properties of different
particles for their separation. Valuable particles, in this case the apatite, are separated
from the gangue by collection of the former on the surface of bubbles. The addition of

82
appropriate chemicals (surfactants and wetting agents) modifies the surface charges of
the mineral to be floated, rendering it hydrophobic (i.e., eliminating its affinity with
water). Air is then bubbled through the pre-conditioned mixture of minerals, water, and
chemicals. The result is that the hydrophobic grains escape the water by attaching to the
air bubbles, rising to the surface. The accumulated foam forms a froth containing
concentrated apatite, which is then collected. At Cajati, scavenging and cleaning flotation
steps are used to increase final apatite recovery. The flotation reject typically contains
less than 1.5% of P2O5, but the company would prefer that this content be consistently
below 1%. In order to determine how to further increase recovery, it is required to know
and understand the variation of the apatite characteristics throughout the deposit, and this
thesis research greatly contributes to advance this understanding.
As recommendation for further studies, the writer suggests that a geochemical and
microscopic analysis of samples from the flotation reject tailings, collected at different
times through a representative period of weeks or few months, compared to the
characterization provided in this work, would more precisely demonstrate which ores are
actually not being adequately recovered. This could further contribute toward an increase
in the effectiveness of the Cajati process for the different types of apatite from the
carbonatite deposit. A similar work has been performed by Toledo and Pereira (2001), for
instance, by studying the final product and reject tailings from processing of apatite at the
Tapira carbonatite deposit, using optical microscopy attached to a CL detector. They
demonstrated that the ore that was not recovered was either not liberated from the gangue
minerals, or was comprised of grains with mixed generations of apatite, such as primary
apatite partially affected by subsequent supergene alteration.

5.2. APATITE CHARACTERISTICS RELATED TO PROCESSING ISSUES

There are three types of apatite ores recognized by the company staff as more
difficult to process:
1) reddish apatite that occurs close to the fault zone,
2) apatite from the carbonatite in the xenolith zones, and
3) hard apatite, mostly concentrated in the northwestern portion of the orebody.

83
As a result of this research, it was demonstrated that the apatite from the fault
zone had its chemical and morphological characteristics affected. For instance, the apatite
closer to the brecciated area (encompassed in sampling area C), where the presence of
zoned, recrystallized calcite was identified by CL, was fragmented into very small,
angular grains. These grains also are softer and have a high probability of being discarded
during the desliming step. The apatite grains from the fault zone that have not been
fragmented show several fractures and have a dull CL that indicates additional iron
probably has entered into its structure, quenching its CL and causing the reddish
appearance of these grains. In addition to the effect on milling and consequently size
classification, the entrance of other elements may also have affected the mineral surface
charge characteristics, further negatively influencing its recovery by flotation.
In relation to the apatite from the xenoliths zone, which is correlated mostly with
the transition area between intrusions C3 and C4 as defined by Gaspar (1989), this thesis
research has shown that there are some chemical composition differences with respect to
apatite from the other intrusions. However, the writer believes that in this case, the
negative effect on flotation recovery is mostly a function of the elevated amounts of fine,
platy silicates in the gangue (phlogopite, serpentine), making the suppression of these
minerals less effective than the suppression of a gangue with a higher content of
carbonates. There probably is an optimum limit for the presence of platy particles, above
which they will increasingly make the adhesion of apatite to the bubbles much more
difficult. In fact, the practice at the time when the writer was part of the company staff
was to limit the mix to less than about 15% weight of mineralized rock from the xenolith
zone, but this limiting number appeared to be still somewhat high. A comparison between
the economic benefit of ore reserve maximization versus process recovery maximization
is necessary to determine the breakeven point and better define the limit for utilization of
the ore from the xenolith zone.
Finally, the apatite described as hard, more difficult to grind, occurs in the
sampling area E (and probably also in area F). This thesis research has demonstrated that
area E was affected by late metasomatism or hydrothermal activity. The CL microscopy
showed that the internal structure and composition of apatite was barely affected, even
though carbonates and sulfide microveins penetrated and formed fractures in apatite. In

84
addition, no evidence of apatite recrystallization was found. The microveins apparently
cemented the apatite fragments, resulting in greater cohesiveness, and consequently the
perception of greater hardness. However, this is not the only effect of the hydrothermal
activity, and it may actually be minor in importance when compared to the changes of the
surface characteristics of apatite. This study has shown that the ore in the area commonly
displays a distinct external zone that exhibits a white CL color. Although the
microtopography and chemical composition of this external zone in apatite were not
analyzed, it still can be inferred that this surface aspect probably is related to the negative
results obtained during flotation. The detrimental effect in flotation, as well as the
potential relevance in comparison to the bulk of the processed ore, suggests that future
investigation of the flotation rejects would be useful.

5.3. DEVELOPMENT OF THE MINERALIZATION: CONTRIBUTIONS FROM

THE GANGUE MINERALS
In order to help better understand the development of the phosphate
mineralization, which is relevant for a better comprehension of the apatite processing
behavior, this microscopic study was extended to include the gangue minerals. The CL
technique was particularly useful to analyze the carbonates, representing a direct method
of distinction between calcite and dolomite, revealing the distribution of these minerals in
the deposit, and recognizing the carbonatite-related variety of textures and structures that
could not have been readily demonstrated through other methods. In addition, baddeleyite
and some olivine crystals also exhibited CL, a feature that was useful for the
identification of the former, and to infer variations in chemical composition of the latter
as compared with non-cathodoluminescent olivine grains.
In most cases, such as for the oxides and silicates, the microscopy and EPMA data
from this research support the hypotheses proposed by Gaspar (1989): 1) that the
carbonatite deposit was emplaced through at least five intrusive episodes, 2) that there is
a time hiatus between the oldest intrusion (C1) and the following ones, based mostly on
compositional differences, and 3) that the second intrusion (C2) is probably the parent of
the youngest ones (C3, C4 and C5), although its time of emplacement may not agree with

85
the continuous sequence of emplacement proposed for the three last intrusions. For
instance, data from this thesis research has demonstrated important differences in terms
of texture and chemical composition between olivine from areas C and E (approximately
equivalent to the intrusions C1 and C4, respectively, as delineated by Gaspar, 1989). The
current research also has provided SEM images showing the complex zoning of
phlogopite and demonstrating the distribution of Ba and Mg. Both elements are present
in highly elevated levels as compared with most other carbonatites (as listed by Brod et
al., 2001). In addition, images of the textures developed for magnetite (containing
variable, but low Ti, Mn, Mg, V and Al), and the effect on the composition of this
mineral in the presence of ilmenite (containing high Mn, Nb, and exceptionally high Mg)
integrate and expand the set of characteristics previously described in the literature
(Gaspar and Wyllie, 1983a and 1983b).
With regard to the sulfides, the reflected light microscopic investigation was
important to show their textures, as described earlier in this thesis. Those textures
confirm that some of the sulfides are related to hydrothermal activity. Such an
interpretation was only a speculation at the time this research was initiated.
Although the scope of this thesis was initially defined to deal only with the apatite
mineralization and the gangue minerals contained in the carbonatite deposit, the results
can be extended to reflect upon the carbonatite petrogenesis in relation to the alkaline
complex. In this respect, the current study has provided geochemical and mineralogical
information indicating that more than one petrological process, such as partial melting
and fractional crystallization, may have been involved in the development of the
individual carbonatite intrusions.

5.4. PETROGENETIC ASSOCIATION OF THE DOLOMITIC CARBONATITE

SP24
The sample SP24-53 was collected from drill cores of a hole drilled in an area
beyond the current open pit mine, just north of the carbonatite deposit. The vertical drill
hole encountered carbonatite with 180 m of continuous apatite mineralization before
bottoming in jacupirangite. It is not known whether it represents an extension of the

86
northernmost intrusion, or it is an individual intrusion or marginal dike. It shows a high
content of fine-grained apatite, as well as chemical and textural characteristics that are
significantly different from the northern intrusions that are currently being mined (C4 and
C5). It has also been considered that this carbonatite perhaps is just a portion of the latest
northern intrusion that was strongly affected by metasomatism or hydrothermal activity.
The microscopic evidence from the current research supports the hypothesis that
the carbonatite in drill hole SP24-53 represents an individual intrusion (or marginal dike).
That carbonatite also exhibits textures and mineralogy that are significantly different
from the other carbonatite intrusions in that it contains only about 3 % fine-grained
magnetite and as much as 5 % modal pyrochlore. The carbonates are almost exclusively
represented by dolomite. It is noteworthy that hand samples of this carbonatite can be
easily distinguished from samples of other intrusions.
Apatite from this dolomitic carbonatite contains the highest concentrations of
LREE and strontium among all intrusions. The level of enrichment of these elements in
apatite is much higher than in apatite from the other two northern intrusions, and these
differences probably have resulted from a temporal and compositional gap with respect to
the carbonatites currently being mined. In addition, the high contents of LREE and
strontium may have inhibited apatite growth, causing the size of this mineral to be below
the average of that from the mined ore.

87
6. CONCLUSIONS

The conclusions from the current study are summarized below and arranged to
correlate with each topic of the completed research.

6.1. STYLES OF MINERALIZATION

The styles of apatite mineralization present in the carbonatites from the Cajati
mine are:
1) veins or veinlets, usually strongly oriented according to magma flow.
2) small pods or patches, either associated with veins, or formed by individual clusters of
short, acicular grains.
3) disseminated, discrete grains.
4) massive aggregates of medium to coarse apatite grains developed in the oldest
carbonatite intrusion.

6.2. ORE CHARACTERIZATION

The apatite from Jacupiranga shows distinctive geochemical trends and textural
characteristics between the five carbonatite intrusions. The replacement of Ca was
characterized by complex substitutions that occurred under conditions of disequilibrium,
simultaneously involving LREE (especially Ce, but also Nd and La), Sr, Na, and other
less important cations.
The total REE oxides level obtained for apatite from Jacupiranga in this thesis
research was low, ranging from 0.04 to 0.49%, with a consistent increase toward the
north as observed for the three latest intrusions. The variation of LREE levels does not
correlate very well with that of Na. The content of Na2O is also low, as was measured to
be within 0.07 and 0.37% in this thesis research. In terms of content variability among the
different intrusions, strontium shows the most regular trend, and also a more pronounced
sequential increase in the northern intrusions than that shown by LREE. In this thesis
study, a wider range for SrO content was found (0.40 to 1.02 %) than that previously

88
reported in the literature. Strontium typically increases towards the later phases of the
carbonatite intrusions. Indeed, in Jacupiranga the higher contents of SrO are restricted
exclusively to the youngest intrusions in the northern portion of the deposit.
Compositional zoning is conspicuous in apatite crystals at Jacupiranga, and it is
shown especially by changes in CL color that typically exhibit the following sequence
from core to rim:
1) pinkish blue/violet core, commonly showing euhedral, hexagonal shape (core).
2) blue CL zone, which can be absent.
3) light blue/greenish blue zone, more persistent during crystallization.
4) blue CL, very similar to zone 2.
5) bright, white CL developed along the borders of some apatite crystals, especially in the
northern intrusions that were locally affected by hydrothermal fluids (rim)

6.3. ASSOCIATION WITH MINERAL PROCESSING

The ore characteristics associated with apatite processing issues were interpreted
as follows:
1) Reddish apatite: was fractured (or even fragmented), and some grains show no CL,
possibly as a result of quenching by iron that entered the apatite structure, also changing
its color. Such chemical and morphological changes can negatively affect flotation
recovery.
2) Apatite from the xenoliths zone: shows some chemical variations in relation to apatite
from other areas, but the flotation recovery is probably being more negatively affected by
the elevated presence of fine, platy silicates in the gangue, which are more difficult to
eliminate previously in the process, and can interfere with the collection of apatite grains
in the flotation froth.
3) Hard apatite: occurs mostly in a northwestern area of the carbonatite that was affected
by hydrothermal fluids. The internal structure of apatite apparently was not affected, but
carbonates and sulfide veins penetrated apatite and recrystallized, possibly leading to
higher cohesiveness and the perception of greater hardness. In addition, a distinct external

89
zone of white CL was developed, probably affecting the surface properties of the apatite,
and modifying its flotation response.
In conclusion, all three problematic ores (reddish apatite, apatite from xenoliths
zone, and hard apatite) can be mined and processed, but the delimitation of their area of
occurrence is necessary to allow the mine planning to consider a limited blend of these
ores in the homogenized pile. Whenever they represent a significant component of the
plant feed material, the overall process recovery will decline, unless process
modifications to permit more flexibility in accepting the described apatite variability are
developed and implemented.
The principal contribution of this thesis research has been to characterize selected
apatite ores from Cajati by petrographic, reflected light, and cathodoluminescence (CL)
microscopic techniques, and to correlate the observed characteristics of the apatite
crystals and associated minerals with the presented difficulties in the beneficiation
process of certain ores. Cathodoluminescence microscopy proved to be a very efficient
technique for the study of apatite ores in carbonatite rocks.

APPENDIX A.
PLATE SHOWING SELECTED DRILL CORES

91

Plate A.1: Drill Cores Showing Various Aspects of the Apatite Mineralization.

b) Veinlets of Fine-Grained Apatite (Green) Oriented by

Magma Flow. Note Association With Subhedral Magnetite.
Sample SP07-106m.

c) Very Coarse Apatite Grains (Green) Occurring With

Coarse Magnetite. Sample SP02-119m.

d) Fine-Grained, Orange (Altered) Apatite Veins and Pods.

Recrystallized Calcite Fills Fractures. Sample SP03-48m.

91

a) Apatite Veins (Yellowish) and Small Pods Crystallized

Around Carbonates, Magnetite and Phlogopite.
Sample SP07-176m.

92

APPENDIX B.
PLATES SHOWING SELECTED MICROGRAPHS

93

a) CL image, sample J157-A: anhedral, fine-grained apatite crystallized

between Mg-rich calcite grains. FOV: 1.5mm.

Cc

Dol

Cc

Dol

b) CL image, sample J128-C: zoned apatite

grains occurring with calcite (Cc) and
dolomite (Dol). FOV: 1.5 mm.

c) CL image, sample J139-C: fractured, nonluminescent, fine apatite grains occurring

with calcite (Cc) and dolomite (Dol). FOV:
1.5 mm.

d) CL image, sample SP23-87: zoned

apatite, showing core with fluid inclusions,
being fractured by dolomite (red), and later
by calcite (yellow). FOV: 3.0 mm.

e) TL image, sample J210-D2: aspect of

fine-grained apatite forming veinlet
mineralization. FOV: 3.6 mm.

Plate B.1: Microscopic Images of Apatite From the Jacupiranga Carbonatite.

94

f) TL image, sample J202-D1: clusters of

fine-grained apatite in parallel to a vein with
angular fragments of apatite, dolomite, and
calcite. FOV: 3.6 mm.

g) CL image, sample J202-D1: detail of the

vein showing dolomite accompanied by
apatite and magnetite. Most calcite (yellow)
occurs outside the vein. FOV: 1.5 mm.

h) TL image, sample J216-D2: fine-grained

apatite forming lineations, and in some cases
conforming to calcite grain boundaries.
FOV: 3.6 mm.

i) TL image, sample J227-D: aspect of

apatite cluster occurring in association to
coarse magnetite grains. Phlogopite, calcite,
dolomite, and twinned baddeleyite are also
present in the image. FOV: 3.6 mm.

j) TL image, sample J169-E: zoned apatite

oriented according to magma flow, and
showing small, primary fluid inclusions.
Matrix is dolomitic. FOV: 2.0 mm.

l) TL image, sample J183-E: close-up on

anhedral apatite grains crystallized on
magnetite face. Calcite is the dominant
carbonate in the sample. FOV: 1.8 mm.

Plate B.1: Microscopic Images of Apatite From the Jacupiranga Carbonatite.

95

m) TL image, sample J179-E: apatite grains,

with different crystallographic orientations,
showing concentration of fluid inclusions in
the core. FOV: 1.5 mm.

n) TL image, sample J179-E: close-up on

previous image, emphasizing the orientation
of the fluid inclusions along the crystal caxis. FOV: 0.25 mm.

o) TL image, sample J179-E: fluid

inclusions in the basal section of apatite, as
seen with un-crossed nicols. Inclusions are
very small (1 to 5 m). FOV: 0.95 mm.

p) CL image, sample J193-E: dolomitic

carbonatite showing zoned dolomite and
apatite. Many fluid inclusions occur in the
apatite core (white spots). FOV: 1.5 mm.

q) CL image, sample SP15-206: apatite

grain showing clustering of smaller crystals
in its core. Calcite (yellow) is the dominant
carbonate in the sample. FOV: 1.5 mm.

r) CL image, sample SP15-215: complexly

zoned apatite showing uncommon white CL
rim. CL color is yellow for calcite, and red
for dolomite. FOV: 1.5 mm.

Plate B.1: Microscopic Images of Apatite From the Jacupiranga Carbonatite.

96

s) TL image, sample SP15-215: large

(width=54m), biphasic (L+V) primary
fluid inclusion in apatite.
FOV: 0.24 mm.

t) TL image, sample SP15-215: close-up on

another large (width=48 m), tri-phase
(L+V+S) fluid inclusion in apatite. FOV:
0.18 mm.

u) TL image, sample SP15-215: set of

elongated, primary fluid inclusions in
apatite, some of which have been necked
down. FOV: 0.96 mm.

v) TL image, sample J103-F: aspect of

anhedral apatite embaying calcite. FOV: 1.0
mm.

x) TL image, sample J112-F11: cluster or

pod of apatite formed by accumulation
induced by magma flow. FOV: 3.6 mm.

z) TL image, sample J112-F1: aspect of vein

of apatite accumulating on magnetite and
dolomite grains. FOV: 3.6 mm.

Plate B.1: Microscopic Images of Apatite From the Jacupiranga Carbonatite.

97

a) TL image, sample J151-A7: exsolution

blebs of dolomite in calcite, and aspect of
irregular grain boundaries. FOV: 1.0 mm.

b) TL image, sample J127-C: calcite with

exsolution spindles of dolomite. Altered
olivine, phlogopite, and small apatite grains
are also seen in the image. FOV: 1.8 mm.

c) CL image, sample J136-C4: close-up on

carbonates vein showing transition from
dolomite (red) to calcite (yellow).
FOV: 1.5 mm.

d) TL image, sample J139-C: aspect of

serrated boundaries (circle) seen in calcite
grains. FOV: 1.8 mm.

e) TL image, sample J210-D2: characteristic

of interstitial carbonate and anhedral,
elongated calcite. FOV: 2.0 mm.

f) TL image, sample J227-D: aspect

interstitial blebs formed among calcite
grains boundaries. FOV: 2.0 mm.

Plate B.2: Microscopic Images of Calcite and Dolomite From the Jacupiranga Carbonatite.

