The Tjårrojåkka Apatite-Iron and Cu (

Transcription

2007:17
DOCTORA L T H E S I S
The Tjårrojåkka Apatite-Iron and Cu (-Au)
Deposits, Northern Sweden
- Products of One Ore Forming Event
Åsa Edfelt
Luleå University of Technology
Department of Chemical Engineering and Geosciences
Division of Ore Geology and Applied Geophysics
2007:17|: -1544|: - -- 07⁄17 -- 
Thesis for the Degree of Doctor of Philosophy
The Tjårrojåkka Apatite-Iron and Cu (-Au)
Deposits, Northern Sweden
– Products of One Ore Forming Event
Åsa Edfelt
Division of Ore Geology and Applied Geophysics
Luleå University of Technology
SE-971 87 Luleå, Sweden
Phone: +46-920-492029
E-mail: [email protected]
May 2007
For Lionel and Adina with love
Abstract
The Tjårrojåkka area is located about 50 km WSW of Kiruna, northern
Sweden, and hosts one of the best examples of spatially related apatite-iron
(Kiruna type) and Cu (-Au) deposits in Sweden. The results from this project
show that the two deposits are genetically related and indicate the presence of a
younger, previously unknown, 1780 Ma generation of apatite-iron ores in
northern Sweden.
The bedrock in the Tjårrojåkka area is dominated by intermediate and
basic extrusive and intrusive rocks. The 1880 Ma intermediate volcanic rocks,
belonging to the Porphyrite Group, formed in association with subductionrelated magmatism in a volcanic arc environment close to the Archaean
continental margin. The overlying basalts and related feeder dykes formed
through extrusion of mantle derived magma during a local extensional event in
a subaquatic back arc setting. The area was metamorphosed at epidoteamphibolite facies and deformed during at least three stages, creating NE-SW,
E-W, and NNW-SSE striking structures.
The Tjårrojåkka deposits can be considered as belonging to the Feoxide-Cu-Au (IOCG) group of deposits representing two “end-members” of
the class. Several generations and overlapping hydrothermal alteration stages
indicate a long, complex history of fluid activity between 1780 and 1700 Ma
related to the formation and post-ore modification of the deposits. The strongly
altered host rock shows enrichment of alkalis related to mineralisation due to
the formation of albite, scapolite, and K-feldspar. It is not obvious whether the
massive part of the apatite-iron ore formed from an iron rich melt or through
hydrothermal replacement, but a hydrothermal system was active at least at a
late stage during the deposition of the iron ore, producing the apatitemagnetite-actinolite breccia, the copper mineralisation, as well as the extensive
hydrothermal alterations.
The ore forming fluids were CO2-bearing, moderately to highly saline
CaCl2-NaCl-rich fluids of most likely magmatic origin. The magnetite ore
deposited at around 500 to 650°C followed by the copper mineralisation
between 150 and 450°C. Cooling along with decrease in salinity were
important factors for metal precipitation at Tjårrojåkka. A NE trending shear
zone acted as a major fluid channel and a structurally favourable location for the
deposition of the copper (-gold) mineralisation.
From apatite chemistry, it is evident that there is a fundamental
difference between typical Kiruna type apatite-iron ores and copper mineralised
apatite-iron deposits of IOCG character and could potentially be used as a tool
for distinguishing copper mineralising apatite-iron systems from barren.
Keywords IOCG deposit, apatite-iron ore, Kiruna type, Sweden, Palaeoproterozoic,
geochemistry, hydrothermal alteration, fluid inclusions, U-Pb dating, stable isotopes,
apatite chemistry.
PREFACE
This PhD project was initiated in 2001 by Dr. Olof Martinsson as part of
the GEORANGE-funded research project P7 on Fe-oxide Cu-Au deposits in
Norrbotten, Sweden. In May the same year, just before I finished my MSc
thesis in Turku, I got an e-mail saying that a PhD position dealing with Feoxide Cu-Au (IOCG) deposits was available at Luleå University of
Technology. Firstly, I looked at a map to find out where Luleå is located,
secondly, I tried to find out what an IOCG deposit is (to the first question I
found the answer, to the second one I still haven’t found one), and thirdly, I
applied for the position not knowing what I was going to study. The week
before midsummer, I got a phone call from Olof saying that they would like to
meet me for an interview the following Monday regarding the PhD position. I
packed my bag, got on the plane, and the rest is history.
Of the papers and manuscripts included in the thesis, I have written the
main part with guidance from my supervisor and advisors at the cooperating
institutions. However, in article I, Dr. Paul Evins, Dr. Craig Storey, and Dr.
Teresa Jeffries did the sampling and analysis of the zircon dating, and Mr.
Alessandro Sandrin and Prof. Sten-Åke Elming did the geophysical sampling
and modelling. In manuscript III, Dr. Curt Broman did the sampling and
measurements on six of the samples in the fluid inclusion study, as well as the
interpretation of raw data, while Dr. Kjell Billstöm performed the age
determinations and assessment of the geochronology data. In manuscript IV,
Dr. Olof Martisson provided the samples from all deposits except Tjårrojåkka
and the LA-ICPMS work was done under supervision of Dr. Teresa Jeffries,
who also did the raw data corrections and evaluation.
Finally, I have never regretted that I took the chance to work in this
project even if it sometimes was hard both physically and mentally. During my
PhD studies, I got the chance to travel to places I could only dream of, I have
met scientists from all over the world who have shared their knowledge with
me, I have made new friends, but most importantly, I have learnt to think
independently and critically. It is now time to move on, but the experience and
knowledge I have obtained during these years, I will always treasure.
Luleå, April 20th, 2007
Åsa Edfelt
CONTENTS
ABSTRACT
PREFACE
CONTENTS
LIST OF PUBLICATIONS
INTRODUCTION ...............................................................................1
OBJECTIVES OF THESIS ....................................................................2
REVIEW OF RESEARCH....................................................................3
Iron-oxide Cu-Au (IOCG) deposits...................................................3
Characteristics.............................................................................3
Ore genesis .................................................................................5
Apatite-iron ores of Kiruna type ........................................................6
Characteristics.............................................................................6
Ore genesis .................................................................................6
METHODOLOGY................................................................................8
Field work and drill core logging .......................................................8
Analytical work .................................................................................8
Whole-rock geochemistry...........................................................8
Microscopy and Scanning Electron Microscopy (SEM)................8
Microprobe ................................................................................9
Fluid inclusions...........................................................................9
Radiogenic isotopes .................................................................. 10
Stable isotopes (O, H, and S)..................................................... 11
LA-ICPMS............................................................................... 11
SUMMARY OF RESULTS AND DISCUSSION ............................... 12
Geology of the Tjårrojåkka area ....................................................... 12
Mineralisation and hydrothermal alteration....................................... 13
Mineralisation ........................................................................... 13
Hydrothermal alteration ............................................................ 13
Fluid characteristics and ore genesis.................................................. 14
The Tjårrojåkka deposits in the IOCG spectrum.............................. 16
CONCLUSIONS ................................................................................. 17
SIGNIFICANCE FOR EXPLORATION AND FUTURE WORK... 18
ACKNOWLEDGEMENTS ................................................................. 20
REFERENCES .................................................................................... 21
LIST OF PUBLICATIONS
The thesis “The Tjårrojåkka Apatite-Iron and Cu (-Au) Deposits,
Northern Sweden – Products of One Ore Forming Event” consists of the following
articles and manuscripts:
I.
Edfelt, Å., Sandrin, A., Billström, K., Evins, P., Jefferies, T., Storey, C.,
Martinsson, O. and Elming, S.-Å., 2006. Stratigraphy and tectonic
setting of the host rocks to the Tjårrojåkka Fe-oxide Cu-Au
occurrences, northern Sweden. GFF 128:221-232
(Reprinted with kind permission from The Geological Society of Sweden)
II. Edfelt, Å., Armstrong, R.N., Smith, M., and Martinsson, O., 2005.
Alteration paragenesis and mineral chemistry of the Tjårrojåkka apatiteiron and Cu (-Au) occurrences, Kiruna area, northern Sweden.
Mineralium Deposita 40:409-434
(Reprinted with kind permission from Springer Science and Business Media)
III. Edfelt, Å., Billström, K., Broman, C., Rye, R.O., Smith, M.P., and
Martinsson, O., 2007. Origin and fluid evolution of the Tjårrojåkka
apatite-iron and Cu (-Au) deposits, Kiruna area, northern Sweden (to
be submitted)
IV. Edfelt, Å., Smith, M., Armstrong, R. N., and Martinsson, O., 2007.
Apatite chemistry: applications for characterising apatite-iron and
IOCG deposits (to be submitted)
The following abstracts and reports have also been published during my PhD
studies, but are not included in the thesis:
1. Edfelt, Å. and Martinsson, O., 2006. Apatite chemistry – a potential
tool for IOCG exploration. The 27th Nordic Geological Winter
Meeting, Oulu, Finland, January 2006. Bulletin of The Geological
Society of Finland, Special Issue 1, p. 29 (Abstract)
2. Edfelt, Å. and Martinsson, O., 2005: Box-3: Fennoscandian Shield Iron Oxide-Copper-Gold deposits, Tjårrojåkka, northern Sweden: Lat
67° 40' N, Long. 19° 10' E. Ore Geology Reviews 27:328-329
3. Berggren, R., Billström, K., Edfelt, Å., Evins, P., Mark, G.,
Martinsson, O., Sandrin, A., Stein, H., Weihed, P., Verco, M., and
Williams, P., 2005. Final report Georange, Project P7 (89120). Feoxide Cu-Au deposits in Northern Sweden. January 2005. (Report)
4. Edfelt, Å., Eilu, P., Martinsson, O., Niiranen, T. and Weihed, P.,
2004. The northern Fennoscandian IOCG-province. SGA News,
December 2004, 18. (Newsletter)
5. Edfelt, Å., Broman, C. and Martinsson, O., 2004. A preliminary fluid
inclusion study of the Tjårrojåkka IOCG-occurrence, Kiruna area,
northern Sweden. The 26th Nordic Geological Winter Meeting,
Uppsala, Sweden, January 2004, GFF 126. (Abstract)
6. Edfelt, Å. and Martinsson, O., 2004. Tjårrojåkka Fe-oxide Cu-Au
deposit. In Eilu, P. Iron oxide-copper-gold excursion and workshop,
Northern Finland and Sweden, 31.5-4.6.2004. GTK Report M
10.3/2004/1/10: 70-72. (Report)
7. Edfelt, Å. and Martinsson, O., 2004. The Tjårrojåkka Fe-oxide and
Cu-Au occurrences, northern Sweden – products of one ore forming
event? IAVCEI General Assembly, 14-19 November 2004, Pucón,
Chile. (Abstract)
8. Martinsson O., Williams P.J., Edfelt Å., Sandrin A., Verco M., Evins
P., Mark G., Billström K., Stein H., Broman, C., and Weihed P.,
2004: Relationships of Kiruna-Type Apatite Iron Ores and Iron
Oxide-Copper-Gold Deposits, Norrbotten, Sweden. IAVCEI General
Assembly, 14-19 November 2004, Pucón, Chile. (Abstract)
9. Edfelt, Å. and Martinsson, O., 2004. Tjårrojåkka Fe-oxide Cu-Au
deposit. In Eilu, P. Iron oxide-copper-gold excursion and workshop,
Northern Finland and Sweden, 31.5-4.6.2004. GTK Report M
10.3/2004/1/10: 70-72. (Report)
10. Edfelt, Å. and Martinsson, O., 2003. The Tjårrojåkka Fe-oxide Cu (Au) occurrence, Kiruna area, northern Sweden. In Proceedings of the
seventh biennial SGA meeting, Athens, August 2003. Eliopoulos et al.,
(Eds.), Mineral Exploration and Sustainable Development, Vol 2,
1069-1071. Millpress, Rotterdam. (Extended abstract)
11. Billström, K., Edfelt, Å., Evins, P., Mark, G., Martinsson, O.,
Sandrin, A., Stein, H., Weihed, P., Verco, M., and Williams, P., 2003.