98

Dol
Cc
Cc

Dol

g) TL image, sample J169-E: few, interstitial

calcite (Cc) in dolomite (Dol) matrix,
accompanied by flow oriented, anhedral
apatite, and one phlogopite grain (top left
corner). FOV: 1.92 mm.

h) CL image, sample J193-E: small grains of

zoned apatite (with fluid inclusions in the
core), within matrix of zoned dolomite.
FOV: 1.5 mm.

i) TL image, sample J103-F: aspect of

interlocking texture formed by irregular
shaped calcite and apatite. FOV: 2.0 mm.

j) TL image, sample J103-F: interstitial

calcite filling gap among apatite crystals. A
small grain of perovskite is present at the top
center of the image. FOV: 0.96 mm.

l) TL image, sample J115-F: twinned calcite

with blebs trapped along crystal edge.
FOV: 1.0 mm.

m) TL image, sample SP24-53: close-up on

small fluid inclusions (L+V) occurring along
dolomite cleavage plans. FOV: 0.25 mm.

Plate B.2: Microscopic Images of Calcite and Dolomite From the Jacupiranga Carbonatite.

99

a) CL image, sample J127-C: resorbed, large

magnetite containing apatite, calcite and
dolomite inclusions. FOV: 1.84 mm.

b) TL image, sample J136-C4: detail of

resorbed magnetite in contact with
carbonates. FOV: 2.0 mm.

c) TL image, sample J227-D: coarse,

subhedral magnetite with apatite inclusions,
in contact with phlogopite, calcite and thin
vein of apatite. FOV: 2.0 mm.

d) TL image, sample J176-E: subhedral

appearance of resorbed magnetite grains.
FOV: 3.6 mm.

e) TL image, sample J176-E: aspect of

magnetite embaying calcite. Note small pod
of apatite on the right side. FOV: 1.92 mm.

f) TL image, sample J106-F: fringed

boundary of large, resorbed magnetite grain,
in contact with calcite. Note inclusions of
carbonates in magnetite. FOV: 2.0 mm.

Plate B.3: Microscopic Images of Magnetite From the Jacupiranga Carbonatite.

100

a) CL image, sample J128-C: altered olivine

showing bright, dark blue CL. Zoned apatite
(light blue), dolomite (red), and calcite
(orange) can also be seen. FOV: 3.0 mm.

b) CL image, sample J128-C: olivine with

blue CL alteration rim, occurring with
apatite, calcite, and minor dolomite.
FOV: 1.5 mm.

c) TL image, sample J127-C: highly

fractured, altering grain of olivine, cut by
later calcite vein. Apatite grains are present
in the right side of the image. FOV: 3.6 mm.

d) TL image, sample J198-D2: Olivine

partially replaced by phlogopite.
FOV: 1.92 mm.

e) TL image, sample J183-E: small olivine

with little alteration, and apatite inclusions.
Apatite grains also occur as lineations
molding on the olivine. FOV: 3.6 mm.

f) TL image, sample J103-F: Olivine

alteration by pseudomorphization. Apatite,
phlogopite (top right corner), and exsolved
calcite are also present. FOV: 2.0 mm.

Plate B.4: Microscopic Images of Olivine From the Jacupiranga Carbonatite.

101

a) TL image, sample J136-C4: aspect of

deformed phlogopite with advanced
alteration. FOV: 2.0 mm.

b) TL image, sample J139-C: deformed,

partially altered phlogopite in contact with
pyrrhotite and calcite. FOV: 2.0 mm.

c) TL image, sample SP23-87: zoned

phlogopite showing alteration along its rims.
FOV: 2.2 mm.

d) TL image, sample J227-D: phlogopite in

apatite vein, together with small amount of
carbonates. Magnetite (opaque) and small
baddeleyite are also present. FOV: 1.8 mm.

e) TL image, sample J169-E: phlogopite

containing small apatite inclusions. Note
accommodating contact of apatite with
phlogopite, and presence of interstitial
carbonate. FOV: 0.9 mm.

f) TL image, sample J179-E: evidence of

zoning in altered phlogopite grain. Opaque
mineral is magnetite. FOV: 0.9 mm.

Plate B.5: Microscopic Images of Phlogopite From the Jacupiranga Carbonatite.

102

Po
Val

a) RL image, sample J151-A7: pyrrhotite

showing hexagonal crystal shape.
FOV: 1.0 mm.

b) RL image, sample J128-C: pyrrhotite (Po)

with valleriite (Val) in contact with calcite.
Light grey mineral is primary magnetite
(bottom right corner). FOV: 0.25 mm.

c) RL image, sample J139-C: pyrrhotite

showing twinning laths, being replaced by
pyrite (light yellow), and secondary
magnetite (grey). FOV: 0.25 mm.

d) RL image, sample SP15-206:

chalcopyrite, magnetite, and minor pyrite, in
calcite matrix. FOV: 1.8 mm.

Cc
e) RL image, sample SP15-215: pyrite
microveins in apatite. Note that pyrite does
not penetrate calcite (Cc). FOV: 2.0 mm.

f) RL image, sample SP15-215: inclusions

of pyrite in secondary magnetite.
FOV: 0.25 mm.

Plate B.6: Microscopic Images of Various Sulfides From the Jacupiranga Carbonatite.

103

a) TL image, sample J108-F11: metamict

pyrochlore forming radioactive halo in
phlogopite. FOV: 1.0 mm.

b) TL image, sample J108-F11: aspect of

subhedral (octahedral) pyrochlore.
FOV: 1.8 mm.

c) RL image, sample J222-D2: twinned

baddeleyite included in phlogopite.
FOV: 1.0 mm.

d) TL image, sample J222-D2: twinned

baddeleyite included in phlogopite.
FOV: 3.6 mm.

e) Darkfield image, sample J179-E: twinned

baddeleyite in contact with magnetite.
Calcite is also seen. FOV: 0.9 mm.

f) CL image, sample J111-F: bright blue

emission from baddeleyite grains included
in phlogopite. FOV: 1.5 mm.

Plate B.7: Microscopic Images of Other Minerals From the Jacupiranga Carbonatite.

104

APPENDIX C.
ESTIMATED MODAL COMPOSITIONS FOR SELECTED THIN SECTIONS

105
Table C.1: Estimated Modal Compositions for Selected Thin Sections.
SAMPLE
J151A
J157A
J126B
J127C
J128C
J136C4
J137C
J139C
SP23-87
J198D2
J202D1
J210D2
J216D2
J222D2
J227D
J169E
J176E
J179E
J183E
J193E
SP15-206
SP15-215
J103F
J106F
J108F11
J111F
J115F
J112F11
SP24-53

Location*
2759, B-30 SW
2763, B-30 SW
B-70
3432, B-60
3435, B-60
2446, B-60
3428, B-60 E
3428, B-60 E
drill hole
2364, B-50
2368, B-50
2364, B-50
2368, B-50
2359
B-50 E
B30 NE
B30 NE
B30 NE
B30 NE
B30 NE
drill hole
drill hole
B70 NE
B70 NE
B70 NE
B70 NE
B70 NE
B70 NE
drill hole

Cc
49
18
37
69
41
48
69
58
61
31
72
46
49
38
30
4
43
30
28
2
52
31
46
45
3
66
58
67
1

Dol
5
0
3
4
3
22
3
13
8
21
8
18
26
18
18
71
14
8
17
70
18
37
12
15
7
5
25
0
74

Apt Mgt Oliv

2
30
0
5
14
28
53
2
0
16
7
1
14
33
5
3
17
0
4
2
18
0
0
4
<1
0
22
37
2
5
12
5
0
13
22
0
17
3
0
<1
38
0
11
33
0
15
0
0
16
19
3
20
30
3
15
25
6
17
8
0
23
5
0
6
0
17
3
8
27
22
14
0
24
5
55
10
15
1
9
0
0
22
5
0
16
3
0

Phl
8
35
5
<1
1
4
1
5
4
3
2
1
1
5
3
4
5
5
4
3
<1
<1
<1
4
4
1
3
0
1

Sulf Others
0
6
0
0
0
0
3
0
3
<1
6
0
3
0
20
<1
2
3
1
0
1
<1
0
0
4
0
0
1
5
0
6
<1
0
<1
<1
4
4
1
0
0
2
0
7
2
4
<1
0
0
<1
2
1
1
5
<1
0
0
0
5

Cc = calcite, Dol = dolomite, Apt = apatite, Mgt = magnetite, Oliv = olivine, Phl =
phlogopite, Sulf = sulfides (pyrrhotite, pyrite, chalcopyrite, valleriite).
* Check Figure 3.1 in the Text for Sampling Point Locations. Example: 2759.
Note: B70N = Mine Bench at Topographic Level 70m, Northern Area of the Pit.

106

APPENDIX D.
DATA FROM MICROPROBE ANALYSES

107
Table D.1: Microprobe Analyses of Apatite.
Weight Percent Components
Label
SiO2 Al2O3 FeO* MnO
Sample J151-A7
Apatite 1 - elongate grain, points along c axis
J151-A7 Ap1-1
0.007 0.000 0.000 0.003
J151-A7 Ap1-2
0.005 0.011 0.004 0.000
J151-A7 Ap1-3
0.038 0.000 0.016 0.005
J151-A7 Ap1-4
0.051 0.000 0.052 0.027
J151-A7 Ap1-5
0.000 0.000 0.008 0.008
J151-A7 Ap1-6
0.010 0.005 0.000 0.011
J151-A7 Ap1-7
0.051 0.000 0.017 0.005
J151-A7 Ap1-8
0.001 0.000 0.014 0.013
J151-A7 Ap1-9
0.054 0.007 0.033 0.003
J151-A7 Ap1-10
0.012 0.005 0.108 0.009

MgO

CaO

SrO

0.000
0.000
0.057
0.038
0.010
0.015
0.026
0.021
0.041
0.000

55.016
55.078
54.882
54.728
54.385
54.511
54.330
54.424
54.836
54.607

Apatite 2
J151-A7 Ap2-1
J151-A7 Ap2-2
J151-A7 Ap2-3
J151-A7 Ap2-4
J151-A7 Ap2-5
J151-A7 Ap2-6

0.028
0.010
0.043
0.051
0.002
0.000

BaO La2O3 Ce2O3 Nd2O3 Sm2O3 Na2O

K2O P2O5

SO3

Cl

0.535
0.559
0.433
0.432
0.506
0.442
0.429
0.512
0.409
0.491

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.070
0.071
0.058
0.006
0.068
0.067
0.019
0.058
0.007
0.040

0.233
0.246
0.062
0.121
0.194
0.114
0.062
0.141
0.004
0.154

0.051
0.078
0.049
0.043
0.107
0.038
0.043
0.083
0.056
0.062

0.006
0.000
0.006
0.000
0.000
0.027
0.000
0.000
0.000
0.017

0.106
0.110
0.125
0.116
0.149
0.123
0.119
0.118
0.136
0.112

0.002
0.000
0.005
0.000
0.002
0.000
0.005
0.000
0.000
0.000

44.312
43.250
42.822
42.905
43.748
43.663
42.982
43.579
42.982
43.814

0.013
0.016
0.008
0.019
0.008
0.061
0.007
0.011
0.022
0.053

2.195
2.167
2.081
2.044
2.155
2.086
2.034
2.171
2.129
2.389

0.017
0.007
0.023
0.018
0.002
0.017
0.001
0.000
0.018
0.000

-0.924
-0.913
-0.876
-0.861
-0.907
-0.878
-0.856
-0.914
-0.896
-1.006

0.209
0.206
0.198
0.194
0.205
0.198
0.193
0.206
0.202
0.227

54.390
48.291
53.765
54.215
54.523
54.281

0.452
0.398
0.470
0.477
0.473
0.500

0.000
0.000
0.000
0.000
0.000
0.000

0.037
0.054
0.084
0.055
0.066
0.081

0.200
0.126
0.126
0.139
0.133
0.160

0.055
0.043
0.065
0.074
0.134
0.155

0.000
0.000
0.000
0.000
0.000
0.000

0.221
0.227
0.281
0.258
0.182
0.147

0.002
0.010
0.000
0.002
0.000
0.017

42.879
37.432
42.555
43.287
42.963
42.813

0.041
0.059
0.063
0.050
0.013
0.055

1.975
2.042
1.757
1.949
2.005
2.006

0.003
0.476
0.019
0.023
0.007
0.004

-0.832
-0.860
-0.740
-0.820
-0.844
-0.845

0.188 99.709
0.194 88.609
0.167 98.776
0.185 100.026
0.191 99.905
0.191 99.660

Sample J179-E
Area 2, apatite 1, line across elongate grain, points 50 um apart
J179-E a2-Ap1-1
0.004 0.000 0.008 0.049 0.047 54.445
J179-E a2-Ap1-2
0.019 0.004 0.007 0.010 0.063 54.751
J179-E a2-Ap1-3
0.015 0.022 0.000 0.028 0.065 54.013
J179-E a2-Ap1-4
0.004 0.010 0.004 0.031 0.015 54.137
J179-E a2-Ap1-5
0.000 0.000 0.015 0.006 0.000 54.181

0.443
0.455
0.452
0.428
0.480

0.000
0.000
0.003
0.000
0.000

0.030
0.047
0.012
0.018
0.072

0.084
0.059
0.046
0.022
0.025

0.000
0.094
0.000
0.071
0.104

0.004
0.000
0.000
0.000
0.000

0.154
0.142
0.120
0.115
0.081

0.000
0.000
0.000
0.012
0.000

42.970
42.778
42.808
42.593
43.159

0.056
0.028
0.036
0.013
0.048

1.516
1.533
1.433
1.440
1.688

0.011
0.000
0.012
0.000
0.000

-0.638
-0.646
-0.603
-0.606
-0.711

0.144
0.146
0.136
0.137
0.160

99.328
99.489
98.597
98.442
99.311

Bright zone in CL image

J179-E a2-Ap1hcl0.003 0.010 0.000 0.006 0.000 54.552 0.452 0.000

0.035

0.057

0.058

0.000 0.093 0.000 42.789 0.047 1.652 0.002 -0.696 0.157

99.217

Area 2, Apatite 2 (cross section), 100 um grain, points from core to rim
J179-E a2-Ap2-1
0.001 0.002 0.000 0.000 0.043 54.427 0.402 0.000
J179-E a2-Ap2-2
0.008 0.006 0.027 0.006 0.063 54.466 0.424 0.000
J179-E a2-Ap2-3
0.010 0.008 0.003 0.000 0.000 54.347 0.440 0.000

0.040
0.041
0.055

0.022
0.025
0.091

0.044
0.040
0.029

0.000 0.101 0.000 42.461 0.020 1.602 0.001 -0.675 0.152

0.000 0.109 0.002 42.602 0.045 1.617 0.003 -0.681 0.154
0.000 0.073 0.000 42.644 0.058 1.775 0.000 -0.747 0.169

98.643
98.958
98.955

Area 1 - apatite inclusion in magnetite

J179-E a1-Apinc3-1
0.013 0.020 0.572 0.024 0.092 54.704 0.476 0.000
J179-E a1-Apinc3-2
0.006 0.019 0.655 0.032 0.063 54.401 0.443 0.000
J179-E a1-Apinc3-3
0.007 0.014 1.131 0.001 0.022 54.100 0.462 0.000

0.012
0.000
0.013

0.017
0.096
0.075

0.075
0.081
0.014

0.000 0.190 0.008 42.741 0.028 1.399 0.007 -0.589 0.133

0.001 0.183 0.010 42.353 0.025 1.552 0.018 -0.654 0.147
0.000 0.071 0.000 42.725 0.040 1.482 0.000 -0.624 0.141

99.923
99.432
99.674

Area 1- apatite outside magnetite

J179-E a1-Ap4-1
0.000 0.000 0.017 0.000 0.029 54.517 0.456 0.000
J179-E a1-Ap4-2
0.006 0.000 0.013 0.000 0.082 54.367 0.435 0.000
J179-E a1-Ap4-3
0.000 0.015 0.003 0.029 0.000 54.569 0.443 0.000

0.016
0.022
0.000

0.062
0.005
0.075

0.044
0.046
0.085

0.000 0.120 0.007 42.523 0.063 1.401 0.000 -0.590 0.133

0.000 0.187 0.005 42.405 0.040 1.550 0.003 -0.652 0.147
0.000 0.073 0.006 42.946 0.040 1.592 0.000 -0.670 0.151

98.800
98.661
99.357

Sample SP24-53
Area 3 - apatite 1, points core to rim, 50 um apart
SP24-53 A3-1
0.000 0.011 0.003 0.010
SP24-53 A3-2
0.004 0.008 0.000 0.015
SP24-53 A3-3
0.005 0.000 0.014 0.030
SP24-53 A3-4
0.003 0.000 0.000 0.056

0.000
0.000
0.000
0.000

0.075
0.080
0.074
0.062

0.209
0.201
0.211
0.254

0.029
0.101
0.079
0.080

0.000
0.000
0.028
0.003

Area 3 - apatite 2, elongate grain

SP24-53 A3-Ap2-1
0.005 0.000 0.016 0.004 0.013 54.282 0.857 0.000
SP24-53 A3-Ap2-2
0.010 0.000 0.023 0.038 0.014 53.861 0.996 0.000
SP24-53 A3-Ap2-3
0.005 0.000 0.025 0.042 0.053 54.111 0.889 0.000

0.092
0.053
0.081

0.261
0.178
0.227

0.141
0.096
0.099

0.000 0.168 0.007 43.168 0.013 2.157 0.010 -0.908 0.205 100.490
0.000 0.247 0.009 42.740 0.029 2.233 0.015 -0.940 0.212 99.813
0.000 0.246 0.002 43.602 0.032 2.113 0.013 -0.890 0.201 100.850

0.007
0.078
0.014
0.016
0.010
0.008

0.004
0.006
0.005
0.009
0.013
0.006

0.054
0.024
0.064
0.043
0.027
0.075

0.006
0.000
0.039
0.014
0.010
0.006

0.000
0.000
0.009
0.003

54.778
54.608
54.263
54.349

0.878
0.857
1.019
0.913

0.134
0.195
0.192
0.174

0.004
0.003
0.000
0.011

43.200
43.355
43.434
43.445

0.016
0.030
0.018
0.000

2.283
2.567
2.305
2.372

0.006
0.003
0.019
0.002

O=F O=Cl

-0.961
-1.081
-0.970
-0.999

0.217
0.244
0.219
0.225

Total

101.851
100.896
99.991
99.934
100.648
100.510
99.466
100.438
100.043
101.093

100.893
101.189
100.948
100.954

108
Table D.1: (continued) Microprobe Analyses of Apatite.
Ions per 12 Oxygen + 1 (OH,F,Cl):sum excludes F and Cl
Label
Si
Al
Fe
Mn
Mg
Ca
Sr
Y
Sample J151-A7
Apatite 1 - elongate grain, points along c axis
J151-A7 Ap1-1
0.001 0.000 0.000 0.000 0.000 4.803 0.025 0.000
J151-A7 Ap1-2
0.000 0.001 0.000 0.000 0.000 4.876 0.027 0.000
J151-A7 Ap1-3
0.003 0.000 0.001 0.000 0.007 4.896 0.021 0.000
J151-A7 Ap1-4
0.004 0.000 0.004 0.002 0.005 4.880 0.021 0.000
J151-A7 Ap1-5
0.000 0.000 0.001 0.000 0.001 4.805 0.024 0.000
J151-A7 Ap1-6
0.001 0.000 0.000 0.001 0.002 4.818 0.021 0.000
J151-A7 Ap1-7
0.004 0.000 0.001 0.000 0.003 4.857 0.021 0.000
J151-A7 Ap1-8
0.000 0.000 0.001 0.001 0.003 4.820 0.025 0.000
J151-A7 Ap1-9
0.005 0.001 0.002 0.000 0.005 4.883 0.020 0.000
J151-A7 Ap1-10
0.001 0.000 0.007 0.001 0.000 4.810 0.023 0.000