Progress report 2003 Georange, Project P7 (89120). (Report)
12. Martinsson, O., Elming, S.-Å., Edfelt, Å., Sandrin, A., Broman, C.
and Billström, K., 2002. Mineralisation processes and geologicalgeophysical targeting of Cu-Au-(Fe) deposits in the Kiruna region,
northern Sweden. Georange, Progress report 1, 2002-02-15. (Report)
The Tjårrojåkka apatite-iron and Cu (-Au) deposits, Northern Sweden
1
INTRODUCTION
Since Hitzman et al. (1992)
classified iron oxide-rich Cu-Au
deposits, including the great Olympic
Dam deposit, as an independent group
of ore deposits, there has been a
growing exploration and research
interest for these types of deposits. The
iron-oxide Cu-Au (IOCG) deposits
show a great variation in the geological
settings, alteration systematics as well as
mineralising fluid compositions. Even
though IOCG deposits are an
important source for copper and gold
all over the world, several fundamental
questions with respect to their genesis
are still unanswered. It is also debated
whether apatite-iron ores of Kiruna Fig. 1 Location of the Tjårrojåkka area.
type should be incorporated in this
group (e.g. Hitzman 2000). Moreover, it remains unclear if there is a genetic
link between some iron-oxide and copper deposits, even if a clear spatial
relation has been observed in both Chile (Gelcich et al., 2005; Marschik and
Fontboté, 2001; Naslund et al., 2002) and Sweden (Edfelt et al., 2005;
Lindskog, 2001; Martinsson and Virkkunen, 2004).
Northern Norrbotten, Sweden, is an important mining district hosting
some of the world’s largest apatite-iron ores (Kiirunavaara and Malmberget) and
the economically significant Aitik Cu-Au deposit. The area has also been
described as an IOCG-district (Hitzman et al., 1992), and at the moment
several exploration companies are using this concept as an exploration model in
the area. The Tjårrojåkka apatite-iron and copper (-gold) deposits are situated
in the northwestern part of the area about 50 km WSW of the town of Kiruna
and the prominent Kiirunavaara apatite-iron ore (Fig. 1). The Tjårrojåkka
apatite-iron ore was discovered by the Geological Survey of Sweden in 1963
through airborne magnetic measurements and a few years later the adjacent
copper-gold prospect was found.
The Tjårrojåkka deposits were chosen for this study because they are the
best example of spatially related apatite-iron and copper (-gold) deposits in
Sweden and there are a large number of drill cores from the deposits accessible
at the Geological Survey’s Mineral Resources Information Office in Malå.
Some preliminary fluid inclusion data and geochemistry were also available
from a pre-study performed by Dr. Olof Martinsson and Dr. Curt Broman.
2
OBJECTIVES OF THESIS
The main objectives of this PhD project have been to study
9The genetic link between the Tjårrojåkka apatite-iron and Cu (-Au) deposits
A clear spatial relationship has been observed between some apatiteiron and copper-gold deposits indicating a possible genetic link between
them. It has important implications for the ore genetic model of IOCG
deposits as well as for exploration purposes if this genetic link can be
established.
9The relation between mineralisation and magmatic and tectonic processes in the area
Having information about when and where the deposits formed is
important for understanding the ore genesis. It also generates a wider
understanding about a relatively new deposit type that has a big economical
potential not only in Norrbotten, but worldwide.
9Geological, petrophysical, and geophysical characteristics useful for targeting IOCG
deposits
The project has been an integrated geological-geophysical study,
which has made it possible to illustrate this type of ore deposit from several
perspectives and identify features possible useful as exploration tools.
Fig. 2 Location of apatite-iron and IOCG districts and some major deposits.
3
REVIEW OF RESEARCH
Apatite-iron and Fe-oxide Cu-Au (IOCG) deposits occur worldwide
(Fig. 2), in different tectonic settings, of a variety of ages, and with shifting
characteristics. There are some common features between Kiruna type apatiteiron ores and IOCG deposits, but there is also much dissimilarity (Table 1).
Below, the main characteristics and proposed genetic models for the two
deposit groups are briefly summarised.
Iron-oxide Cu-Au (IOCG) deposits
Characteristics
Fe-oxide Cu-Au (IOCG) deposits are a relatively new class of ore
deposits first defined by Hitzman et al. in 1992. It does not represent a single
style of deposits but includes a family of loosely related deposits from iron oxide
dominated, to copper, U, and REE-rich deposits. However, there are some
characteristics that IOCG deposits share and that can be used as a guideline to
whether a deposit should be included in the IOCG family, or not.
1. The age of IOCG deposits vary widely and they occur from Archaean
(Salobo; (Requia et al., 2003)) to Cretaceous (Candelaria; (Marschik and
Fontboté, 2001)). There is no specific time that seems to be more
favourable for IOCG deposits (Hitzman, 2000).
2. IOCG deposits occur in a variety of tectonic settings from intra-continental
extensional settings to subduction zones and are generally structurally
controlled (Barton and Johnson, 1996; Hitzman, 2000). According to
Barton and Johnson (1996) they form in global arid zones or former
evaporite-bearing basins.
3. IOCG deposits are hosted in mafic to felsic igneous (volcanic and plutonic)
as well as sedimentary rocks, and their metamorphic equivalents (Barton
and Johnson, 1996; Hitzman et al., 1992).
4. The morphology varies from stratabound to discordant, brecciated and
irregular masses (Barton and Johnson, 1996; Hitzman, 2000).