Ba

La

Ce

Nd

Sm

Gd

Na

Cl

Sum

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.002
0.002
0.002
0.000
0.002
0.002
0.001
0.002
0.000
0.001

0.007
0.007
0.002
0.004
0.006
0.003
0.002
0.004
0.000
0.005

0.001
0.002
0.001
0.001
0.003
0.001
0.001
0.002
0.002
0.002

0.000
0.000
0.000
0.000
0.000
0.001
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.017
0.018
0.020
0.019
0.024
0.020
0.019
0.019
0.022
0.018

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

3.057
3.025
3.019
3.023
3.054
3.049
3.036
3.050
3.024
3.049

0.001
0.001
0.000
0.001
0.000
0.004
0.000
0.001
0.001
0.003

0.566
0.566
0.548
0.538
0.562
0.544
0.537
0.568
0.560
0.621

0.002
0.001
0.003
0.003
0.000
0.002
0.000
0.000
0.003
0.000

7.914
7.960
7.974
7.964
7.921
7.922
7.947
7.927
7.965
7.921

Apatite 2
J151-A7 Ap2-1
J151-A7 Ap2-2
J151-A7 Ap2-3
J151-A7 Ap2-4
J151-A7 Ap2-5
J151-A7 Ap2-6

0.001
0.007
0.001
0.001
0.001
0.001

0.000
0.001
0.000
0.001
0.001
0.001

0.004
0.002
0.005
0.003
0.002
0.005

0.000
0.000
0.003
0.001
0.001
0.000

0.003
0.001
0.005
0.006
0.000
0.000

4.860
4.904
4.842
4.819
4.864
4.857

0.022
0.022
0.023
0.023
0.023
0.024

0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000

0.001
0.002
0.003
0.002
0.002
0.003

0.006
0.004
0.004
0.004
0.004
0.005

0.002
0.001
0.002
0.002
0.004
0.005

0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000

0.036
0.042
0.046
0.041
0.029
0.024

0.000
0.001
0.000
0.000
0.000
0.002

3.027
3.003
3.028
3.040
3.029
3.027

0.003
0.004
0.004
0.003
0.001
0.003

0.521
0.612
0.467
0.511
0.528
0.530

0.000
0.076
0.003
0.003
0.001
0.001

7.965
7.995
7.965
7.947
7.961
7.956

Sample J179-E
Area 2, apatite 1, line across elongate grain, points 50 um apart
J179-E a2-Ap1-1
0.000 0.000 0.001 0.003 0.006 4.861
J179-E a2-Ap1-2
0.002 0.000 0.000 0.001 0.008 4.891
J179-E a2-Ap1-3
0.001 0.002 0.000 0.002 0.008 4.850
J179-E a2-Ap1-4
0.000 0.001 0.000 0.002 0.002 4.876
J179-E a2-Ap1-5
0.000 0.000 0.001 0.000 0.000 4.838

0.021
0.022
0.022
0.021
0.023

0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000

0.001
0.001
0.000
0.001
0.002

0.003
0.002
0.001
0.001
0.001

0.000
0.003
0.000
0.002
0.003

0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000

0.025
0.023
0.019
0.019
0.013

0.000
0.000
0.000
0.001
0.000

3.031
3.019
3.037
3.032
3.045

0.004
0.002
0.002
0.001
0.003

0.400
0.404
0.380
0.383
0.445

0.002
0.000
0.002
0.000
0.000

7.956
7.974
7.946
7.959
7.930

4.884 0.022 0.000

0.000

0.001

0.002

0.002 0.000 0.000

0.015 0.000 3.027 0.003 0.437 0.000

7.958

Area 2, Apatite 2 (cross section), 100 um grain, points from core to rim
J179-E a2-Ap2-1
0.000 0.000 0.000 0.000 0.005 4.903 0.020 0.000
J179-E a2-Ap2-2
0.001 0.001 0.002 0.000 0.008 4.890 0.021 0.000
J179-E a2-Ap2-3
0.001 0.001 0.000 0.000 0.000 4.883 0.021 0.000

0.000
0.000
0.000

0.001
0.001
0.002

0.001
0.001
0.003

0.001 0.000 0.000

0.001 0.000 0.000
0.001 0.000 0.000

0.016 0.000 3.022 0.001 0.426 0.000

0.018 0.000 3.022 0.003 0.428 0.000
0.012 0.000 3.027 0.004 0.471 0.000

7.971
7.968
7.954

Area 1 - apatite inclusion in magnetite

J179-E a1-Apinc3-1
0.001 0.002 0.040 0.002 0.011
J179-E a1-Apinc3-2
0.000 0.002 0.046 0.002 0.008
J179-E a1-Apinc3-3
0.001 0.001 0.079 0.000 0.003

4.873 0.023 0.000

4.882 0.022 0.000
4.834 0.022 0.000

0.000
0.000
0.000

0.000
0.000
0.000

0.000
0.003
0.002

0.002 0.000 0.000

0.002 0.000 0.000
0.000 0.000 0.000

0.031 0.001 3.008 0.002 0.368 0.001

0.030 0.001 3.003 0.002 0.411 0.003
0.011 0.000 3.016 0.003 0.391 0.000

7.996
8.003
7.973

Area 1- apatite outside magnetite

J179-E a1-Ap4-1
0.000 0.000 0.001 0.000 0.004
J179-E a1-Ap4-2
0.000 0.000 0.001 0.000 0.010
J179-E a1-Ap4-3
0.000 0.001 0.000 0.002 0.000

4.898 0.022 0.000

4.896 0.021 0.000
4.875 0.021 0.000

0.000
0.000
0.000

0.000
0.001
0.000

0.002
0.000
0.002

0.001 0.000 0.000

0.001 0.000 0.000
0.003 0.000 0.000

0.020 0.001 3.019 0.004 0.372 0.000

0.030 0.000 3.018 0.003 0.412 0.000
0.012 0.001 3.031 0.003 0.420 0.000

7.972
7.982
7.951

Sample SP24-53
Area 3 - apatite 1, points core to rim, 50 um apart
SP24-53 A3-1
0.000 0.001 0.000 0.001
SP24-53 A3-2
0.000 0.001 0.000 0.001
SP24-53 A3-3
0.000 0.000 0.001 0.002
SP24-53 A3-4
0.000 0.000 0.000 0.004

4.858
4.834
4.807
4.814

0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000

0.002
0.002
0.002
0.002

0.006
0.006
0.006
0.008

0.001
0.003
0.002
0.002

0.022
0.031
0.031
0.028

0.001
0.000
0.003
0.000

7.962
7.954
7.944
7.945

4.828 0.041 0.000

4.830 0.048 0.000
4.784 0.043 0.000

0.000
0.000
0.000

0.003
0.002
0.002

0.008
0.005
0.007

0.004 0.000 0.000

0.003 0.000 0.000
0.003 0.000 0.000

0.027 0.001 3.034 0.001 0.566 0.001

0.040 0.001 3.028 0.002 0.591 0.002
0.039 0.000 3.046 0.002 0.551 0.002

7.950
7.966
7.938

Bright zone in CL image

J179-E a2-Ap1hcl0.000 0.001 0.000 0.000 0.000

0.000
0.000
0.001
0.000

Area 3 - apatite 2, elongate grain

SP24-53 A3-Ap2-1
0.000 0.000 0.001 0.000 0.002
SP24-53 A3-Ap2-2
0.001 0.000 0.002 0.003 0.002
SP24-53 A3-Ap2-3
0.000 0.000 0.002 0.003 0.007

0.042
0.041
0.049
0.044

0.000
0.000
0.001
0.000

0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.001

3.027
3.033
3.040
3.041

0.001
0.002
0.001
0.000

0.598
0.671
0.603
0.620

109
Table D.1: (continued) Microprobe Analyses of Apatite.
Weight Percent Components
Label
SiO2 Al2O3 FeO* MnO
Sample J137-C
Apatite 1: points in core along C axis
J137-C Ap1L1-1
0.062 0.003 0.021 0.012
J137-C Ap1L1-2
0.069 0.005 0.000 0.036
J137-C Ap1L1-3
0.064 0.000 0.032 0.011
J137-C Ap1L1-4
0.067 0.005 0.000 0.015
J137-C Ap1L1-5
0.029 0.014 0.015 0.029
J137-C Ap1L1-6
0.030 0.015 0.012 0.017
J137-C Ap1L1-7
0.023 0.012 0.000 0.026

MgO

CaO

SrO

0.083
0.056
0.037
0.054
0.033
0.044
0.030

54.648
54.320
54.819
54.491
54.676
54.652
54.628

0.399
0.406
0.421
0.405
0.410
0.465
0.439

0.000
0.000
0.006
0.000
0.000
0.001
0.000

0.040
0.029
0.010
0.001
0.060
0.008
0.033

0.038
0.049
0.041
0.058
0.011
0.116
0.047

0.044
0.042
0.052
0.023
0.014
0.007
0.070

0.000
0.000
0.012
0.000
0.000
0.000
0.000

0.210
0.234
0.224
0.212
0.162
0.169
0.174

0.005
0.006
0.007
0.003
0.000
0.000
0.006

Apatite 1: points on rim

J137-C Ap1r-8
0.018
J137-C Ap1r-9
0.032
J137-C Ap1r-10
0.020
J137-C Ap1r-11
0.030

K2O P2O5

SO3

Cl

O=F O=Cl

Total

42.786
42.491
42.424
42.742
43.028
42.826
43.522

0.051
0.012
0.034
0.046
0.043
0.032
0.052

1.960
1.864
1.835
1.944
1.998
1.924
1.917

0.025
0.018
0.011
0.008
0.006
0.015
0.007

-0.825
-0.785
-0.773
-0.818
-0.841
-0.810
-0.807

0.186 99.747
0.177 99.029
0.174 99.442
0.185 99.441
0.190 99.877
0.183 99.705
0.182 100.361

0.019
0.023
0.000
0.000

0.000
0.000
0.027
0.016

0.034
0.036
0.040
0.035

54.200
54.186
54.786
54.716

0.452
0.455
0.447
0.438

0.000
0.006
0.001
0.000

0.021
0.025
0.027
0.044

0.063
0.091
0.071
0.070

0.044
0.032
0.000
0.024

0.000
0.000
0.000
0.000

0.148
0.177
0.186
0.160

0.004
0.009
0.000
0.010

43.429
43.489
43.787
43.360

0.056
0.012
0.036
0.016

1.910
2.095
1.974
1.890

0.009
0.000
0.001
0.007

-0.804
-0.882
-0.831
-0.796

0.181 99.795
0.199 99.985
0.188 100.761
0.180 100.205

Area 2 - Apatite 2 included in Olivine

J137-C c2Ap2-1
0.048 0.012 0.011
J137-C c2Ap2-2
0.076 0.003 0.036
J137-C c2Ap2-3
0.077 0.000 0.048
J137-C c2Ap2-4
0.059 0.000 0.093

0.017
0.019
0.026
0.012

0.054
0.100
0.110
0.072

54.485
54.232
54.044
54.666

0.433
0.445
0.454
0.436

0.000
0.014
0.000
0.000

0.029
0.043
0.010
0.030

0.080
0.071
0.094
0.074

0.054
0.090
0.013
0.047

0.000
0.000
0.000
0.000

0.165
0.343
0.372
0.196

0.003
0.015
0.000
0.000

43.780
42.515
42.571
43.043

0.030
0.022
0.052
0.031

2.266
1.999
1.953
1.956

0.014
0.007
0.030
0.012

-0.954
-0.842
-0.822
-0.823

0.215 100.741
0.190 99.376
0.186 99.217
0.186 100.088

Olivine; points across from Ol to calcite

0.000 0.019 0.017 0.041 54.389 0.396
0.000 0.020 0.019 0.000 54.929 0.496
0.002 0.019 0.006 0.037 54.760 0.441
0.015 0.021 0.000 0.060 54.290 0.438
0.000 0.001 0.003 0.017 54.640 0.416
0.030 0.036 0.019 0.058 54.124 0.421
0.001 0.013 0.039 0.034 54.234 0.414
0.003 0.032 0.037 0.004 54.167 0.482

0.000
0.000
0.000
0.000
0.000
0.000
0.004
0.000

0.068
0.030
0.000
0.020
0.024
0.029
0.042
0.048

0.070
0.112
0.056
0.033
0.100
0.092
0.000
0.144

0.073
0.072
0.030
0.038
0.032
0.015
0.000
0.094

0.004
0.000
0.000
0.000
0.000
0.015
0.001
0.000

0.190
0.137
0.145
0.177
0.136
0.132
0.151
0.147

0.000
0.000
0.000
0.002
0.002
0.004
0.000
0.002

42.539
43.058
43.310
42.613
42.806
43.665
43.320
43.081

0.000
0.028
0.036
0.025
0.000
0.014
0.000
0.013

1.964
1.909
1.985
1.901
1.952
1.916
1.834
1.926

0.009
0.012
0.009
0.005
0.000
0.010
0.007
0.012

-0.827
-0.804
-0.836
-0.800
-0.822
-0.807
-0.772
-0.811

0.187 99.179
0.181 100.212
0.189 100.214
0.181 99.078
0.185 99.538
0.182 100.005
0.174 99.518
0.183 99.577

Area 2 - Apatite 3 outside of

J137-C c2Ap3-1
0.042
J137-C c2Ap3-2
0.012
J137-C c2Ap3-3
0.024
J137-C c2Ap3-4
0.060
J137-C c2Ap3-5
0.045
J137-C c2Ap3-6
0.049
J137-C c2Ap3-7
0.023
J137-C c2Ap3-8
0.012

0.010
0.000
0.002
0.006

BaO La2O3 Ce2O3 Nd2O3 Sm2O3 Na2O

Apatite 4, points along core parallel to C axis

J137-C c2Ap4-1
0.082 0.002 0.017 0.000
J137-C c2Ap4-2
0.045 0.011 0.048 0.044
J137-C c2Ap4-3
0.045 0.000 0.011 0.004
J137-C c2Ap4-4
0.029 0.000 0.073 0.000
J137-C c2Ap4-5
0.023 0.000 0.117 0.045

0.089
0.040
0.046
0.067
0.000

53.977
54.205
54.721
54.178
54.384

0.456
0.407
0.443
0.433
0.449

0.000
0.007
0.001
0.000
0.000

0.024
0.000
0.000
0.031
0.058

0.058
0.095
0.061
0.028
0.060

0.050
0.037
0.052
0.041
0.086

0.000
0.000
0.000
0.000
0.000

0.170
0.163
0.157
0.153
0.124

0.000
0.000
0.006
0.006
0.000

42.471
42.438
43.069
43.968
43.174

0.016
0.013
0.041
0.008
0.043

1.974
1.872
1.847
1.838
2.095

0.000
0.006
0.007
0.000
0.000

-0.831
-0.788
-0.778
-0.774
-0.882

0.188 98.741
0.178 98.819
0.176 99.909
0.175 100.252
0.199 99.976

Sample J106-F
Apatite 1: points in core along C axis
J106-F Ap1-1
0.025 0.001 0.022
J106-F Ap1-2
0.018 0.013 0.019
J106-F Ap1-3
0.016 0.000 0.026
J106-F Ap1-4
0.022 0.009 0.000
J106-F Ap1-5
0.020 0.000 0.023
J106-F Ap1-6
0.015 0.009 0.029
J106-F Ap1-7
0.015 0.012 0.015
J106-F Ap1-8
0.000 0.009 0.019

0.028
0.061
0.045
0.000
0.008
0.000
0.000
0.000

0.108
0.092
0.087
0.074
0.078
0.076
0.037
0.010

53.619
53.970
53.968
54.418
53.530
53.676
53.682
53.876

0.583
0.603
0.606
0.611
0.641
0.623
0.772
0.896

0.000
0.000
0.005
0.000
0.000
0.000
0.000
0.000

0.069
0.044
0.059
0.054
0.028
0.071
0.074
0.088

0.136
0.198
0.139
0.156
0.102
0.164
0.116
0.229

0.055
0.026
0.096
0.090
0.044
0.088
0.075
0.149

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.257
0.237
0.247
0.221
0.247
0.247
0.226
0.216

0.000
0.009
0.000
0.005
0.005
0.003
0.008
0.013

42.932
43.328
42.947
42.724
43.107
42.616
42.874
43.554

0.028
0.068
0.051
0.034
0.037
0.021
0.054
0.041

1.735
1.769
1.781
1.673
1.754
1.725
1.651
1.698

0.000
0.000
0.010
0.000
0.008
0.000
0.017
0.003

-0.730
-0.745
-0.750
-0.704
-0.739
-0.726
-0.695
-0.715

0.165 99.031
0.168 99.877
0.169 99.502
0.159 99.545
0.167 99.060
0.164 98.801
0.157 99.088
0.161 100.248

Apatite 1: perpendicular to C axis, core to rim

J106-F Ap1l2-1
0.000 0.000 0.031 0.000
J106-F Ap1l2-2
0.008 0.007 0.004 0.026
J106-F Ap1l2-3
0.009 0.009 0.017 0.022
J106-F Ap1l2-4
0.011 0.005 0.000 0.017
J106-F Ap1l2-5
0.000 0.000 0.000 0.034
J106-F Ap1l2-6
0.008 0.000 0.036 0.024
J106-F Ap1l2-7
0.010 0.017 0.042 0.023
J106-F Ap1l2-8
0.020 0.000 0.007 0.029

0.085
0.043
0.065
0.078
0.118
0.119
0.094
0.082

54.180
54.097
54.098
54.128
54.093
53.711
54.467
54.435

0.610
0.560
0.591
0.609
0.595
0.609
0.600
0.515

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.013
0.037
0.062
0.037
0.072
0.036
0.060
0.043

0.129
0.102
0.102
0.155
0.178
0.129
0.133
0.050

0.060
0.088
0.103
0.068
0.053
0.017
0.068
0.007

0.002
0.000
0.018
0.000
0.000
0.009
0.000
0.000

0.278
0.192
0.235
0.227
0.238
0.222
0.204
0.146

0.003
0.001
0.003
0.000
0.006
0.002
0.000
0.004

43.004
43.176
42.666
43.897
43.506
42.622
42.481
42.697

0.013
0.037
0.061
0.035
0.025
0.032
0.051
0.026

1.658
1.587
1.730
1.769
1.606
1.744
1.769
1.758

0.010
0.000
0.000
0.002
0.007
0.030
0.008
0.000

-0.698
-0.668
-0.729
-0.745
-0.676
-0.734
-0.745
-0.740

0.157 99.536
0.151 99.448
0.164 99.228
0.168 100.460
0.153 100.008
0.166 98.782
0.168 99.450
0.167 99.247

Apatite 2, in cluster near Ap1, points core to rim

J106-F Ap2-1
0.009 0.012 0.019 0.026 0.097 54.674 0.604 0.000
J106-F Ap2-2
0.008 0.004 0.017 0.016 0.073 54.630 0.549 0.000
J106-F Ap2-3
0.012 0.000 0.016 0.026 0.091 54.093 0.492 0.000

0.065
0.040
0.031

0.080
0.072
0.051

0.047
0.089
0.047

0.000 0.213 0.003 43.250 0.000 2.027 0.000 -0.854 0.193 100.464
0.000 0.197 0.000 42.945 0.000 1.775 0.001 -0.747 0.169 99.838
0.009 0.170 0.000 42.725 0.017 1.816 0.008 -0.765 0.173 99.012

Apatite 3, in cluster far from Ap2, points core to rim

J106-F Ap3-1
0.019 0.010 0.020 0.009 0.096
J106-F Ap3-2
0.011 0.004 0.000 0.067 0.085
J106-F Ap3-3
0.019 0.021 0.013 0.000 0.078
J106-F Ap3-4
0.011 0.000 0.015 0.018 0.055

0.060
0.000
0.066
0.075

0.135
0.122
0.084
0.068

0.069
0.102
0.064
0.028

0.000
0.000
0.000
0.006

54.161
54.669
54.454
54.505

0.591
0.556
0.517
0.521

0.000
0.000
0.002
0.000

0.221
0.233
0.162
0.138

0.004
0.014
0.004
0.007

43.532
43.196
43.166
42.802

0.001
0.034
0.030
0.004

1.871
1.800
1.801
1.859

0.001
0.003
0.007
0.008

-0.788
-0.758
-0.758
-0.783

0.178 100.188
0.171 100.310
0.171 99.898
0.177 99.515

110
Table D.1: (continued) Microprobe Analyses of Apatite.
Ions per 12 Oxygen + 1 (OH,F,Cl):sum excludes F and Cl
Ca
Sr
Y
Label
Si
Al
Fe
Mn
Mg
Sample J137-C
Apatite 1: points in core along C axis
J137-C Ap1L1-1
0.005 0.000 0.001 0.001 0.010 4.879 0.019 0.000
J137-C Ap1L1-2
0.006 0.000 0.000 0.003 0.007 4.884 0.020 0.000
J137-C Ap1L1-3
0.005 0.000 0.002 0.001 0.005 4.915 0.020 0.000
J137-C Ap1L1-4
0.006 0.000 0.000 0.001 0.007 4.876 0.020 0.000
J137-C Ap1L1-5
0.002 0.001 0.001 0.002 0.004 4.870 0.020 0.000
J137-C Ap1L1-6
0.003 0.001 0.001 0.001 0.005 4.881 0.023 0.000
J137-C Ap1L1-7
0.002 0.001 0.000 0.002 0.004 4.832 0.021 0.000

Ba

La

Ce

Nd

Sm

Gd

Na

Cl

Sum

0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.001
0.001
0.000
0.000
0.002
0.000
0.001

0.001
0.002
0.001
0.002
0.000
0.004
0.001

0.001
0.001
0.002
0.001
0.000
0.000
0.002

0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.034
0.038
0.036
0.034
0.026
0.027
0.028

0.000
0.001
0.001
0.000
0.000
0.000
0.001

3.018
3.019
3.006
3.022
3.028
3.022
3.042

0.003
0.001
0.002
0.003
0.003
0.002
0.003

0.516
0.495
0.486
0.513
0.525
0.507
0.500

0.003
0.003
0.002
0.001
0.001
0.002
0.001

7.976
7.981
7.997
7.971
7.960
7.971
7.939

Apatite 1: points on rim

J137-C Ap1r-8
0.001
J137-C Ap1r-9
0.003
J137-C Ap1r-10
0.002
J137-C Ap1r-11
0.003

0.001
0.002
0.000
0.000

0.000
0.000
0.002
0.001

0.004
0.005
0.005
0.004

4.816
4.812
4.825
4.851

0.022
0.022
0.021
0.021

0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000

0.001
0.001
0.001
0.001

0.002
0.003
0.002
0.002

0.001
0.001
0.000
0.001

0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000

0.024
0.028
0.030
0.026

0.000
0.001
0.000
0.001

3.049
3.052
3.047
3.037

0.003
0.001
0.002
0.001

0.501
0.549
0.513
0.495

0.001
0.000
0.000
0.001

7.926
7.930
7.937
7.950

Area 2 - Apatite 2 included in Olivine

J137-C c2Ap2-1
0.004 0.001 0.001
J137-C c2Ap2-2
0.006 0.000 0.003
J137-C c2Ap2-3
0.006 0.000 0.003
J137-C c2Ap2-4
0.005 0.000 0.006

0.001
0.001
0.002
0.001

0.007
0.013
0.014
0.009

4.806
4.867
4.851
4.862

0.021
0.022
0.022
0.021

0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000

0.001
0.001
0.000
0.001

0.002
0.002
0.003
0.002

0.002
0.003
0.000
0.001

0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000

0.026
0.056
0.060
0.032

0.000
0.002
0.000
0.000

3.051
3.015
3.020
3.025

0.002
0.001
0.003
0.002

0.590
0.530
0.518
0.513

0.002
0.001
0.004
0.002

7.925
7.992
7.985
7.967

Olivine; points across from Ol to calcite

0.000 0.001 0.001 0.005 4.888 0.019
0.000 0.001 0.001 0.000 4.883 0.024
0.000 0.001 0.000 0.005 4.857 0.021
0.001 0.001 0.000 0.008 4.875 0.021
0.000 0.000 0.000 0.002 4.887 0.020
0.003 0.003 0.001 0.007 4.795 0.020
0.000 0.001 0.003 0.004 4.831 0.020
0.000 0.002 0.003 0.000 4.838 0.023

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.002
0.001
0.000
0.001
0.001
0.001
0.001
0.001

0.002
0.003
0.002
0.001
0.003
0.003
0.000
0.004

0.002
0.002
0.001
0.001
0.001
0.000
0.000
0.003

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.031
0.022
0.023
0.029
0.022
0.021
0.024
0.024

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

3.021
3.024
3.035
3.023
3.025
3.056
3.049
3.040

0.000
0.002
0.002
0.002
0.000
0.001
0.000
0.001

0.521
0.501
0.520
0.504
0.515
0.501
0.482
0.508

0.001
0.002
0.001
0.001
0.000
0.001
0.001
0.002

7.976
7.965
7.950
7.968
7.966
7.916
7.936
7.942

Area 2 - Apatite 3 outside of

J137-C c2Ap3-1
0.004
J137-C c2Ap3-2
0.001
J137-C c2Ap3-3
0.002
J137-C c2Ap3-4
0.005
J137-C c2Ap3-5
0.004
J137-C c2Ap3-6
0.004
J137-C c2Ap3-7
0.002
J137-C c2Ap3-8
0.001

0.001
0.000
0.000
0.001

Apatite 4, points along core parallel to C axis

J137-C c2Ap4-1
0.007 0.000 0.001 0.000
J137-C c2Ap4-2
0.004 0.001 0.003 0.003
J137-C c2Ap4-3
0.004 0.000 0.001 0.000
J137-C c2Ap4-4
0.002 0.000 0.005 0.000
J137-C c2Ap4-5
0.002 0.000 0.008 0.003

0.011
0.005
0.006
0.008
0.000

4.865
4.884
4.868
4.780
4.841

0.022
0.020
0.021
0.021
0.022

0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000

0.001
0.000
0.000
0.001
0.002

0.002
0.003
0.002
0.001
0.002

0.001
0.001
0.002
0.001
0.003

0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000

0.028
0.027
0.025
0.024
0.020

0.000
0.000
0.001
0.001
0.000

3.025
3.021
3.028
3.065
3.037

0.001
0.001
0.003
0.000
0.003

0.525
0.498
0.485
0.479
0.550

0.000
0.001
0.001
0.000
0.000

7.964
7.972
7.960
7.909
7.942

Sample J106-F
Apatite 1: points in core along C axis
J106-F Ap1-1
0.002 0.000 0.002
J106-F Ap1-2
0.001 0.001 0.001
J106-F Ap1-3
0.001 0.000 0.002
J106-F Ap1-4
0.002 0.001 0.000
J106-F Ap1-5
0.002 0.000 0.002
J106-F Ap1-6
0.001 0.001 0.002
J106-F Ap1-7
0.001 0.001 0.001
J106-F Ap1-8
0.000 0.001 0.001

0.002
0.004
0.003
0.000
0.001
0.000
0.000
0.000

0.014
0.011
0.011
0.009
0.010
0.010
0.005
0.001

4.807
4.797
4.824
4.867
4.793
4.833
4.814
4.776

0.028
0.029
0.029
0.030
0.031
0.030
0.037
0.043

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.002
0.001
0.002
0.002
0.001
0.002
0.002
0.003

0.004
0.006
0.004
0.005
0.003
0.005
0.004
0.007

0.002
0.001
0.003
0.003
0.001
0.003
0.002
0.004

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.042
0.038
0.040
0.036
0.040
0.040
0.037
0.035

0.000
0.001
0.000
0.001
0.001
0.000
0.001
0.001

3.042
3.043
3.033
3.020
3.050
3.032
3.038
3.051

0.002
0.004
0.003
0.002
0.002
0.001
0.003
0.003

0.459
0.464
0.470
0.442
0.464
0.459
0.437
0.444

0.000
0.000
0.001
0.000
0.001
0.000
0.002
0.000

7.948
7.940
7.956
7.976
7.936
7.961
7.947
7.926

Apatite 1: perpendicular to C axis, core to rim

J106-F Ap1l2-1
0.000 0.000 0.002 0.000
J106-F Ap1l2-2
0.001 0.001 0.000 0.002
J106-F Ap1l2-3
0.001 0.001 0.001 0.002
J106-F Ap1l2-4
0.001 0.000 0.000 0.001
J106-F Ap1l2-5
0.000 0.000 0.000 0.002
J106-F Ap1l2-6
0.001 0.000 0.003 0.002
J106-F Ap1l2-7
0.001 0.002 0.003 0.002
J106-F Ap1l2-8
0.002 0.000 0.000 0.002

0.011
0.005
0.008
0.010
0.015
0.015
0.012
0.010

4.837
4.824
4.852
4.773
4.796
4.836
4.885
4.878

0.030
0.027
0.029
0.029
0.029
0.030
0.029
0.025

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.001
0.002
0.001
0.002
0.001
0.002
0.001

0.004
0.003
0.003
0.005
0.005
0.004
0.004
0.002

0.002
0.003
0.003
0.002
0.002
0.001
0.002
0.000

0.000
0.000
0.001
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

0.045
0.031
0.038
0.036
0.038
0.036
0.033
0.024

0.000
0.000
0.000
0.000
0.001
0.000
0.000
0.000

3.034
3.042
3.024
3.059
3.048
3.032
3.010
3.023

0.001
0.002
0.004
0.002
0.002
0.002
0.003
0.002

0.437
0.418
0.458
0.460
0.420
0.464
0.468
0.465

0.001
0.000
0.000
0.000
0.001
0.004
0.001
0.000

7.966
7.942
7.968
7.919
7.939
7.962
7.987
7.970

Apatite 2, in cluster near Ap1, points core to rim

J106-F Ap2-1
0.001 0.001 0.001 0.002 0.012
J106-F Ap2-2
0.001 0.000 0.001 0.001 0.009
J106-F Ap2-3
0.001 0.000 0.001 0.002 0.011

4.849 0.029 0.000

4.870 0.027 0.000
4.857 0.024 0.000

0.000
0.000
0.000

0.002
0.001
0.001

0.002
0.002
0.002

0.001 0.000 0.000

0.003 0.000 0.000
0.001 0.000 0.000

0.034 0.000 3.031 0.000 0.531 0.000

0.032 0.000 3.025 0.000 0.467 0.000
0.028 0.000 3.031 0.001 0.481 0.001

7.966
7.972
7.960

Apatite 3, in cluster far from Ap2, points core to rim

J106-F Ap3-1
0.002 0.001 0.001 0.001 0.012
J106-F Ap3-2
0.001 0.000 0.000 0.005 0.010
J106-F Ap3-3
0.002 0.002 0.001 0.000 0.010
J106-F Ap3-4
0.001 0.000 0.001 0.001 0.007

4.800
4.849
4.844
4.877

0.000
0.000
0.000
0.000

0.002
0.000
0.002
0.002

0.004
0.004
0.003
0.002

0.002
0.003
0.002
0.001

0.035
0.037
0.026
0.022

7.937
7.967
7.952
7.967

0.028
0.027
0.025
0.025

0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000

0.000
0.001
0.000
0.001

3.049
3.027
3.034
3.026

0.000
0.002
0.002
0.000

0.490
0.471
0.473
0.491

0.000
0.000
0.001
0.001

111
Table D.2: Microprobe Analyses of Calcite and Dolomite.

Label

C and O done by stoichiometry

FeO* as total iron
Weight Percent Oxides
FeO* MnO MgO CaO SrO BaO Na2O
CO3 SO3 Total

Cations per 6 Oxygen

Fe Mn Mg
Ca

Sr

Ba

Na

Sum

Sample J151-A7
Dolomite-1
J151-A7 Dol1-1
J151-A7 Dol1-2
J151-A7 Dol1-3
J151-A7 Dol1-4
J151-A7 Dol1-5
J151-A7 Dol1-6
J151-A7 Dol1-7
J151-A7 Dol1-8

0.532
0.610
0.570
0.497
0.574
0.561
0.566
0.500

0.202
0.189
0.183
0.189
0.178
0.177
0.156
0.219

20.651
20.845
20.726
20.696
20.734
20.397
20.829
20.642

29.381
29.618
29.734
29.454
29.899
29.745
29.724
29.667

0.280
0.309
0.334
0.289
0.318
0.322
0.290
0.279

0.000
0.021
0.040
0.000
0.030
0.000
0.000
0.000

0.004
0.007
0.000
0.000
0.022
0.012
0.000
0.000

46.222
46.645
46.579
46.285
46.728
46.219
46.648
46.399

0.006
0.002
0.000
0.013
0.000
0.000
0.000
0.013

97.278
98.246
98.166
97.423
98.482
97.433
98.214
97.718

0.014
0.016
0.015
0.013
0.015
0.015
0.015
0.013

0.005
0.005
0.005
0.005
0.005
0.005
0.004
0.006

0.976
0.976
0.972
0.976
0.969
0.964
0.975
0.971

0.998
0.997
1.002
0.999
1.004
1.010
1.000
1.004

0.005
0.006
0.006
0.005
0.006
0.006
0.005
0.005

0.000
0.000
0.001
0.000
0.000
0.000
0.000
0.000

0.000
0.001
0.000
0.000
0.001
0.001
0.000
0.000

2.000
2.000
2.000
2.000
2.000
2.000
2.000
2.000

0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

3.998
4.000
4.000
3.999
4.000
4.000
4.000
3.999

Calcite-1
J151-A7 CC1-1
J151-A7 CC1-2
J151-A7 CC1-3
J151-A7 CC1-4
J151-A7 CC1-5
J151-A7 CC1-6
J151-A7 CC1-7
J151-A7 CC1-8

0.055
0.076
0.084
0.039
0.076
0.060
0.078
0.082

0.137
0.155
0.153
0.122
0.125
0.106
0.125
0.133

1.017
1.209
1.495
1.273
1.229
1.430
1.600
1.439

54.206
54.041
53.278
54.153
53.960
53.362
53.300
53.209

0.817
0.776
0.737
0.777
0.727
0.773
0.799
0.769

0.080
0.102
0.088
0.133
0.103
0.106
0.224
0.078

0.016
0.036
0.033
0.030
0.021
0.006
0.001
0.001

44.151
44.272
43.951
44.388
44.167
43.940
44.106
43.862

0.000
0.005
0.000
0.000
0.001
0.021
0.000
0.032

100.479
100.672
99.819
100.915
100.409
99.804
100.233
99.604

0.002
0.002
0.002
0.001
0.002
0.002
0.002
0.002

0.004
0.004
0.004
0.003
0.004
0.003
0.004
0.004

0.050
0.060
0.074
0.063
0.061
0.071
0.079
0.072

1.927
1.916
1.903
1.915
1.918
1.906
1.897
1.904

0.016
0.015
0.014
0.015
0.014
0.015
0.015
0.015

0.001
0.001
0.001
0.002
0.001
0.001
0.003
0.001

0.001
0.002
0.002
0.002
0.001
0.000
0.000
0.000

2.000
2.000
2.000
2.000
2.000
2.000
2.000
2.000

0.000
0.000
0.000
0.000
0.000
0.001
0.000
0.001

4.000
4.001
4.001
4.000
4.001
3.999
4.000
3.998

Dolomite inclusions (in Calcite)

J151-A7 DolInc-1
0.523 0.209
J151-A7 DolInc-2
0.635 0.215
J151-A7 DolInc-3
0.569 0.173
J151-A7 DolInc-4
0.622 0.217
J151-A7 DolInc-5
0.599 0.188

21.036
20.957
20.672
20.951
20.581

29.674
29.804
30.476
29.610
29.978

0.376
0.315
0.338
0.306
0.330

0.017
0.021
0.000
0.008
0.000

0.019
0.000
0.001
0.000
0.010

46.881
46.968
47.105
46.786
46.654

0.000
0.023
0.013
0.003
0.006

98.734
98.937
99.346
98.503
98.346

0.014
0.017
0.015
0.016
0.016

0.006
0.006
0.005
0.006
0.005

0.980
0.974
0.958
0.978
0.963

0.993
0.996
1.016
0.993
1.009

0.007
0.006
0.006
0.006
0.006

0.000
0.000
0.000
0.000
0.000

0.001
0.000
0.000
0.000
0.001

2.000
2.000
2.000
2.000
2.000

0.000
0.001
0.000
0.000
0.000

4.000
3.999
3.999
3.999
3.999

Calcite-2
J151-A7 CC2-1
J151-A7 CC2-2
J151-A7 CC2-3

0.079 0.119
0.067 0.140
0.078 0.112

1.682 53.446 0.738 0.119 0.019 44.279 0.010 100.491

1.639 53.048 0.718 0.192 0.023 43.964 0.022 99.812
1.325 53.270 0.794 0.165 0.008 43.759 0.000 99.511