5. The ore mineralogy is characterised by an abundance of Fe-oxides (either
magnetite or hematite) and a lack of Fe-sulphides, Pb, and Zn (Hitzman,
2000; Hitzman et al., 1992). Fe-oxides ± apatite generally occur in the
proximal part of a system and hematite ± Cu-Fe-sulphide ± REE in the
distal part or superimposed on the proximal part (Barton and Johnson,
1996). CO3, Ba, P, and F minerals are also common (Hitzman et al., 1992).
Uranium is often enriched in IOCG deposits with the Olympic Dam being
the word’s largest producer of U (Hitzman and Valenta, 2005). According
4
to Hitzman et al. (1992), U is more common in hematite-dominated
systems and usually post-dates iron mineralisation and alteration.
6. The wall rock is commonly intensely altered (Hitzman et al., 1992) with
large alteration halos. The type of alteration is largely dependent on host
rock. Mafic rocks tend to have early scapolite and late chlorite and
carbonate alteration, while felsic rocks is characterised by early proximal
albite alteration related to magnetite ± apatite mineralisation followed by a
later more distal K-feldspar, silicic, and sericite alteration (Barton and
Johnson, 1996).
Table 1. Summarised general characteristics of Kiruna type apatite-iron ores and
IOCG deposits.
Age
Apatite-iron deposits
(Kiruna type)
Paleoproterozoic to PliocenePleistocene
IOCG deposits
Archaean to Cretaceous
Tectonic setting
Intracratonic settings to subduction zones, emplacement
related to regional fault zones
Intracratonic settings to subduction zones (generally structurally
controlled)
Host rock
Calc-alkaline to alkaline volcanic rocks (andesite to rhyolite)
Igneous and sedimentary rocks
(mafic to felsic)
Morphology
Large disk-like bodies, vein
systems, impregnations, lava
flows, pyroclastic material
Stratabound to discordant, brecciated tabular to irregular masses
Ore (gangue)
mineralogy
Magnetite-hematite-apatite
(calcite, actinolite, diopside)
Proximal magnetite+apatite;
distal or superimposed hematite
± Cu-Fe-sulphides ± REE ± U
(CO3, Ba, P, and F minerals)
Alteration
Locally silicification, sericitization, albitization with minor
actinolite and carbonates
Intensively altered, sodicpotassic-hydrolytic
Ore genesis
Magmatic melt and/or hydrothermal replacement from
magmatic fluid
Hydrothermal (magmatic or
non-magmatic) in come cases
with evaporites as source for
ligands
5
Ore genesis
Regarding the ore genesis of IOCG deposits, several different models
have been proposed involving both magmatic and non-magmatic fluids as well
as evaporites as a prerequisite for IOCG mineralisation. Hitzman et al. (1992)
proposed that IOCG deposits formed in upper crustal environments from
volatile-rich magmatic-hydrothermal fluids originating from deeper-seated
intrusions. The fluids reached shallower levels of the crust through deep-seated
fractures. This would result in deep sodic alteration and leaching of iron where
the fluid is interacting with the heat source and potassic alteration together with
metal deposition at higher levels where the fluids cool down due to interaction
with the wall rock or through mixing with meteoric water.
Barton and Johnson (1996) noted the lack of correlation between IOCG
deposits and composition of spatially related igneous rocks as well as the vast
hydrothermal alterations present also in mafic systems, suggesting that
evaporites and non-magmatic fluids played an important role in the ore genesis.
They used the spatial association with evaporites, sodic alteration, and
geochemical data (e.g. presence of marialitic scapolite, salinities >20 wt. %, G34S
>5‰ in many deposits) as evidences for the involvement of an evaporitic
component. The proposed model explains the formation of IOCG deposits
through circulation of highly saline fluids where evaporites supplied the Cl
needed for metal transport and Na for the sodic alterations. Magmatism would
only provide the heat necessary and the igneous host rocks serve as a source for
metals.
Pollard (2000) strongly argue that the presence of evaporites is not a
requirement for the formation of IOCG deposits because of the lack of
evaporites in several IOCG districts, and promoted a magmatic source for the
ore-forming fluids as well as metals. He also suggests that IOCG deposits are
part of a spectrum of intrusion-related Cu-Au deposits with porphyry-copper
deposits representing the other end-member of the group. According to Mark
et al. (2000) there is a also a spectrum of deposit within the IOCG group
ranging from relatively lower gO2, hotter and deeper deposits (e.g. Ernest
Henry) to those forming at a higher crustal levels from more oxidized lower
temperature fluids (e.g. Olympic Dam) and that fluid mixing could be the cause
of the diversity. The continuum is also seen in the copper sulphide association
with chalcopyrite being the most dominant copper sulphide in the first
mentioned and chalcocite-bornite-chalcopyrite in the other.
The diversity within the IOCG class of deposits probably reflects a
variety of ore forming processes and environments. Hence, it is not likely that a
single ore genetic model explains the formation of all IOCG deposits, but
rather every deposit has to be carefully studied and the genetic model adjusted
to meet local conditions.
6
Apatite-iron ores of Kiruna type
Characteristics
In 1931, Geijer defined the “Kiruna type” iron ores as “all those deposits
that are, in their geological features, closely comparable to those at Kiruna”.
After Hitzman et al. (1992) included apatite-iron ores as a “subgroup” of
IOCG deposits the centre of attention was once again back on them. The focus
has the last decade been on the El Laco deposit in Chile since it is the maybe
best preserved magnetite-apatite ore of Kiruna type (Henríquez et al., 2003;
Henríquez and Nyström, 1998; Naslund et al., 2003; Naslund et al., 2002;
Rhodes and Oreskes, 1999; Rhodes et al., 1999; Sillitoe and Burrows, 2002).