0.002 0.003 0.083 1.895 0.014 0.002 0.001 2.000 0.000 4.000
0.002 0.004 0.081 1.894 0.014 0.003 0.002 2.000 0.001 4.000
0.002 0.003 0.066 1.911 0.015 0.002 0.001 2.000 0.000 4.000

Dolomite Exsolution (in Calcite)

J151-A7 DolExsolv-1 0.523 0.192 20.574 29.839 0.330 0.000 0.006 46.466 0.000 97.931
J151-A7 DolExsolv-2 0.433 0.180 20.936 29.660 0.282 0.053 0.007 46.655 0.004 98.209
J151-A7 DolExsolv-3 0.418 0.138 20.699 29.798 0.294 0.000 0.006 46.460 0.001 97.813

0.014 0.005 0.967 1.008 0.006 0.000 0.000 2.000 0.000 4.000
0.011 0.005 0.980 0.998 0.005 0.001 0.000 2.000 0.000 4.000
0.011 0.004 0.973 1.007 0.005 0.000 0.000 2.000 0.000 4.000

Area-4: Calcite
J151-A7 CCa4-1
J151-A7 CCa4-2
J151-A7 CCa4-3
J151-A7 CCa4-4
J151-A7 CCa4-5

0.074
0.063
0.073
0.041
0.073

0.112
0.113
0.134
0.110
0.118

1.323
1.324
1.132
1.067
1.021

53.797
53.592
53.890
54.266
54.458

0.729
0.810
0.700
0.775
0.655

0.079
0.224
0.124
0.151
0.048

0.033
0.017
0.024
0.000
0.035

44.139
44.033
44.034
44.243
44.298

0.000
0.001
0.018
0.015
0.000

100.284
100.177
100.129
100.668
100.706

0.002
0.002
0.002
0.001
0.002

0.003
0.003
0.004
0.003
0.003

0.065
0.066
0.056
0.053
0.050

1.913
1.910
1.921
1.925
1.930

0.014
0.016
0.014
0.015
0.013

0.001
0.003
0.002
0.002
0.001

0.002
0.001
0.002
0.000
0.002

2.000
2.000
2.000
2.000
2.000

0.000
0.000
0.000
0.000
0.000

4.001
4.000
4.000
3.999
4.001

Area 4: Dolomite
J151-A7 DolA4-1
J151-A7 DolA4-2
J151-A7 DolA4-3
J151-A7 DolA4-4
J151-A7 DolA4-5

0.470
0.453
0.529
0.499
0.476

0.173
0.162
0.149
0.162
0.190

21.171
21.188
20.877
21.151
20.939

29.802
29.739
29.864
29.649
29.875

0.304
0.275
0.300
0.316
0.278

0.000
0.000
0.000
0.067
0.052

0.000
0.013
0.008
0.000
0.000

47.068
46.986
46.799
46.942
46.859

0.011
0.000
0.000
0.014
0.000

98.999
98.816
98.526
98.800
98.669

0.012
0.012
0.014
0.013
0.012

0.005
0.004
0.004
0.004
0.005

0.982
0.985
0.974
0.984
0.976

0.994
0.993
1.002
0.991
1.001

0.006
0.005
0.005
0.006
0.005

0.000
0.000
0.000
0.001
0.001

0.000
0.001
0.001
0.000
0.000

2.000
2.000
2.000
2.000
2.000

0.000
0.000
0.000
0.000
0.000

3.999
4.000
3.999
3.999
3.999

112
Table D.2: (continued) Microprobe Analyses of Calcite and Dolomite.

Label

C and O done by stoichiometry

FeO* as total iron
Weight Percent Oxides
FeO* MnO MgO CaO SrO BaO Na2O
CO3 SO3 Total

Sample J179-E
Dolomite
J179-E Carb1-1
J179-E Carb1-2
J179-E Carb1-3
J179-E Carb2-1
J179-E Carb2-2
J179-E Carb2-3

0.510
0.492
0.653
0.213
0.207
0.258

Matrix Calcite
J179-E MatCC-1
J179-E MatCC-2
J179-E MatCC-3

0.020 0.099
0.011 0.096
0.002 0.103

0.148
0.385
0.147
0.123
0.163
0.150

21.268
21.341
21.428
20.950
21.078
20.907

29.790
29.679
29.952
30.053
30.110
30.357

0.481
0.114
0.311
0.289
0.318
0.296

0.000
0.000
0.000
0.031
0.000
0.087

0.003
0.000
0.000
0.000
0.014
0.005

47.224
47.192
47.535
46.830
47.016
47.059

0.009
0.008
0.000
0.019
0.000
0.000

99.433
99.211
100.026
98.509
98.907
99.118

Cations per 6 Oxygen

Fe Mn Mg
Ca

0.013
0.013
0.017
0.006
0.005
0.007

0.004
0.010
0.004
0.003
0.004
0.004

0.983
0.987
0.984
0.977
0.979
0.970

0.990
0.987
0.989
1.007
1.005
1.013

Sr

Ba

Na

Sum

0.009
0.002
0.006
0.005
0.006
0.005

0.000
0.000
0.000
0.000
0.000
0.001

0.000
0.000
0.000
0.000
0.001
0.000

2.000
2.000
2.000
2.000
2.000
2.000

0.000
0.000
0.000
0.001
0.000
0.000

4.000
4.000
3.999
3.999
4.000
4.000

1.163 54.127 0.751 0.000 0.013 44.165 0.000 100.337

1.149 54.233 0.714 0.066 0.024 44.229 0.005 100.526
1.037 54.380 0.746 0.039 0.022 44.218 0.000 100.547

0.001 0.003 0.058 1.924 0.015 0.000 0.001 2.000 0.000 4.000
0.000 0.003 0.057 1.925 0.014 0.001 0.002 2.000 0.000 4.000
0.000 0.003 0.051 1.930 0.014 0.001 0.001 2.000 0.000 4.001

Dolomite on Fracture/Vein
J179-E DolBl-1
0.190 0.104 21.145 30.516 0.296 0.000 0.010 47.356 0.000 99.617
J179-E DolBl-2
0.230 0.110 21.179 30.524 0.308 0.000 0.000 47.431 0.000 99.783
J179-E DolBl-3
0.188 0.157 21.087 30.494 0.301 0.000 0.010 47.321 0.005 99.562

0.005 0.003 0.975 1.011 0.005 0.000 0.001 2.000 0.000 4.000
0.006 0.003 0.975 1.010 0.006 0.000 0.000 2.000 0.000 3.999
0.005 0.004 0.973 1.011 0.005 0.000 0.001 2.000 0.000 4.000

Dolomite Blebs in Calcite

J179-E Dol-1
0.107 0.119 21.438 30.614 0.264 0.000 0.029 47.734 0.019 100.323
J179-E Dol-2
0.067 0.153 21.236 30.413 0.343 0.000 0.002 47.393 0.036 99.642

0.003 0.003 0.981 1.007 0.005 0.000 0.002 2.000 0.000 4.000
0.002 0.004 0.978 1.007 0.006 0.000 0.000 2.000 0.001 3.998

Sample J106-F
Dolomite Inclusions
J106-F A1-DolInc-1
J106-F A1-DolInc-2
J106-F A1-DolInc-3
J106-F A1-DolInc-4
J106-F A1-DolInc-5

0.569
0.635
0.658
0.809
0.939

0.015
0.016
0.017
0.021
0.024

Sample SP24-53
Calcite in Dolomite
SP24-53 CCinDol-1
SP24-53 CCinDol-2

0.069 0.081
0.094 0.107

0.621 54.013 1.410 0.112 0.033 43.813 0.000 100.151

0.582 54.117 1.273 0.061 0.012 43.820 0.006 100.072

0.002 0.002 0.031 1.935 0.027 0.002 0.002 2.000 0.000 4.001
0.003 0.003 0.029 1.938 0.025 0.001 0.001 2.000 0.000 4.000

Martrix Dolomite
SP24-53 matDol-1
SP24-53 matDol-2
SP24-53 matDol-3

0.746 0.180 20.771 29.610 0.577 0.029 0.001 46.737 0.000 98.651
0.893 0.174 20.610 29.667 0.567 0.000 0.000 46.702 0.011 98.623
1.086 0.276 20.569 29.576 0.633 0.000 0.000 46.791 0.000 98.930

0.020 0.005 0.970 0.994 0.011 0.000 0.000 2.000 0.000 4.000
0.023 0.005 0.964 0.997 0.010 0.000 0.000 2.000 0.000 3.999
0.028 0.007 0.960 0.992 0.012 0.000 0.000 2.000 0.000 3.999

0.131
0.142
0.168
0.181
0.227

21.332
21.230
21.105
20.688
20.988

30.362
30.452
30.206
30.173
29.785

0.409
0.358
0.369
0.397
0.437

0.022
0.030
0.000
0.000
0.000

0.000
0.009
0.000
0.013
0.000

47.738
47.733
47.411
47.074
47.205

0.007
0.002
0.000
0.006
0.009

100.570
100.590
99.916
99.343
99.591

0.003
0.004
0.004
0.005
0.006

0.976
0.971
0.972
0.960
0.971

0.998
1.001
1.000
1.006
0.990

0.007
0.006
0.007
0.007
0.008

0.000
0.000
0.000
0.000
0.000

0.000
0.001
0.000
0.001
0.000

2.000
2.000
2.000
2.000
2.000

0.000
0.000
0.000
0.000
0.000

4.000
4.000
4.000
4.000
4.000

113

Table D.3: Microprobe Analyses of Magnetite.

Magnetite (calculated iron, excluding minor Nb and Ta).
Label
Sample J151-A
J151-A-Mag1-1
J151-A-Mag1-2
J151-A-Mag1-3
J151-A-Mag1-4
J151-A-Mag1-5
J151-A-Mag1-6
J151-A-Mag1-7
J151-A-Mag1-8

SiO2 TiO2 Al2O3 Fe2O3

FeO

V2O3 MnO MgO ZnO

Total

Si

Ti

Al(VI) Fe3+ Fe2+

Mn

Mg

Zn

Sum

1.800
2.060
1.820
1.070
1.020
1.130
1.340
1.800

0.640
0.900
1.040
0.800
0.780
0.660
0.420
0.440

66.220
66.130
66.530
67.760
68.190
68.140
66.720
65.910

27.430
26.110
25.910
26.700
26.690
26.940
27.670
28.360

0.380
0.360
0.400
0.430
0.480
0.470
0.450
0.470

0.420
0.600
0.570
0.450
0.430
0.490
0.430
0.580

3.260
4.210
4.280
3.350
3.410
3.300
2.700
2.460

0.040
0.070
0.070
0.070
0.110
0.080
0.080
0.120

100.190
100.450
100.630
100.630
101.100
101.200
99.840
100.120

0.001
0.000
0.001
0.000
0.000
0.000
0.001
0.000

0.051
0.057
0.050
0.030
0.028
0.031
0.038
0.051

0.028
0.039
0.045
0.035
0.034
0.029
0.019
0.019

1.859
1.835
1.841
1.892
1.895
1.894
1.890
1.865

0.855
0.805
0.797
0.829
0.824
0.832
0.871
0.892

0.011
0.011
0.012
0.013
0.014
0.014
0.014
0.014

0.013
0.019
0.018
0.014
0.013
0.015
0.014
0.018

0.181
0.232
0.234
0.185
0.188
0.182
0.151
0.138

0.001
0.002
0.002
0.002
0.003
0.002
0.002
0.003

3.000
3.000
3.000
3.000
3.000
3.000
3.000
3.000

Sample J137-C
J137-C-A1-Mag1-1
J137-C-A1-Mag1-2
J137-C-A1-Mag1-3
J137-C-A1-Mag1-4
J137-C-A1-Mag1-5
J137-C-A1-Mag1-6

0.010
0.000
0.000
0.010
0.020
0.010

0.600
0.500
0.430
2.030
0.530
0.340

0.100
0.130
0.090
0.060
0.060
0.040

67.490
67.990
68.310
65.260
67.790
68.350

29.150
28.950
29.370
29.780
29.680
29.780

0.530
0.550
0.580
0.440
0.580
0.560

0.170
0.150
0.090
0.250
0.140
0.070

1.360
1.490
1.280
1.790
1.080
1.000

0.050 99.460
0.100 99.870
0.110 100.270
0.090 99.710
0.100 99.970
0.050 100.200

0.000
0.000
0.000
0.000
0.001
0.000

0.017
0.014
0.012
0.058
0.015
0.010

0.004
0.006
0.004
0.003
0.003
0.002

1.944
1.948
1.954
1.867
1.948
1.961

0.933
0.922
0.934
0.947
0.948
0.949

0.016
0.017
0.018
0.013
0.018
0.017

0.006
0.005
0.003
0.008
0.004
0.002

0.078
0.085
0.073
0.101
0.061
0.057

0.001
0.003
0.003
0.003
0.003
0.002

3.000
3.000
3.000
3.000
3.000
3.000

Sample J179-E
J179-E-Mag1-1
J179-E-Mag1-2
J179-E-Mag1-3
J179-E-Mag1-4
J179-E-Mag1-5

0.000
0.010
0.020
0.010
0.010

0.190
0.210
0.250
0.170
0.200

2.190
0.880
1.510
1.540
1.170

70.080
70.700
69.990
70.090
70.090

19.620
21.040
20.660
20.630
21.220

0.280
0.200
0.250
0.260
0.260

0.620
0.590
0.790
0.730
0.760

7.420
6.310
6.530
6.520
6.070

0.080 100.490
0.040 99.980
0.080 100.090
0.080 100.000
0.060 99.840

0.000
0.000
0.001
0.000
0.000

0.005
0.006
0.007
0.005
0.005

0.093
0.038
0.065
0.066
0.051

1.889
1.944
1.913
1.917
1.930

0.588
0.643
0.628
0.627
0.650

0.008
0.006
0.007
0.007
0.008

0.019
0.018
0.024
0.022
0.024

0.396
0.344
0.354
0.353
0.331

0.002
0.001
0.002
0.002
0.002

3.000
3.000
3.000
3.000
3.000

Sample J106-F
J106-F-A1-Mag-1
J106-F-A1-Mag-2
J106-F-A1-Mag-3
J106-F-A1-Mag-4
J106-F-A1-Mag-5
J106-F-A1-Mag-6

0.010
0.010
0.000
0.010
0.010
0.000

0.780
1.010
1.200
0.970
1.190
0.770

0.730
2.150
0.980
2.770
0.620
0.720

66.870
65.630
66.270
65.300
66.070
66.610

30.050
30.200
29.980
29.820
30.410
30.400

0.310
0.300
0.250
0.310
0.260
0.250

0.200
0.170
0.300
0.150
0.220
0.110

1.070
1.450
1.390
1.760
1.000
0.820

0.000
0.070
0.020
0.150
0.030
0.020

100.020
100.990
100.400
101.240
99.820
99.710

0.000
0.000
0.000
0.000
0.000
0.000

0.022
0.028
0.034
0.027
0.034
0.022

0.033
0.094
0.043
0.120
0.028
0.032

1.913
1.840
1.881
1.816
1.895
1.915

0.955
0.941
0.946
0.921
0.969
0.971

0.010
0.009
0.008
0.009
0.008
0.008

0.006
0.005
0.010
0.005
0.007
0.003

0.061
0.080
0.078
0.097
0.057
0.047

0.000
0.002
0.001
0.004
0.001
0.001

3.000
3.000
3.000
3.000
3.000
3.000

Sample SP24-53
SP24-53-Mag1-1
SP24-53-Mag1-2
SP24-53-Mag1-3
SP24-53-Mag1-4
SP24-53-Mag2-1
SP24-53-Mag2-2
SP24-53-Mag2-3

0.210
0.240
0.410
0.340
0.010
0.010
0.010

0.010
0.000
0.000
0.010
1.750
2.160
2.140

0.020
0.020
0.020
0.000
0.030
0.040
0.040

68.440
68.560
68.000
68.390
64.890
63.970
64.230

31.210
31.320
31.440
31.430
31.350
30.970
31.200

0.020
0.000
0.000
0.000
0.700
0.720
0.720

0.000
0.000
0.000
0.000
0.200
0.250
0.270

0.070
0.070
0.090
0.090
0.660
1.020
0.930

0.000 99.970
0.000 100.210
0.000 99.960
0.000 100.260
0.010 99.580
0.030 99.170
0.010 99.550

0.008
0.009
0.016
0.013
0.000
0.001
0.000

0.000
0.000
0.000
0.000
0.051
0.062
0.062

0.001
0.001
0.001
0.000
0.001
0.002
0.002

1.982
1.980
1.967
1.973
1.875
1.850
1.852

1.005
1.005
1.011
1.008
1.007
0.996
1.000

0.001
0.000
0.000
0.000
0.022
0.022
0.022

0.000
0.000
0.000
0.000
0.006
0.008
0.009

0.004
0.004
0.005
0.005
0.038
0.058
0.053

0.000
0.000
0.000
0.000
0.000
0.001
0.000

3.000
3.000
3.000
3.000
3.000
3.000
3.000

113

0.010
0.010
0.020
0.000
0.000
0.010
0.020
0.000

114

Table D.4: Microprobe Analyses of Ilmenite.