1. The age of apatite-iron ores varies from Paleoproterozoic (Kiirunavaara) to
Pliocene (El Laco). No Archaean examples are known (Frietsch and
Perdahl, 1995).
2. The emplacement of apatite-iron ores is related to regional fault zones
(Frietsch and Perdahl, 1995) either in intracratonic settings (e.g.
Kiirunavaara) or subduction zones (e.g. El Laco).
3. The host rock comprises calc-alkaline to alkaline volcanic rocks (andesite to
rhyolite) (e.g. Frietsch and Perdahl, 1995; Geijer, 1931; Rhodes et al.,
1999; Treloar and Colley, 1996).
4. The morphology of the ore bodies includes disk-like, concordant bodies,
vein systems, and impregnations (Frietsch and Perdahl, 1995). At the El
Laco deposit the ore also occur as lava flows and pyroclastic material (e.g.
Naslund et al., 2002).
5. The ore mineralogy is simple with magnetite and/or hematite as ore minerals
(Martinsson, 2004). The amount of gangue minerals is low but F-rich
apatite, amphibole or pyroxene often occur (Geijer, 1931).
6. Alterations are generally not as prominent a feature in apatite-iron ores as in
for example porphyry copper and IOCG systems. Where alterations occur,
they generally include silicification, sericitisation, albitisation, and
epidotisation, with actinolite, scapolite, tourmaline, biotite, and carbonates
as less common constituents (Martinsson, 2004; Treloar and Colley, 1996).
Ore genesis
The genesis of apatite-iron ores of Kiruna type have been subject of
discussion for more than 100 years, with the main focus on magmatic or
hydrothermal origins. The magmatic model explains the formation of these
types of deposits from high temperature, volatile-rich iron oxide melts, mainly
based on textural magmatic features like columnar and dendritic magnetite,
igneous structures, and the relation between the ores and their host rocks with
El Laco as the most spectacular example (Henríquez et al., 2003; Henríquez
and Nyström, 1998; Naslund et al., 2002; Nyström and Henríquez, 1994; Park,
7
1961). Chemical data from magnetite and apatite is also used to support the
model (Frietsch and Perdahl, 1995; Naslund et al., 2002; Nyström and
Henríquez, 1994). Broman et al. (1999) interpreted fluid inclusion data from
pyroxene and apatite at El Laco to have formed from a late-magmatic remnant
fluid gradually becoming lower in temperature and salinity.
The hydrothermal model, on the other hand, favours metasomatic
replacement from Fe-rich hydrothermal hypersaline fluids as a model for the
formation of these types of deposits (Hildebrand, 1986; Hitzman et al., 1992;
Rhodes et al., 1999; Sillitoe and Burrows, 2002). Based on theoretical grounds
the existence of iron oxide magmas was questioned by Hildebrand (1986),
whereas Rhodes and Oreskes (1999) used oxygen isotopes as an evidence to
support the replacement theory. Barton and Johnson (1996) proposed a model
for the formation of Fe-oxide deposits by hydrothermal processes involving
evaporitic ligand sources.
Although apatite-iron ores have common characteristics, there is a large
variation in alteration and mineralisation style between deposits. This have led
several authors to the conclusion that all deposits of this type did not form by
one and the same process, but probably both magmatic and/or hydrothermal
mechanisms were involved in the formation of them (Barton and Johnson,
1996; Martinsson, 2004; Naslund et al., 2002).
8
METHODOLOGY
Field work and drill core logging
The Tjårrojåkka area is located about 50 km WSW of Kiruna close to
the Caledonian front at 600-1000 metres above sea level (Fig. 1). The study
area covers 8 x 8 km between 7512000-7520000 N and 1639000-1647000 E in
the national grid RT90. The area is remote and access is only possible by
helicopter. The topography shows great variation and to some areas access is
difficult due to steep hill sides covered with debris from frost wedging, bush
vegetation, or marsh. Fieldwork was carried out during the summers 20012004 and seventy-two outcrops were sampled for whole-rock geochemical and
petrological analyses.
A total of 5108 metres of drill core were logged and sampled at the
Geological Survey’s Mineral Resources Information Office in Malå.
Unfortunately, most drill cores from the apatite-iron deposit have been
disposed and only part of them are kept. Four drill sections, one in the apatiteiron ore (400W) and three in the copper deposit (120E, 320E, and 600E), were
logged and approximately 140 samples were collected for whole-rock,
petrographical, radiogenic isotope, and stable isotope analyses as well as fluid
inclusion work.
Analytical work
Whole-rock geochemistry
Whole-rock analyses for major and trace elements were carried out at
Activation Laboratories Ltd in Canada. The major elements were analysed
using the inductively coupled plasma method (ICP-OES), while trace elements
were analysed by inductively coupled plasma mass spectrometry (ICP-MS) and
instrumental neutron activation analysis (INAA).
Microscopy and Scanning Electron Microscopy (SEM)
Thin and polished sections representing different rock and alteration
types from both outcrops and drill cores were examined in transmitted and
reflected light at Luleå University of Technology. A Jeol 5900LV scanning
electron microscope (SEM) at the Natural History Museum, London, was used
to characterise alteration textures and micron-sized minerals not detectable
9
under an ordinary microscope. SEM observations were made using a backscattered electron detector (BSE), with an accelerating voltage of 20 kV and a
beam current of 1 nA measured specimen current in pure cobalt metal.
Microprobe
Mineral analyses were performed using a Cameca SX50 WDS electron
microprobe at the Natural History Museum, London, with the technique
described in Potts et al. (1995). Silicate analyses were carried out using an
accelerating voltage of 15 or 20 kV, a beam current of 20 nA, and a 5 Pm beam
diameter. Apatites were analysed using an accelerating voltage of 15 kV, a beam
current of 20 nA, and a 5 Pm beam diameter. For sulphides and oxides a 1 Pm
beam diameter, an accelerating voltage of 15 or 20 kV, and a beam current of
20 nA were used, except for one set of sulphide analyses for which a 60 nA
beam current was used. Different pure metals, natural minerals, and synthetic
glasses were used as standards. Interferences between X-ray peaks for Ba/Ti,
Ce/Ti, Ce/Ba, Nd/Ce, Co/Fe, F/Ce, Mo/S, and V/Ti were corrected
empirically using previously collected data from standards.
Fluid inclusions
Fluid inclusions were studied at the Fluid Research Laboratory at the
Department of Geology and Geochemistry, Stockholm University and at the
University of Brighton, by optical microscopy, microthermometry, and Raman
microspectrometry in doubly polished thin sections obtained from drill cores.
Fluid inclusions in quartz, calcite, apatite, and actinolite were analysed in eight
samples from five different drill cores.
A conventional microscope was first used to get an outlook of the
samples and the distribution of fluid inclusions. At the Stockholm University
the microthermometric low temperature measurements, 180 to +35oC, were
made on a Linkam THM 600 stage with a reproducibility of ±0.1oC. The
cooling was obtained by a flow of liquid nitrogen through the stage. The high
temperature measurements, +35 to +600oC were done with a Chaixmeca
heating/freezing stage with a reproducibility of ±2oC. At the University of
Brighton a Linkam MDS600 heating/freezing system was used with similar
precision. The instruments were calibrated with synthetic fluid inclusion
standards and small amounts of high-purity melting-point standards. In order to
identify solid phases and check for the presence of gases in the inclusions,
Raman analyses were made with a multichannel Dilor XY Raman
spectrometer on some of the samples. Exciting radiation was provided by the
green line (514.5 nm) of an Innova 70 argon laser. The laser beam was focused
on the sample with a 100 X objective in an optical microscope. Calibration was
made with respect to wave number using a neon laser and a silicon standard.
10
Radiogenic isotopes
Radiogenic U-Pb isotope analyses were performed on zircons and
titanites, while Sm-Nd analyses were carried out on two apatite-magnetiteamphibole samples from the apatite-iron ore.
Zircon was separated from an andesite for LA-ICPMS analysis. The
crystals were 30-50 Pm, colourless, equant grains to ca. 100 Pm long colourless,
stubby prisms with axial ratios less than 2:1 or chips of terminations from larger
crystals from an andesite. They were mounted in epoxy resin and polished
down through approximately half the diameter of the grains. All sites chosen
for analysis were from optically clear zircons with CL oscillatory zoning typical
of magmatic growth (Pidgeon, 1992). The LA-ICPMS analysis were made at
the Museum of Natural History in London with frequency quintupled
Nd:YAG laser (UP213), with a homogenised flat beam, operating at 213 nm
wavelength. The ablation was carried out in a He atmosphere in order to
enhance transport efficiency and limit mass fractionation (Jeffries et al., 2003).
The ablated particles were transported to, ionized and measured in a
quadrupole (Thermo Elemental) Plasmaquad 3 ICP-MS with enhanced
sensitivity (S-option) interface. All analyses are standardised to the 1065 Ma old
zircon geostandard 91500 (Wiedenbeck et al., 1995), which effectively corrects
for mass bias.
Titanites from different alteration parageneses were separated from drill
cores and handpicked under a binocular microscope. They were initially treated
in a clean laboratory, washed in acetone in an ultra-sonic bath, then with
diluted HNO3 on a hot plate, and finally rinsed in double distilled water.
Briefly, isotope dilution analysis was performed as follows. Each sample was
spiked with a 233-236U/205Pb solution and a mixture of HF and HNO3 was
added. Following this, it was dissolved in a Teflon bomb at ca. 200qC for five
days. After evaporation and dissolution in HBr an initial ion exchange step was
carried out from which a purified Pb aliquot resulted. The uranium fraction
went through a second ion exchange procedure in HCl where eventually
remaining Fe was removed. Finally, the resulting Pb fraction was loaded on a
single filament, while the uranium was loaded using a double-filament
arrangement, and the appropriate isotopic ratios were measured on a Finnigan
MAT 261 spectrometer. A software package from Ludwig (1991a; 1991b) was
used to calculate and plot relevant ages and associated errors.
Two samples taken from the massive part of the apatite-iron ore were
selected with the aim to derive a Sm-Nd mineral isochron. It was possible to
separate the same three minerals (amphibole, magnetite, and apatite) from each
of them, and these phases underwent conventional ion exchange techniques to
obtain Sm and Nd aliquots (Pin and Zalduegui, 1997), which subsequently
were analyzed on a Finnigan MAT 261 spectrometer (see Mellqvist et al.
(1999) for further analytical details). All the chemical procedures and mass
spectrometry related to radiogenic isotope work were carried out at the
Laboratory for isotope geology at the Swedish Museum of Natural History in
Stockholm.
11
Stable isotopes (O, H, and S)
Stable isotope analyses were carried out at the isotope laboratory at the
U.S. Geological Survey in Denver, USA. Oxygen isotope data were obtained
from quartz, K-feldspar, magnetite, apatite, and amphiboles by use of the BrF5
method described by Clayton and Mayeda (1963) and a Finnigan 252 mass
spectrometer. Reproducibility was generally ±0.2 per mil or better. Hydrogen
isotope data were collected by continuous flow isotope ratio mass spectrometry
using a Thermo Finnigan TC/EA pyrolysis device coupled to a Thermo Delta
Plus XL mass spectrometer (Sharp et al., 2001). Reproducibility was generally
±4 per mil or better for GD. Oxygen and hydrogen isotopic compositions are
reported relative to Vienna Standard Mean Ocean Water (VSMOW) in
conventional G-notation. An analysis of the standard material that was run along
with the unknowns gave í96 per mil, which almost matches within error the
accepted value of í100 ± 2 per mil (Coplen et al., 2001). Sulphur isotope
analyses were conducted on chalcopyrite, bornite, and pyrite following the
method of Giesemann et al. (1994) using a Carlo Erba Elemental Analyzer
coupled to a Micromass Optima mass spectrometer. Reproducibility was ±0.2
per mil or better. The isotopic compositions are expressed in G-notation
relative to Cañon Diablo Troilite (CDT).