Ilmenite
Weight Percent Oxides
Label
SiO2 TiO2 Al2O3
Sample J151-A
Ilmenite exterior to Mag-1
J151-Ilmex-1
0.013 50.326 0.010
J151-Ilmex-2
0.001 50.191 0.009
J151-Ilmex-3
0.008 51.501 0.005
J151-Ilmex-4
0.005 50.535 0.016
J151-Ilmex-5
0.000 50.537 0.008

V2O5 Nb2O5 Ta2O5 FeO*

MnO

MgO

ZnO

CaO

Total

Cations per 12 Oxygen

Si
Ti
Al
V

Na

Ta

Fe

Mn

Mg

Zn

Ca

Sum

0.000
0.000
0.000
0.000
0.000

0.576
1.029
0.247
0.622
0.612

0.062
0.086
0.032
0.112
0.075

30.393
30.310
29.195
30.303
30.660

2.385
2.425
2.499
2.589
2.795

11.846
11.827
12.300
11.725
11.158

0.039
0.037
0.050
0.021
0.000

0.009
0.011
0.097
0.012
0.007

95.659
95.925
95.934
95.938
95.852

0.001
0.000
0.001
0.001
0.000

3.736
3.719
3.785
3.742
3.756

0.001
0.001
0.001
0.002
0.001

0.000
0.000
0.000
0.000
0.000

0.026
0.046
0.011
0.028
0.027

0.002
0.002
0.001
0.003
0.002

2.509
2.497
2.386
2.496
2.534

0.199
0.202
0.207
0.216
0.234

1.743
1.737
1.792
1.721
1.644

0.003
0.003
0.004
0.002
0.000

0.001
0.001
0.010
0.001
0.001

8.221
8.209
8.196
8.210
8.199

0.010
0.019
0.026
0.028
0.027

0.000
0.000
0.000
0.000
0.000

0.051
0.000
0.049
0.042
0.054

0.027
0.013
0.000
0.000
0.007

23.931
23.806
24.041
24.108
23.892

2.459
2.469
2.443
2.472
2.471

15.795
15.632
15.724
15.624
15.804

0.067
0.051
0.058
0.048
0.063

0.005
0.005
0.011
0.010
0.000

95.685
95.900
96.225
95.743
96.345

0.001
0.000
0.001
0.000
0.000

3.819
3.846
3.834
3.825
3.837

0.001
0.002
0.003
0.003
0.003

0.000
0.000
0.000
0.000
0.000

0.002
0.000
0.002
0.002
0.002

0.001
0.000
0.000
0.000
0.000

1.906
1.889
1.903
1.920
1.887

0.198
0.198
0.196
0.199
0.198

2.242
2.211
2.218
2.218
2.225

0.005
0.004
0.004
0.003
0.004

0.001
0.001
0.001
0.001
0.000

8.175
8.152
8.161
8.171
8.157

Sample J106-F
Area 1 - Ilmenite-1 in Magnetite
J106-A1-USp?-1
0.005 52.765
J106-A1-USp?-2
0.003 52.425
J106-A1-USp?-3
0.010 52.738
J106-A1-USp?-4
0.001 52.831
J106-A1-USp?-5
0.012 52.719

0.054
0.070
0.041
0.041
0.037

0.000
0.000
0.000
0.000
0.000

0.894
0.798
1.098
0.621
0.777

0.223
0.358
0.306
0.381
0.255

23.015
22.887
23.433
23.240
22.235

2.570
2.630
2.664
2.690
2.996

16.554
16.731
16.474
16.390
16.998

0.027
0.028
0.021
0.033
0.017

0.000
0.000
0.018
0.009
0.008

96.106
95.929
96.803
96.236
96.053

0.001
0.000
0.001
0.000
0.001

3.757
3.741
3.738
3.764
3.748

0.006
0.008
0.005
0.005
0.004

0.000
0.000
0.000
0.000
0.000

0.038
0.034
0.047
0.027
0.033

0.006
0.009
0.008
0.010
0.007

1.822
1.816
1.847
1.841
1.758

0.206
0.211
0.213
0.216
0.240

2.336
2.367
2.315
2.314
2.395

0.002
0.002
0.002
0.002
0.001

0.000
0.000
0.002
0.001
0.001

8.174
8.189
8.176
8.179
8.189

Area 1 - Ilmenite-2 in Magnetite

J106-A1-USp?2-1
0.000 53.439
J106-A1-USp?2-2
0.000 53.156
J106-A1-USp?2-3
0.006 53.096
J106-A1-USp?2-4
0.009 54.277
J106-A1-USp?2-5
0.000 51.824

0.040
0.041
0.025
0.028
0.008

0.000
0.000
0.000
0.000
0.000

0.752
0.795
0.848
0.732
0.229

0.251
0.304
0.242
0.314
0.047

22.691
21.653
21.749
17.874
29.408

3.373
3.821
3.890
5.017
5.085

16.112
16.171
16.398
18.652
9.635

0.000
0.034
0.021
0.028
0.038

0.025
0.067
0.018
0.007
0.022

96.682
96.042
96.293
96.936
96.296

0.000
0.000
0.001
0.001
0.000

3.787
3.787
3.773
3.775
3.847

0.004
0.005
0.003
0.003
0.001

0.000
0.000
0.000
0.000
0.000

0.032
0.034
0.036
0.031
0.010

0.006
0.008
0.006
0.008
0.001

1.788
1.715
1.719
1.382
2.428

0.269
0.307
0.311
0.393
0.425

2.263
2.283
2.310
2.571
1.418

0.000
0.002
0.002
0.002
0.003

0.003
0.007
0.002
0.001
0.002

8.153
8.148
8.162
8.166
8.135

Area 1 - Ilmenite exsolution in magnetite

J106-A1-IlmExslv-1 0.000 48.282 0.030
J106-A1-IlmExslv-2 0.001 47.797 0.032
J106-A1-IlmExslv-3 0.007 50.248 0.023
J106-A1-IlmExslv-4 0.003 50.421 0.026
J106-A1-IlmExslv-5 0.000 49.648 0.035

0.000
0.000
0.000
0.000
0.000

1.608
1.595
0.351
0.244
0.242

0.203
0.230
0.108
0.218
0.269

33.111
32.987
30.050
30.650
30.197

3.448 9.478
3.484 9.520
4.008 10.945
4.002 10.975
4.077 11.068

0.021
0.000
0.026
0.009
0.007

0.000
0.006
0.007
0.010
0.000

96.182
95.651
95.773
96.557
95.544

0.000
0.000
0.001
0.000
0.000

3.650
3.636
3.749
3.739
3.721

0.004
0.004
0.003
0.003
0.004

0.000
0.000
0.000
0.000
0.000

0.073
0.073
0.016
0.011
0.011

0.006
0.006
0.003
0.006
0.007

2.783
2.790
2.493
2.527
2.517

0.294
0.298
0.337
0.334
0.344

1.420
1.435
1.618
1.613
1.644

0.002
0.000
0.002
0.001
0.001

0.000
0.001
0.001
0.001
0.000

8.231
8.243
8.221
8.235
8.250

Sample J137-C
Area 1 - Ilmenite
J137-A1-Ilm1-1
J137-A1-Ilm1-2
J137-A1-Ilm1-3
J137-A1-Ilm1-4
J137-A1-Ilm1-5

0.000
0.000
0.000
0.000
0.000

0.627
0.653
0.601
0.580
0.617

0.067
0.032
0.088
0.094
0.037

30.348
31.295
31.324
31.856
28.884

6.219
5.455
4.711
3.857
8.119

0.022
0.026
0.039
0.013
0.000

0.012
0.007
0.020
0.006
0.018

96.291
96.256
96.051
95.313
95.517

0.001
0.000
0.000
0.001
0.000

3.756
3.743
3.753
3.725
3.743

0.002
0.001
0.002
0.001
0.003

0.000
0.000
0.000
0.000
0.000

0.028
0.030
0.027
0.026
0.028

0.002
0.001
0.002
0.003
0.001

2.537
2.620
2.620
2.684
2.443

0.527
0.463
0.399
0.329
0.696

1.341
1.351
1.392
1.460
1.298

0.002
0.002
0.003
0.001
0.000

0.001
0.001
0.002
0.001
0.002

8.196
8.211
8.201
8.230
8.212

0.009
0.000
0.004
0.007
0.000

49.970
49.720
49.903
49.167
49.212

0.018
0.012
0.020
0.010
0.022

8.997
9.057
9.341
9.721
8.608

114

Ilmenite inclusion within Mag-1

J151-Ilmint-1
0.007 53.334
J151-Ilmint-2
0.005 53.901
J151-Ilmint-3
0.005 53.868
J151-Ilmint-4
0.002 53.409
J151-Ilmint-5
0.004 54.023

115

Table D.5: Microprobe Analyses of Olivine.

Weight Percent Oxides
Label
SiO2 TiO2 Al2O3 Cr2O3
Sample J137-C
J137-C Ol1-1 41.625 0.002 0.009 0.000
J137-C Ol1-2 41.840 0.000 0.007 0.001
J137-C Ol1-3 41.800 0.002 0.000 0.005
J137-C Ol1-4 41.835 0.006 0.007 0.011
J137-C Ol1-5 41.956 0.000 0.002 0.025
J137-C Ol1-6 41.723 0.000 0.007 0.000

FeO* MnO

CaO Na2O

K2O

Total

0.065
0.065
0.079
0.064
0.031
0.059

0.000
0.000
0.007
0.006
0.007
0.001

100.837
100.667
101.014
101.121
100.998
100.728

Sample J179-E
J179-E Ol1-1 38.088 0.412 0.001 0.000 1.509 0.206 56.094 0.000 0.007 0.009 0.004
J179-E Ol1-2 38.414 0.425 0.014 0.000 1.527 0.210 56.107 0.000 0.003 0.000 0.000
J179-E Ol1-3 38.145 0.479 0.022 0.025 1.501 0.232 56.411 0.020 0.011 0.017 0.012

96.330
96.700
96.873

4.271
4.094
4.226
4.220
4.188
4.237

0.319
0.332
0.347
0.323
0.320
0.300

MgO

NiO

54.538
54.318
54.547
54.642
54.468
54.381

0.009
0.000
0.000
0.006
0.000
0.016

0.000
0.009
0.000
0.000
0.001
0.004

Cations per 4 Oxygen

Si
Ti
Al
Cr

Fe

Mn

Mg

Ni

Ca

Na

Sum

0.085
0.081
0.084
0.084
0.083
0.084

0.006
0.007
0.007
0.007
0.006
0.006

1.930
1.923
1.926
1.927
1.922
1.925

0.000
0.000
0.000
0.000
0.000
0.000

0.002
0.002
0.002
0.002
0.001
0.002

0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000

3.012
3.006
3.010
3.010
3.007
3.009

0.941 0.008 0.000 0.000 0.031 0.004 2.066 0.000 0.000 0.000 0.000
0.945 0.008 0.000 0.000 0.031 0.004 2.058 0.000 0.000 0.000 0.000
0.938 0.009 0.001 0.001 0.031 0.005 2.068 0.000 0.000 0.001 0.000

3.051
3.047
3.053

0.988
0.994
0.990
0.990
0.993
0.991

0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.000
0.000

0.000
0.000
0.000
0.000
0.001
0.000

115

116

Table D.6: Microprobe Analyses of Phlogopite.

Label
Sample J137-C
Olivine alteration
J137-C OlAltn-1
J137-C OlAltn-2
J137-C OlAltn-3
J137-C OlAltn-4
J137-C OlAltn-5

Weight Percent Components

SiO2 TiO2 Al2O3 V2O3 FeO* MnO

Cl

Sum

0.002
0.001
0.002
0.001
0.001

0.001
0.003
0.002
0.001
0.001

0.017
0.070
0.022
0.000
0.000

0.004
0.004
0.003
0.006
0.003

7.536
7.622
7.544
7.579
7.625

Sample J179-E
Phlogopite: low average mass (dark in BSEI)
J179-E Phl1-lm-1
30.571 0.039 14.360 0.042 1.808 0.029 36.312 0.031 0.052 2.427 0.023 0.268 0.016 -0.113 -0.004 85.862
J179-E Phl1-lm-2
30.311 0.000 14.048 0.007 1.811 0.020 36.505 0.033 0.064 2.647 0.044 0.272 0.021 -0.114 -0.005 85.663
J179-E Phl1-lm-3
30.577 0.008 14.017 0.011 1.817 0.016 36.317 0.018 0.119 2.609 0.035 0.304 0.005 -0.128 -0.001 85.724

2.323 0.002 1.286 0.002 0.115 0.002 4.113 0.003 0.002 0.358 0.002 0.065 0.002
2.314 0.000 1.264 0.000 0.116 0.001 4.155 0.003 0.002 0.392 0.004 0.066 0.003
2.332 0.000 1.260 0.001 0.116 0.001 4.128 0.002 0.004 0.386 0.003 0.073 0.001

8.208
8.251
8.232

Phlogopite: high average mass (bright in BSEI)

J179-E Phl1-hm-1
36.049 0.037 14.746 0.099 1.310 0.000 25.622 0.017 6.646 0.868 7.069 0.157 0.000 -0.066 0.000 92.553
J179-E Phl1-hm-2
36.209 0.036 14.935 0.027 1.287 0.021 26.114 0.004 6.484 0.971 7.103 0.256 0.000 -0.108 0.000 93.339
J179-E Phl1-hm-3
33.705 0.052 19.295 0.077 1.703 0.008 24.222 0.017 7.109 2.728 4.173 0.096 0.000 -0.040 0.000 93.144

2.723 0.002 1.313 0.005 0.083 0.000 2.884 0.001 0.197 0.127 0.681 0.037 0.000
2.710 0.002 1.318 0.001 0.081 0.001 2.914 0.000 0.190 0.141 0.678 0.061 0.000
2.516 0.003 1.697 0.004 0.106 0.001 2.695 0.001 0.208 0.395 0.397 0.023 0.000

8.016
8.036
8.023

Phlogopite: intermediate average mass

J179-E Phl1-im-1
35.758 0.032 17.285
J179-E Phl1-im-2
36.022 0.035 17.524
J179-E Phl1-im-3
34.077 0.014 19.535
J179-E Phl1-im-4
36.097 0.001 18.549
J179-E Phl1-im-5
34.164 0.039 18.921
J179-E Phl1-im-6
35.218 0.024 18.251
J179-E Phl1-im-7
35.266 0.025 18.421

2.636
2.642
2.530
2.621
2.549
2.596
2.579

0.000
0.000
0.000
0.000
0.000
0.000
0.000

8.038
8.027
8.008
8.012
8.004
8.012
8.037

32.948 0.053 19.957 0.000 1.855 0.018 23.472 0.034 8.540 2.173 4.577 0.179 0.000 -0.075 0.000 93.730
33.562 0.083 20.800 0.011 1.809 0.004 23.622 0.032 7.094 3.406 3.235 0.259 0.001 -0.109 0.000 93.806
36.617 0.005 18.003 0.062 1.709 0.017 24.953 0.062 4.111 2.740 5.341 0.137 0.001 -0.058 0.000 93.699

2.479 0.003 1.770 0.000 0.117 0.001 2.632 0.003 0.252 0.317 0.439 0.043 0.000
2.479 0.005 1.811 0.001 0.112 0.000 2.600 0.003 0.205 0.488 0.305 0.060 0.000
2.658 0.000 1.540 0.003 0.104 0.001 2.700 0.005 0.117 0.386 0.495 0.032 0.000

8.012
8.007
8.007

Olivine alteration phase

J179-E OlAlt1-2
37.483 0.042 4.897 0.056 2.028 0.026 38.228 0.057 0.000 0.559 0.097 0.362 0.122 -0.153 -0.027 83.778
J179-E OlAlt2-1
1.800 0.000 19.184 0.000 0.969 0.012 38.715 0.041 0.021 0.000 0.004 0.120 0.011 -0.050 -0.003 60.825

2.881 0.002 0.444 0.003 0.130 0.002 4.379 0.005 0.000 0.083 0.010 0.088 0.016
0.206 0.000 2.588 0.000 0.093 0.001 6.606 0.005 0.001 0.000 0.001 0.043 0.002

7.938
9.500

Sample J106-F
Area 2 - Phlogopite: Low-mass (dark in BSEI)
J106-F A2-PhlLM-1
38.446 0.204 15.872 0.000 2.243 0.019 25.567 0.000 2.228 0.162 9.924 0.449 0.006 -0.189 -0.001 94.930
J106-F A2-PhlLM-2
38.322 0.227 15.501 0.000 2.236 0.021 25.625 0.009 2.081 0.140 9.992 0.455 0.001 -0.192 0.000 94.418
J106-F A2-PhlLM-3
37.938 0.212 15.780 0.005 2.213 0.031 25.611 0.008 2.305 0.156 9.915 0.385 0.007 -0.162 -0.002 94.400

2.771 0.011 1.348 0.000 0.135 0.001 2.747 0.000 0.063 0.023 0.912 0.102 0.001
2.777 0.012 1.324 0.000 0.136 0.001 2.768 0.001 0.059 0.020 0.924 0.104 0.000
2.754 0.012 1.350 0.000 0.134 0.002 2.771 0.001 0.066 0.022 0.918 0.089 0.001

8.011
8.021
8.029

Area 2 - Phlogopite: High-mass (bright in BSEI)

J106-F A2-PhlHM-1
36.865 0.342 15.917 0.020 2.142 0.023 25.285 0.000 3.676 0.153 9.386 0.368 0.000 -0.155 0.000 94.021
J106-F A2-PhlHM-2
37.105 0.423 15.879 0.027 2.110 0.022 25.243 0.004 3.277 0.437 9.006 0.284 0.000 -0.120 0.000 93.697
J106-F A2-PhlHM-3
36.714 0.316 16.189 0.000 2.103 0.020 25.098 0.000 3.965 0.165 9.231 0.357 0.000 -0.150 0.000 94.007

2.713 0.019 1.380 0.001 0.132 0.001 2.773 0.000 0.106 0.022 0.881 0.086 0.000
2.724 0.023 1.374 0.001 0.130 0.001 2.762 0.000 0.094 0.062 0.843 0.066 0.000
2.705 0.018 1.406 0.000 0.130 0.001 2.756 0.000 0.114 0.024 0.868 0.083 0.000

8.028
8.016
8.020

Phlogopite-2
J179-E Phl2-1
J179-E Phl2-2
J179-E Phl2-3

0.080
0.102
0.098
0.066
0.048

0.007
0.000
0.000
0.000
0.000

0.018
0.027
0.066
0.086
0.024
0.090
0.110

7.272
7.233
7.136
6.504
6.595

1.743
1.711
1.780
1.721
1.734
1.699
1.720

0.076
0.101
0.130
0.123
0.128

0.024
0.014
0.009
0.034
0.015
0.007
0.026

32.087
32.915
32.225
33.226
33.775

0.171
0.144
0.150
0.189
0.154

25.271
25.126
24.053
24.862
24.041
24.681
25.071

0.048
0.039
0.025
0.045
0.055
0.094
0.215

BaO Na2O

0.036
0.000
0.015
0.000
0.000

5.239
5.356
6.694
4.771
7.741
6.270
5.880

0.015
0.004
0.017
0.005
0.006

2.501
2.597
2.586
2.765
2.643
2.695
2.670

K2O

Cl

0.011
0.030
0.020
0.009
0.013

0.070
0.290
0.093
0.001
0.001

0.032
0.034
0.020
0.044
0.023

5.301
5.225
4.480
5.127
4.135
4.610
4.928

0.085
0.179
0.105
0.027
0.108
0.084
0.231

0.003
0.000
0.003
0.000
0.000
0.000
0.000

O=F O=Cl

-0.029
-0.122
-0.039
0.000
0.000

-0.036
-0.076
-0.044
-0.011
-0.045
-0.035
-0.097

-0.007
-0.008
-0.005
-0.010
-0.005

-0.001
0.000
-0.001
0.000
0.000
0.000
0.000

Total

85.973
84.853
85.829
85.657
85.362

93.270
93.778
93.382
94.074
93.574
93.686
94.466

3.462
3.375
3.453
3.418
3.374

0.000
0.000
0.001
0.001
0.000

0.002
0.002
0.001
0.000
0.002
0.001
0.001

0.007
0.009
0.009
0.006
0.004

1.502
1.515
1.709
1.587
1.664
1.586
1.588

0.000
0.000
0.000
0.000
0.000

0.001
0.001
0.003
0.004
0.001
0.004
0.005

0.456
0.463
0.448
0.409
0.417

0.108
0.105
0.111
0.105
0.108
0.105
0.105

0.005
0.007
0.008
0.008
0.008

0.002
0.001
0.001
0.002
0.001
0.000
0.002

3.587
3.753
3.609
3.721
3.806

2.777
2.746
2.661
2.690
2.673
2.712
2.733

0.014
0.012
0.012
0.015
0.013

0.004
0.003
0.002
0.004
0.004
0.007
0.017

0.001
0.000
0.000
0.000
0.000

0.151
0.154
0.195
0.136
0.226
0.181
0.169

0.357
0.369
0.372
0.389
0.382
0.385
0.379

0.499
0.489
0.424
0.475
0.393
0.434
0.460

0.020
0.042
0.025
0.006
0.025
0.020
0.054

116

0.001
0.000
0.009
0.014
0.000

CaO

Ions per 10 Oxygen + 2 (OH,F,Cl): sum excludes F & Cl

Si
Ti
Al
V
Fe Mn Mg
Ca
Ba

Na

46.152
44.130
45.959
45.486
44.625

MgO

117
Table D.7: List and Range of Results of the Applied Sets of Standards.

APATITE
SiO2
Al2O3
FeO*
MnO
MgO
CaO
SrO
Y2O3
BaO
La2O3
Ce2O3
Nd2O3
Sm2O3
Gd2O3
Na2O
K2O
P2O5
SO3
F
Cl
O=F
O=Cl

MIN %
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
-9.000
0.000

MAX %
68.469
58.706
29.993
35.743
49.917
54.383
68.069
79.105
65.640
4.476
4.190
4.404
4.508
4.683
26.887
14.897
41.273
34.582
21.374
7.741
-0.006
2.031

STANDARDS RUN
FAP test
SGKF-1
FAP-1
SGKF-2
FAP-2
SGKF-3
FAP-3
RDN-1
FAP-4
RDN-2
FAP-5
RDN-3
FTOZ-1
AUGI-1
FTOZ-2
AUGI-2
FTOZ-3
AUGI-3
AMAB-1
STR-1
AMAB-2
STR-2
AMAB-3
STR-3
SCOL-1
YSiO-1
SCOL-2
YSiO-2
SCOL-3
YSiO-3
SWAN-1
REGL3-1
SWAN-2
REGL3-2
SWAN-3
REGL3-3
BRT-1
REGL3-4
BRT-2
REGL2-1
BRT-3
REGL2-2
TUG-1
REGL2-3
TUG-2
REGL2-4
TUG-3
REGL2-5
REGL1-1
REGL1-2
REGL1-3
REGL1-4

OXIDES
SiO2
TiO2
Al2O3
V2O5
Nb2O5
Ta2O5
FeO*
MnO
MgO
ZnO
CaO

MIN %
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000

SiO2
TiO2
Al2O3
V2O3
FeO*
MnO
MgO
CaO
BaO
Na2O
K2O
F
Cl
O=F
O=Cl

MAX %
64.359
40.301
34.257
0.456
30.200
0.761
29.109
27.696
15.016
1.691
14.869
9.619
0.016
0.000
0.000

STANDARDS RUN
synth Phlog
synth Phlog
synth Phlog
SWAN-1
SWAN-2
SWAN-3
SWAN-4
SGKF-1
SGKF-2
TITGl-1
TITGl-2
AUGI-1
AUGI-2
AUGI-3
K309-1
K309-2
K309-3

STANDARDS RUN
Ilm Test
Mn-Tanatalite
Mg-Chromite Mn-Tanatalite
Mg-Chromite Mn-Tanatalite
Mg-Chromite MG Magnetite
Gahnite
MG Magnetite
Gahnite
MG Magnetite
Wollastonite La-Niobate
Ilmenite
La-Niobate
Ilmenite
La-Niobate
Ilmenite
V-grossular
V-grossular
V-grossular

CARBONATES

FeO*
MnO
MgO
CaO
SrO
BaO
Na2O
CO3
SO3

MIN %
0.003
0.000
0.000
2.190
0.008
0.000
0.000
30.507
0.000

MAX %
0.090
0.016
21.928
30.341
67.733
0.091
0.000
47.788
0.029

SiO2
TiO2
Al2O3
Cr2O3
FeO*
MnO
MgO
NiO
CaO
Na2O
K2O

MIN %
28.707
0.000
0.000
0.000
9.778
0.030
0.001
0.000
0.011
0.000
0.000

MAX %
40.892
0.026
0.045
0.023
71.240
0.169
49.642
0.380
0.110
0.001
0.003

MICAS AND HYDROUS ALTERATIONS

MIN %
29.810
0.000
0.003
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.001
0.000
-4.050
-0.004

MAX %
50.340
46.573
55.848
3.380
41.101
82.840
92.862
14.069
18.314
41.497
47.013

STANDARDS RUN
Dol-1
Dol-2
Dol-3
STR-1
STR-2

OLIVINE
STANDARDS RUN
San Carlos
San Carlos
San Carlos
Synth Fay
Synth Fay

118

APPENDIX E.
STANDARLESS QUANTITATIVE ANALYSES (SEM-EDS) OF PYROCHLORE

119
User: Paula Alves

Analyst: G. Morgan

NbL
700

Pyrochlore Core
600

500

400

CaK
300

NbL
200

TiK
ThM TiK
NaK
CaK

100

ThL
NbK

ThL

0
0

10

keV

15

Acquisition Parameters

Analysis

Accelerating Voltage (kV)

20.0

Correction Method

PAP

Beam Current (nA)

4.990

Analysis Type

StdLess

Magnification

5000

Number of Oxygens

Measures & Results

Elem

Line

Intens

W%
29.24

A%

Formula

61.16

Cat#

0.00

0.00

4.84

0.26

Na

Ka

15.8

3.59

Ca

Ka

224.7

18.93

15.80 CaO

26.49

0.78

Ti

Ka

42.0

4.19

2.92 TiO2

6.98

0.14

Nb

La

414.4

39.52

14.23 Nb2O5

56.54

0.70

Th

Ma

20.9

4.53

0.65 ThO2

5.16

0.03

100.00

1.91

100.00

5.23 Na2O

Ox%

100.00

Figure E.1: Standardless Quantitative Analysis (SEM-EDS) of Core Zone of Pyrochlore Crystal.
Sample SP24-53.

120
User: Paula Alves

Analyst: G. Morgan

NbL
700

Pyrochlore Rim
600

500

400

CaK
300

NbL
200

TiK
ThM TiK
NaK
CaK

100

ThL
NbK

ThL

0
0

10

keV

15

Acquisition Parameters

Analysis

Accelerating Voltage (kV)

20.0

Correction Method

PAP

Beam Current (nA)

2.010

Analysis Type

StdLess

Magnification

5000

Number of Oxygens

Measures & Results

Elem

Line

Intens

W%
27.97

A%

Formula

62.00

Cat#

0.00

0.00

3.27

0.18

Na

Ka

10.8

2.42

Ca

Ka

205.5

16.90

14.96 CaO

23.65

0.72

Ti

Ka

59.3

5.72

4.24 TiO2

9.54

0.20

Nb

La

367.3

34.44

13.15 Nb2O5

49.27

0.64

Th

Ma

61.7

12.54

1.92 ThO2

14.27

0.09

100.00

1.84

100.00

3.74 Na2O

Ox%

100.00

Figure E.2: Standardless Quantitative Analysis (SEM-EDS) of Rim Zone of Pyrochlore Crystal.
Sample SP24-53.

121

APPENDIX F.
TABLES WITH MINERALOGICAL DESCRIPTIONS PER AREA OF STUDY

122
Table F.1: Microscopic Characteristics of the Apatite.

AREA
A

DESCRIPTION
Generally coarse-grained, anhedral, zoned, it may form inclusions in
magnetite.

Medium-grained showing blue CL zoning, with a violet core. Grain may

show more than one violet core by aggregation of independently grown units.
CL also shows transition from earlier euhedral to later subhedral/anhedral
shapes, and later development of mutual boundaries among grains, suggesting
re-accommodation of apatite crystals.

Occurs in clusters, forms lineations, some grains mold on other apatite or

calcite grains and these grains may develop sigmoidal shape that indicates
magma flow direction. Most apatites contain microfractures filled by calcite
or sulfides, showing dull CL, whereas other grains show the characteristic
blue CL. In general, apatite is subhedral (fairly rounded), zoned, and it may
contain fluid inclusions in the core. Crystallization of apatite appears to have
a certain affinity with magnetite. Grain size varies from 0.1 to 2 mm.

Generally subhedral, exhibiting blue CL zoning with violet core, and some
large fluid inclusions. Apatite is also present as angular fragments in the
carbonate groundmass. Mineralized veins and lineations were developed.
Elongated grains contour carbonates boundaries. Apatite commonly
crystallized in between calcite grains. Also occurs as small, isolated pods.
Grain size is < 1.5 mm.

Fine to medium-grained (< 2 mm), strongly-oriented by magmatic foliation.

Apatite occurs associated with magnetite, sometimes as inclusions. Grains are
anhedral and show characteristic blue, light blue, greenish blue CL zoning.
Oriented, primary fluid inclusions can be observed in the core of larger
grains. Apatite forms veinlets, elongated clusters and pods. It apparently
shows crystallization also in association with olivine and sulfides. Grains may
be fractured.

123
Table F.1: (continued) Microscopic Characteristics of the Apatite.

AREA

DESCRIPTION

Grains are fine and have rounded or irregular shapes, showing blue CL zoning,
and commonly calcite inclusions. Apatite forms oriented veins/clusters. Some
grains crystallized in junctions of dolomite grains. Others conform with
magnetite and sulfide grains boundaries, resulting in sigmoidal shapes that
indicate the direction of magma flow. Fewer fluid inclusions are present.

SP24

Fine-grained apatite (< 0.6 mm) forms veinlets and clusters oriented by
magma flow. Grains show blue CL zoning.

124
Table F.2: Microscopic Characteristics of the Carbonates.

AREA

DESCRIPTION

Calcite is much more abundant than dolomite. Dolomite blebs occur exsolved
in calcite. Calcite is anhedral, and commonly exhibits twinning. Texture is
dominantly interlocking, with late carbonates filling spaces.

Calcite is much more abundant than dolomite. There is no evidence of

exsolution textures. Yellow CL calcite formed earlier than red CL dolomite,
the latter occurring filling spaces (interstitial).

Calcite is much more abundant than dolomite. Dolomite blebs occur exsolved
in calcite, and interstitial to apatite and phlogopite grains. Carbonates form
interlocking texture and can show sutured boundaries. Grains are mostly
anhedral, and vary in size from 0.2 to 5 mm. Calcite is commonly twinned.
Recrystallized grains showing CL zoning occur in veins. Calcite CL is yellow
to red orange. Yellow calcite blebs also occur within orange calcite.

Calcite is more abundant than dolomite, but the latter assumes greater
importance locally. Small sized, brown CL dolomite occurs associated with
late veins of calcite. Elongated carbonate grains can be interstitial, forming
interlocking texture, and follow the magma flow. Grain size varies from 0.3 to
6 mm. Exsolution textures are present, and serrated grain boundaries were
developed. Other features that can be observed are recrystallization, presence
of small fluid inclusions, and some deformational twinning. Calcite may
contain inclusions of apatite.

Amount of calcite is still higher, but much closer to that of dolomite.

Carbonates crystals follow magmatic foliation, but also occur interstitially.
They are mostly elongated, anhedral. Calcite shows orange CL, whereas
dolomite CL is red, with reddish brown rims (zoning). Calcite and dolomite
can occur as inclusions in magnetite. Twinning in calcite is common, and it
may also contain small fluid inclusions. Exsolution features were rarely
observed. Interlocking and granular textures are dominant.

125
Table F.2: (continued) Microscopic Characteristics of the Carbonates.
AREA
F

DESCRIPTION
Calcite is more abundant than dolomite, but there is increased relevance of
dolomite presence. Rounded, irregular shapes of carbonates form inclusions
in apatite, magnetite, and olivine. Exsolution textures can be seen (such as
brown CL blebs and spindles in red CL dolomite), as well as interstitial,
elongated crystals, forming interlocking texture. Calcite is twinned in some
cases, and may contain small fluid inclusions.

SP24

Dolomite is the dominant carbonate. It is medium-grained (< 2 mm), and

zoned. Fluid inclusions occur in dolomite. Calcite is present only in veins and
microfractures after dolomite.

126
Table F.3: Microscopic Characteristics of the Oxides.

AREA
A

DESCRIPTION
Magnetite is coarse, shows resorbed, embayed grain boundaries and
inclusions of ilmenite (no exsolution laths), apatite, calcite and phlogopite.

Subhedral magnetite grains showing resorption features and development of

poikilitic texture, with inclusions of apatite and dolomite. No ilmenite was
observed.

Most magnetite contains no ilmenite, but a few grains show ilmenite as

exsolution laths and inclusions. In many cases, magnetite engulfed small
apatite grains, calcite, dolomite, phlogopite, and some pyrrhotite, forming
poikilitic texture. Magnetite locally shows dolomite vein penetrating its
cleavage plans. Resorption developed on previously euhedral crystal faces.
Magnetite also occurs as secondary phase replacing pyrrhotite.

In general, magnetite is subhedral, very coarse-grained (up to 25 mm), shows

resorption features, and no ilmenite. Small inclusions of carbonates and
euhedral apatite can be present. Dolomite, in a few cases, penetrates
magnetite grains. Secondary magnetite occurs in small amounts, replacing
pyrrhotite.

Magnetite is medium to coarse-grained (up to 8 mm), and shows poikilitic

texture with apatite, calcite and dolomite inclusions, as well as some
phlogopite and pyrrhotite. In most cases, magnetite boundaries are lobated,
irregular, suggesting resorption, although some crystals faces may have been
preserved. Calcite occurs interstitially to magnetite. No ilmenite is present.
Magmatic flow banding, with magnetite crystals size segregation, is readily
observed in some samples.

Magnetite contains ilmenite, mostly as inclusions, but also forming laths.

Resorption features are commonly observed along grain boundaries.
Secondary magnetite occurs after pyrite.

SP24

Magnetite is fine-grained (< 0.7 mm), anhedral, contains no ilmenite, and its
modal content is only about 3%, much lower than observed in other areas.

127
Table F.4: Microscopic Characteristics of the Silicates.

AREA
A

DESCRIPTION
Olivine is not present. Phlogopite is medium to coarse-grained, subhedral to
anhedral, slightly altered, and formed after apatite. Some grains show
undulatory extinction.

Olivine is not present. Phlogopite is anhedral to subhedral, and shows

differential alteration, mainly due to varying Ba content. Phlogopite growth
partially overlaps that of the apatite and calcite. It commonly shows
inclusions of calcite and anhedral apatite. An aureole of apatite formed
around phlogopite suggests some preference of crystallization of the former in
the proximity of phlogopite.

Olivine is anhedral to subhedral, mostly medium sized (ranging from 0.6 to 6

mm), fractured, very altered, and in some samples it was penetrated by late
calcite veins. Anhedral apatite can be seen molding on olivine crystals.
Phlogopite occurs as anhedral to euhedral crystals, it is zoned, altered
(forming red-brown rims), and deformed. In some cases, calcite and
magnetite inclusions can be observed in phlogopite.

There are very few olivine remnants present. Phlogopite is anhedral,

deformed, altered, and can form olivine pseudomorphs. It may contain
inclusions of carbonates, apatite, and twinned baddeleyite. Size can vary from
0.3 to 4.2 mm.

Olivine is medium to coarse-grained (1 to 6 mm), fractured but not very

altered. Olivine contains apatite inclusions, indicating that its crystallization
timing overlaps that of apatite growth to a certain extent. Olivine may contain
irregular strings of very small (< 2 m) fluid inclusions. Phlogopite is
euhedral to subhedral, zoned, deformed, and shows differential alteration.
Some grains can contain inclusions of pyrrhotite, apatite, or carbonates.

128
Table F.4: (continued) Microscopic Characteristics of the Silicates.

AREA
F

DESCRIPTION
Olivine is generally medium to coarse-grained and commonly altered, which
in some cases resulted in pseudomorphization. Inclusions of apatite, calcite,
magnetite, phlogopite and pyrochlore can occur in olivine. Phlogopite is
medium to coarse-grained, mostly euhedral, deformed, and altered (especially
along rims and cleavages). It may show radioactive haloes due to inclusions
of pyrochlore. Small inclusions of apatite and calcite can also be present.

SP24

Olivine is absent. Phlogopite is fine-grained, zoned, and very altered.

129
Table F.5: Microscopic Characteristics of the Sulfides.

AREA

DESCRIPTION

Pyrrhotite is euhedral (hexagonal) to subhedral, and shows some replacement

by pyrite and chalcopyrite. Secondary magnetite forms rims along fractures
after pyrite and chalcopyrite.

Presence of sulfides is incipient.

Pyrrhotite size varies from 0.1 to 5 mm, and is frequently being replaced by
either of the following associations: a) pyrite, secondary magnetite, then
valleriite; b) chalcopyrite and pyrite; c) twinned pyrrhotite replaced by pyrite,
then secondary magnetite and chalcopyrite; d) partial replacement to pyrite
only. Sulfides can occur filling fractures in apatite, and as microveins along
calcite cleavage. Pyrrhotite can show inclusions of carbonates and apatite.

Pyrrhotite is mainly replaced by colloform pyrite and secondary magnetite.

Grain size ranges from 0.4 to 3 mm. Pyrrhotite may contain inclusions of
anhedral apatite.

Pyrrhotite crystallization overlaps that of the apatite. It occurs interstitially

and molding on apatite grains. There are a few round apatite crystals attached
to a pyrrhotite crystal face, suggesting some growth affinity. Pyrrhotite size is
< 1mm, and is being replaced by pyrite, secondary magnetite (especially
along rims), and chalcopyrite. Other minor replacements are goethite and
marcasite. Pyrrhotite may form microveins penetrating along carbonates
cleavage.

Pyrrhotite is being replaced by pyrite, secondary magnetite (it may form

disease texture), then chalcopyrite (forming atoll-like texture), and late
valleriite. Pyrrhotite can occur enveloping primary magnetite and carbonates.
Pyrite and some chalcopyrite occur filling carbonates grain boundaries, and
microfractures in primary magnetite and apatite.

SP24

Pyrrhotite is being replaced by pyrite and chalcopyrite.

130
Table F.6: Microscopic Characteristics of the Other Minerals.

AREA

DESCRIPTION

None observed.