LA-ICPMS
LA-ICPMS analyses were carried out on apatite samples from five
apatite-iron and two IOCG deposit in Norrbotten using a UP-213 laser
ablation system coupled to a VG Plasmaquad 3 ICP-MS. The apatites were
ablated at a laser energy of 0.1 mJ/pulse and a rate of 20 Hz or 10 Hz, resulting
in a spot size of about 45 mm. National Institute of Science and Technology
(NIST) standard glass SRM612 was used as a calibration standard and isotope
ratios were converted to ppm concentrations using 43Ca as an internal standard,
and Ca concentrations previously determined by electron microprobe.
Accuracy was monitored using US Geological Survey (USGS) standard SRM
BCR-2G.
12
SUMMARY OF RESULTS AND DISCUSSION
Geology of the Tjårrojåkka area
The Tjårrojåkka area is dominated by extrusive and intrusive rocks of
basic to intermediate composition. Primary structures are generally not well
preserved, clear stratigraphic indicators are few, and hardly any contacts
between the different lithologies have been observed in outcrop.
The intermediate volcanic rocks belong to the Porphyrite Group and are
associated with volcaniclastic rocks and later quartz-monzodioritic intrusions.
They formed during subduction-related magmatism in a volcanic arc
environment close to the Archaean continental margin above the Kiruna
Greenstone Group. A U-Pb LA-ICPMS dating of zircon gives the andesites an
age of 1878 ± 7 Ma. The overlying basalts and related feeder dykes do not
chemically correlate with any known basaltic Svecofennian unit in northern
Norrbotten (i.e. the Porphyrite Group or the Kiirunavaara Group). They may
therefore have formed during a local extensional event in a back arc setting
with extrusion of mantle-derived magma showing only minor contamination of
continental crust. The presence of pillow lavas in the basalts indicates that they
deposited in a subaquatic environment. Associated with this event, basic
intrusions were also formed in the Tjårrojåkka area. Based on geological and
petrophysical information from outcrops as well as geophysical interpretations,
it can be interpreted that the area was deformed during at least three events,
creating NE-SW and E-W striking foliations, as well as NNW-SSE trending
folds and deformation zones. The area has been metamorphosed at epidoteamphibolite facies with an increase of the metamorphic grade towards the S.
The bedrock has been affected by several stages of alteration related to
metamorphic and mineralisation processes. The most widespread alteration
occurs within and adjacent to major deformation zones and mineral
occurrences, and is characterised by scapolite, K-feldspar, epidote, and albite.
Scapolite often occurs in the basic rocks but rarely in the intermediate. Kfeldspar alteration postdates the scapolite alteration and occurs in the
intermediate rocks either as pervasive alteration, replacing plagioclase in the
matrix and showing foam textures, or as veins formed along fissures. In the
basic rocks, K-feldspar locally occurs as veins. Epidotisation is frequently
associated with K-feldspar occurring as fissure fillings.
13
Mineralisation and hydrothermal alteration
Mineralisation
The apatite-iron ore at Tjårrojåkka consists of a massive core (60-67% Fe
and 0.5-1.3% P) surrounded by an ore breccia (25-60% Fe and 0.4-3% P) with
low-grade copper mineralisation (Bergman et al., 2001), whereas the copper
(-gold) deposit forms an elongated body of disseminated copper sulphides with
magnetite-apatite veining in the footwall.
Drill core investigations indicate that the Tjårrojåkka apatite-iron deposit
was the first of the occurrences to form since copper sulphides occur in
fractures and veins crosscutting the massive magnetite. Magnetite is by far the
most common ore mineral in the apatite-iron ore with minor hematite
occurring as veins cutting the magnetite or as partly hematite-altered magnetite
grains. Within the massive magnetite ore, veinlets of red or green apatite,
tremolite, and carbonate fill fractures. Chalcopyrite, bornite, pyrite, and minor
molybdenite occur as veins and disseminations in the breccia and more rarely in
fractures in the massive magnetite body. Gold (electrum) and silver telluride are
trace minerals found in chalcopyrite. Based on textural relationships the
sulphides in general post-date the massive magnetite, but occur in some cases
intergrown with magnetite in the massive ore and in veins in the breccia.
The Tjårrojåkka Cu (-Au) deposit essentially consists of chalcopyrite,
bornite, pyrite, and magnetite as disseminations, patches and in veinlets, locally
with disseminated molybdenite. Magnetite and apatite ± actinolite is found in
footwall and is cut by later chalcopyrite and carbonate veinlets. The magnetite
exhibits in some cases martite replacement textures. Chalcopyrite and bornite
occur as single grains or intergrown and are mainly associated with pervasive Kfeldspar alteration and veins of amphibole ± K-feldspar ± quartz ± magnetite ±
carbonate in both metaandesites and metadolerites. Chalcopyrite has also been
identified intergrown with pyrite and magnetite. Bornite occurs in the part of
the mineralisation richest in copper, while pyrite is more abundant in the
Eastern part of the deposit and at deeper levels. Silver telluride, silver sulphide,
and native gold occur as micron-sized minor phases. Gold has been observed in
quartz in a vein together with amphibole and chalcopyrite. Ekström (1978) also
observed gold as inclusions in silicates associated with chalcocite and bornite.
Chalcocite and covellite have been observed as secondary minerals replacing
chalcopyrite and bornite (Ekström, 1978) and locally oxidation of copper
sulphides has resulted in the formation of malachite and chrysocolla.