None observed.

Presence of striated, twinned baddeleyite, and possibly perovskite.

Few perovskite subhedral grains are present, showing some preserved crystal
faces. Twinned baddeleyite occurs as inclusions in calcite and phlogopite, or
in contact with magnetite.

Small amounts of baddeleyite are common, and typically occur associated

with magnetite. In general, grains are < 0.5 mm. Pyrochlore is also present.

Pyrochlore is zoned, twinned, and may cause radioactive halo in host

phlogopite.

SP24

Pyrochlore is present in higher amount (up to 5% modal composition) than in

other areas. Grains are small and complexly zoned, with decrease of Nb
towards the rim, and increase of Th and Ti, in the same direction.

131
BIBLIOGRAPHY

Alves, P. R. and Hagni, R. D. (2004). Bunges Cajati Apatite Mine, Southeastern Brazil:
Mineralogy and Petrography of the Carbonatite Intrusions and the Relationship to
Mineral Processing. In: Pechio, M.; Andrade, F. R. D.; DAgostino, L. Z.; Kahn,
H.; SantAgostino, L. M.; Tassinari, M. M. M. L. (eds). Applied Mineralogy Developments in Science and Technology, ICAM , 2, pp. 653-656.
Alves, P. R. and Hagni, R. D. (2006). The Carbonatite-Hosted Cajati (Jacupiranga)
Apatite Mine, Southeastern Brazil: a Cathodoluminescence Approach to
Mineralogical Characterization. Geological Association of Canada Mineralogical Association of Canada (GAC-MAC) Annual Meeting, Montreal,
Canada, Abstracts, pp. 35.
Amaral, G. (1978). Potassium-Argon Age Studies on the Jacupiranga Alkaline District,
State of So Paulo, Brazil. Proceedings of the International Symposium of
Carbonatites, 1, pp. 297-302.

Basu, A. R.; Renne, P. R.; Mertz, D.; Poreda, R. J. (1993). Alkalic Igneous Complexes of
the Deccan and Paran: Implications for the Origin of Continental Flood Basalts
(CFB). American Geophysical Union Meeting, 74 (43), Abstracts, pp. 552.
Bell, K. (1989). Carbonatites: Genesis and Evolution. Unwin Hyman Ltd, London, 618 p.
Boggs, S. and Krinsley, D. (2006). Application of Cathodoluminescence Imaging to the
Study of Sedimentary Rocks. Cambridge University Press, New York, 176 p.
Brod, J. A.; Gaspar, J. C.; Araujo, D. P.; Gibson, S. A.; Thompson, R. N.; Junqueira, T.
C. (2001). Phlogopite and Tetra-Ferriphlogopite from Brazilian Carbonatite
Complexes; Petrogenetic Constraints and Implications for Mineral-Chemistry
Systematics. Journal of Asian Earth Sciences, 19 (3), pp. 265-296.

132
Bhn, B.; Wall, F.; Le Bas, M. J. (2001). Rare-Earth Element Systematics of Carbonatitic
Fluorapatites, and Their Significance for Carbonatite Magma Evolution.
Contributions to Mineralogy and Petrology, 141 (5), pp. 572-591.
Byrnes, A. P. and Wyllie, P. J. (1981). Subsolidus and Melting Relations for the Join
CaCO3-MgCO3 at 10 kbar. Geochimica et Cosmochimica Acta, 45, pp. 321-328.
Constanzo, A., Moore, K. R., Wall, F., Feely, M. (2006). Fluid Inclusions in Apatite from
Jacupiranga Calcite Carbonatites: Evidence for a Fluid-Stratified Carbonatite
Magma Chamber. Lithos, 91 (1-4), pp. 208-228.
Dawson, J. B. (1966). Oldoinyo Lengai - an Active Volcano With Sodium Carbonatite
Lava Flows. In: Tuttle, O. F. and Gittins, J. (eds.), Carbonatites, Wiley, New
York, pp. 155-168.
Deer, W. A.; Howie, R. A.; Zussman, J. (1992). An Introduction to the Rock Forming
Minerals. 2nd edition, Prentice Hall, Harlow, 696 p.
DNPM (2003). Anurio Mineral Brasileiro (Brazilian Mineral Yearbook). Departamento
Nacional de Produo Mineral, Braslia, 31, pp. 303-304.
Drake, M. J. and Weill, D. F. (1972). New Rare-Earth Element Standards for Electron
Microprobe Analysis. Chemical Geology, 10 (2), pp. 179-181.
Ewing, R. C. and Wang, L. (2002). Phosphates as Nuclear Waste Forms. In: Kohn, M. J.;
Rakovan, J.; Hughes, J. M. (eds). Phosphates: Geochemical, Geobiological, and
Materials Importance. Mineralogical Society of America and Geochemical
Society, Reviews in Mineralogy and Geochemistry, 48, pp. 673-699.
Fleet, M. E. and Pan, Y. (1995). Site Preference of Rare-Earth Elements in Fluorapatite.
American Mineralogist, 80 (3-4), pp. 329-335.

133
Fleischer, M. and Altschuler, Z. S. (1986). The Lanthanides and Yttrium in Minerals of
the Apatite Group - an Analysis of the Available Data. Neues Jahrbuch
Mineralogie, 10, pp. 467-480.
Gaspar, J. C. and Wyllie, P. J. (1982). Barium Phlogopite from the Jacupiranga
Carbonatite, Brazil. American Mineralogist, 67 (9-10), pp. 997-1000.

Gaspar, J. C. and Wyllie, P. J. (1983a). Magnetite in the Carbonatites from the

Jacupiranga Complex, Brazil. American Mineralogist, 68 (1-2), pp. 195-213.

Gaspar, J. C. and Wyllie, P. J. (1983b). Ilmenite (High Mg, Mn, Nb) in the Carbonatites
from the Jacupiranga Complex, Brazil. American Mineralogist, 68 (9-10), pp.
960-971.

Gaspar, J. C. and Wyllie, P. J. (1987). The Phlogopites from the Jacupiranga Carbonatite
Intrusions. Contributions to Mineralogy and Petrology, 36, pp. 121-134.

Gaspar, J. C. (1989). Geologie et Mineralogie du Complexe Carbonatitique de

Jacupiranga, Bresil. PhD Dissertation, U.E.R. de Sciences Fondamentales et
Apliques de la Universit DOrleans, France, 343 p.

Gaspar, J. C. (1991). The Magmatic Evolution of the Jacupiranga Complex, Brazil.

Proceedings of the International Kimberlite Conference, 5, pp. 127-129.

Gaspar, J. C. (1992). Titanian Clinohumite in the Carbonatites from the Jacupiranga

Complex, Brazil: Mineral Chemistry and Comparison With Titanian Clinohumite
from Other Environments. American Mineralogist, 77 (1-2), pp. 168-172.

134
Germann, A.; Marker, A.; Friedrich, G. (1987). The Alkaline Complex of Jacupiranga,
Brazil; Petrology and Genetic Considerations. Zentralblatt fr Geologie und
Palaeontologie, 1 (7-8), pp. 807-818.

Goldsmith, J. R. (1983). Phase Relations of Rhombohedral Carbonates. In: Reeder, R. J.

(ed.). Carbonates: Mineralogy and Chemistry. Mineralogical Society of America,
Reviews in Mineralogy, 11, pp. 49-76.
Gomes, C. B.; Ruberti, E.; Morbidelli, L. (1990). Carbonatite Complexes from Brazil: a
Review. Journal of South American Earth Sciences, 3, pp. 51-63.
Groves, D. I. and Vielreicher, N. M. (2001). The Phalabowra (Palabora) CarbonatiteHosted Magnetite-Copper Sulfide Deposit, South Africa: an End-Member of the
Iron Oxide-Copper-Gold-Rare Earth Element Deposit Group. Mineralium
Deposita, 36 (2), pp. 189-194.
Hoggarth, D. D. (1989). Pyrochlore, Apatite and Amphibole: Distinctive Minerals in
Carbonatite. In: Bell, K. (ed.). Carbonatites - Genesis and Evolution, Unwin
Hyman Ltd., London, pp. 105-148.
Hughes, J. M.; Cameron, M.; Mariano, A. N. (1991). Rare-Earth Element Ordering and
Structural Variations in Natural Rare-Earth Bearing Apatites. American
Mineralogist, 76 (7-8), pp. 1165-1173.
Hughes, J. M. and Rakovan, J. (2002). Phosphates as Nuclear Waste Forms. In: Kohn, M.
J.; Rakovan, J.; Hughes, J. M. (eds). Phosphates: Geochemical, Geobiological,
and Materials Importance. Mineralogical Society of America and Geochemical
Society, Reviews in Mineralogy and Geochemistry, 48, pp. 1-12.
Kasputin, Y. L. (1966). Geochemistry of REE in Carbonatites. Geochemistry
International, 3, pp. 1054-1064.

135
Kogarko, L. N. ; Kononova, V. A.; Orlova, M. P.; Woolley, A. R. (1995). Alkaline Rocks
and Carbonatites of the World, Chapman and Hall, London, 226 p.

Lenharo, S. L. R. (1994). Caracterizao Mineralgica/Tecnolgica das Apatitas de

Alguns Depsitos Brasileiros de Fosfato. Master Thesis, Escola Politcnica,
Universidade de So Paulo, Brasil, 131 p.

Liu, Y. and Comodi, P. (1993). Some Aspects of the Crystal-Chemistry of Apatites.

Mineralogical Magazine, 57, pp. 709-719.

Mariano, A. N. and Ring, P. I. (1975). Europium Activated Cathodoluminescence in

Minerals. Geochimica et Cosmochimica Acta, 39, pp. 649-660.

Mariano, A. N. (1978). The Application of Cathodoluminescence for Carbonatite

Exploration and Characterization. Proceedings of the International Symposium of
Carbonatites, 1, pp. 39-57.
Marshall, D. J. (1988). Cathodoluminescence of Geological Materials. Unwin Hyman
Ltd., London, 146 p.
McClellan, G. H. (1980). Mineralogy of Carbonate Fluorapatites. Journal of the
Geological Society, 137 (6), pp. 675-681.

McCormick, G. R. and LeBas, M. J. (1996). Phlogopite Crystallization in Carbonatitic

Magmas from Uganda. Canadian Mineralogist, 34 (2), pp. 469-478.

Menezes Jr, L. A. D. and Martins, J. M. (1984). The Jacupiranga Mine, So Paulo.

Mineralogical Record, 15 (5), pp. 261-270.

136
Mitchell, R. H. (1978). Manganoan Magnesian Ilmenite and Titanian Clinohumite from
the Jacupiranga Carbonatite, So Paulo, Brazil. American Mineralogist, 63 (5-6),
pp. 544-547.

Morse, J. W. (1983). The Kinetics of Calcium Carbonate Dissolution and Precipitation.

In: Reeder, R. J. (ed), Carbonates: Mineralogy and Geochemistry. Mineralogical
Society of America, Reviews in Mineralogy, 11, pp. 227-264.
Murray, J. R. and Oreskes, N. (1997). Uses and Limitations of Cathodoluminescence in
the Study of Apatite Paragenesis. Economic Geology, 92, pp. 368-376.

Nesbitt, B. E. and Kelly, W. C. (1977). Magmatic and Hydrothermal Inclusions in

Carbonatites of the Magnet Cove Complex, Arkansas. Contributions to
Mineralogy and Petrology, 63 (3), pp. 271-294.
Pagel, M.; Barbin, V.; Blanc, P.; Ohnenstetter, D. (2000). Cathodoluminescence in
Geosciences, SpringerVerlag, New York, 514 p.
Pan, Y. and Fleet, M. (2002). Compositions of the Apatite-Group Minerals: Substitution
Mechanisms and Controlling Factors. In: Kohn, M. J.; Rakovan, J.; Hughes, J. M.
(eds). Phosphates: Geochemical, Geobiological, and Materials Importance.
Mineralogical Society of America and Geochemical Society, Reviews in
Mineralogy and Geochemistry, 48, pp. 13-49.
Piccoli, P. M. and Candela, P. A. (2002). Apatite in Igneous Systems. In: Kohn, M. J.;
Rakovan, J.; Hughes, J. M. (eds). Phosphates: Geochemical, Geobiological, and
Materials Importance. Mineralogical Society of America and Geochemical
Society, Reviews in Mineralogy and Geochemistry, 48, pp. 255-292.

137
Pouchou, J. L. and Pichoir, F. (1991). Electron Probe Quantification. In: Heinrich, K. F.
J. and Newbury, D. E. (eds). Workshop at the National Bureau of Standards,
Gaithersburg, Maryland, 1988, Plenum Press, New York, pp. 31-75.
Rakovan, J. (2002). Growth and Surface Properties of Apatite. In: Kohn, M. J.; Rakovan,
J.; Hughes, J. M. (eds). Phosphates: Geochemical, Geobiological, and Materials
Importance. Mineralogical Society of America and Geochemical Society,
Reviews in Mineralogy and Geochemistry, 48, pp. 51-86.
Raposo, D. B. (2002). Investigao Tcnolgica em Minrio Carbonattico de Cajati, SP,
Utilizado como Matria-Prima na Produo de Fosclcio. Senior Thesis, Instituto
de Geocincias, Universidade de So Paulo, Brasil, 92 p.
Reed, R. M., and Milliken, K. L. (2003). SEM-Based Cathodoluminescence Imaging in
Sandstone Provenance Analysis: Quartz and Feldspar Grains, Zircons, and
Siliceous Rock Fragments. Geological Society of America. Abstracts with
Programs, 35 (6), pp. 391.
Roden, M. F.; Murthy, V. R.; Gaspar, J. C. (1985). Sr and Nd Isotopic Composition of
the Jacupiranga Carbonatite. Journal of Geology, 93 (2), pp. 212-220.

Roedder, E. (1984). Fluid Inclusions. Mineralogical Society of America, Reviews in

Mineralogy, 12, 644 p.

Roeder, P. L.; MacArthur, D.; Ma, X. P.; Palmer, G. R.; Mariano, A. N. (1987).
Cathodoluminescence and Microprobe Study of Rare-Earth Elements in Apatite.
American Mineralogist, 72 (7-8), pp. 801-811.

138
Ruberti, E.; Gomes, C. B.; Melcher, G. C. (2000). The Jacupiranga Carbonatite Complex:
Geological and Petrological Aspects of the Jacupiranga Alkaline-Carbonatite
Association, Southern Brazil. Post-Congress Field Trip Guidebook, 31st
International Geological Congress, Rio de Janeiro, 21 p.
Speer, J. A. (1983). Crystal Chemistry and Phase Relations of Orthorhombic Carbonates.
In: Reeder, R. J. (ed). Carbonates: Mineralogy and Geochemistry. Mineralogical
Society of America, Reviews in Mineralogy, 11, pp. 145-190.
Steele, I. M. (1986). Cathodoluminescence and Minor Elements in Forsterites from
Extraterrestrial Samples. American Mineralogist, 71 (7-8), pp. 966-970.
Stormer, J. C.; Pierson, M. L.; Tacker, R. C. (1993). Variation of F and Cl X-Ray
Intensity due to Anisotropic Diffusion in Apatite During Electron Microprobe
Analysis. American Mineralogist, 78 (5-6), pp. 641-648.
Toledo, M. C. M. and Pereira, V. P. (2001). A Variabilidade da Composio da Apatita
Associada a Carbonatitos. Revista do Instituto Geolgico, 22 (1-2), pp. 27-64.
Torres, M. G. (1996). Caracterizao Mineralgica do Minrio Fosftico da Arafrtil
S.A., no Complexo Alcalino Carbonattico do Barreiro, Arax, MG. Master
Thesis, Universidade de Braslia, Brasil, 149 p.
Uytenbogaardt, W. and Burke, E. A. J. (1971). Tables for Microscopic Identification of
Ore Minerals, Elsevier, Amsterdam, 430 p.
Vasconcelos, C. S.; Dehler, N. M.; Yamato, A. A.; Lopes Jr., I. (1999). Projeto
Jacupiranga - Rio Guara. CPRM: Servio Geolgico do Brasil, 233 p.

139
Veizer, J. (1983). Trace Elements and Isotopes in Sedimentary Carbonates. In: Reeder, R.
J. (ed). Carbonates: Mineralogy and Geochemistry. Mineralogical Society of
America, Reviews in Mineralogy, 11, pp. 227-264.
Waychunas, G. A. (2002). Apatite Luminescence. In: Kohn, M. J.; Rakovan, J.; Hughes,
J. M. (eds). Phosphates: Geochemical, Geobiological, and Materials Importance.
Mineralogical Society of America and Geochemical Society, Reviews in
Mineralogy and Geochemistry, 48, pp. 701-742.
Wenk, H. R.; Barber, D. J.; Reeder, R. J. (1983). Microstructures in Carbonates. In:
Reeder, R. J. (ed). Carbonates: Mineralogy and Geochemistry. Mineralogical
Society of America, Reviews in Mineralogy, 11, pp. 301-368.
Winter, J. D. (2001). An Introduction to Igneous and Metamorphic Petrology, Prentice
Hall, New Jersey, 697 p.
Wyllie, P. J., and Tuttle, O. F. (1960). The System CaCO3-H2O and the Origin of
Carbonatites. Journal of Petrology, 1, pp. 1-46.
Wyllie, P. J.; Cox, K. G.; Biggar, G. M. (1962). The Habit of Apatite in Synthetic
Systems and Igneous Rocks. Journal of Petrology, 3, pp. 238-242.

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VITA

Paula Regina P. C. Alves was born in So Paulo, Brazil, on June 3, 1976. In

January 2000, she received her B.S. in Geology from the University of So Paulo. She
received a scholarship from CNPq, the Brazilian science and technology funding agency,
for her undergraduate research in mineralogy from 1996 until 1998. In 1999, she was
selected for a trainee program with Bunge, a company that mines phosphate deposits in
Brazil to produce fertilizers. She developed her senior thesis in the phosphate process
technology while working for this project, and she was hired upon graduation.
In July 2001, she left her job to pursue a M.S. degree in Geology with the
Missouri University of Science and Technology (formerly University of Missouri-Rolla).
There, she was teaching assistant in Stratigraphy, Structural Geology, and Igneous
Petrology. While a graduate student, she was the recipient of the second highest grant for
M.S. research provided by the Society of Economic Geologists in 2002. In recognition of
her involvement with the industrial minerals, she also received the Robert L. Bates
memorial scholarship in 2002, and the Society of Mining, Metallurgy and Exploration,
Industrial Minerals Division student award, in 2003.
She published several papers on the mineralogy of phosphates from pegmatites,
and in applied mineralogy of carbonatite-hosted phosphate ores, two of which are cited in
this thesis.
Paula has been a mineral scientist with Imerys Pigments since 2003. She has led
projects related to mineral resources and process technology in the companys facilities in
the USA and in Brazil.