Hydrothermal alteration
The hydrothermal alteration assemblages at Tjårrojåkka are highly
variable with several of the alteration minerals occurring in numerous
generations and settings, overlapping alteration stages indicating a complex,
long history of fluid activity in the area. The most widespread alteration
14
minerals are albite, magnetite, apatite, scapolite, biotite, K-feldspar, and
amphiboles (tremolite, actinolite, Mg-hornblende, and tschermakite). Based on
ore mineral and alteration assemblages, the mineralisation and hydrothermal
alteration have been divided into the following stages: (I) magnetite ore stage,
(II) copper (chalcopyrite) ore stage, (III) post-ore stage, and (IV) low T stage.
Stage I represents the formation of the massive magnetite ore and late stage
magnetite ± apatite ± amphibole ± quartz ± chalcopyrite veins occurring in the
breccia and the footwall of the copper (-gold) deposit. Stage II overlaps with stage
I and includes the main copper ore forming event characterized by chalcopyrite
and bornite. Stage III (post ore stage) involved the formation of lower temperature
veins with quartz ± amphibole and some minor copper sulphides. The low
temperature stage (IV) did not involve mineralization and is characterized by low
temperature assemblages.
The alteration paragenesis in the two deposits is similar with albite
forming at an early stage associated with magnetite and apatite (stage I).
Scapolite is generally accompanied by biotite and formed mainly before the
main copper sulphide stage. The albitised and scapolitised rocks are overprinted
by later K-feldspar alteration, which is spatially associated with copper sulphides
(stage II). Several different types and generations of amphibole occur both
associated with magnetite and copper mineralisation (stages I and II) and in
post-mineralisation assemblages (stage III). Epidote and zeolites were the last
phases to form from post main-ore stage low-temperature fluids (stage IV).
The whole-rock geochemistry shows enrichment of alkalis related to
mineralisation due to the formation of albite and K-feldspar. There was
enrichment in Na and depletion of K, Ba, and Mn related to albitisation, with
the inverse relationship of these elements associated with K-feldspar alteration.
Fe and V show depletion in the altered zones and addition in mineralised
samples. REE were enriched in the system, with the greatest addition related to
mineralisation. Y was mobile associated with albite alteration and copper
mineralisation.
Fluid characteristics and ore genesis
Fluid inclusion data indicate that the ore forming fluids at Tjårrojåkka
were CO2-bearing, moderately to highly saline, CaCl2-NaCl-rich fluids, with
the dominant magnetite and chalcopyrite association point towards a relatively
high oxidation state. However, the presence of some hematite, barite, and SO4
in scapolite in the copper (-gold) deposit suggests that the conditions were
more oxidising at the deposition of stages II and III than at the formation of the
massive apatite-iron ore (stage I). The source of the fluids and salts (magmatic
or metamorphic) could not be unequivocally determined from the available
data; nevertheless, the G18O and GD values together with sulfur isotope data
imply that magmatic fluids, or fluids that equilibrated with wall rocks, played an
15
important role in the formation of the Tjårrojåkka deposits. Such fluids could
have provided the system with both ligands and metals needed for the
mineralisation. However, due to the high Ca content of the fluids, the
possibility of incorporation of a formation water brine whose sulphate was
removed by prior reaction with wall rocks can not be ruled out. The lowtemperature assemblage (stage IV) shows a trend towards lighterG18O
composition due to mixing with meteoric water. Sm-Nd data also imply that
the ore-forming fluids in the apatite-iron system at Tjårrojåkka has its source in
the Archaean basement and it is likely that the local, 1.9 Ga rocks contributed
to the Nd budget during interaction between wall rocks and fluid(s) that
penetrated the area.
The magnetite ore-forming stage (stage I) deposited at a minimum
temperature of 500 to 650°C followed by the main copper mineralisation (stage
II) at around 400-450°C. The last stage of copper mineralisation associated with
quartz veining (stage III) occurred at around 150-200°C. The heat required for
the hydrothermal system was most likely provided by a deep-seated intrusion.
At present, it is not possible to establish a genetic link between the Tjårrojåkka
deposits and a particular intrusion in the area; however, regionally there was
igneous activity at the time of mineralisation.
Fluid inclusion data indicate that cooling, along with decrease in salinity
(from stage II to III), were important factors for iron (stage I) and copper (stage
II) precipitation at Tjårrojåkka. A NE trending shear zone in the area probably
acted as a major fluid channel and a structurally favourable location for the
deposition of the copper (-gold) mineralisation. U-Pb ages of titanites and
indications from Sm-Nd analyses of magnetite, apatite, and amphibole, point to
an age of the mineralisation close to 1780 Ma. The ore deposition was a
relatively short-lived event, while the low-temperature assemblages (stage IV)
most likely formed during several phases for a long period with the youngest
indicated age of about 1700 Ma.
From the existing data, it cannot be concluded whether the massive part
of the apatite-iron ore is of magmatic melt or hydrothermal origin. However, it
can be said that it originated from a source with a dominant Archaean H-Nd
isotopic composition, and that a hydrothermal system was active at least at a late
stage during ore formation, creating the apatite-magnetite-actinolite breccia,
copper mineralisation, as well as the extensive Na and K alterations surrounding
the massive ore body.
Similarities in stable isotope and fluid composition, temperature of ore
deposition, and age of alterations and mineralisation imply that the Tjårrojåkka
apatite-iron and copper (-gold) deposits formed during the same ore forming
event around 1780 Ma, demonstrating a genetic link between at least some
apatite-iron and copper-gold deposits. This study also shows the presence of
another younger, previously unknown, 1780 Ma generation of apatite-iron ores
in Northern Sweden.
16
The Tjårrojåkka deposits in the IOCG spectrum
The Tjårrojåkka apatite-iron and Cu (-Au) deposits share many
characteristics (structural control, abundance of iron oxides, anomalous
concentrations of REE, albite-scapolite-K-feldspar alteration) with deposits
classified as IOCG-type (e.g. Hitzman et al., 1992; Marschik and Fontboté,
2001; Porter, 2000 and references therein). The apatite-iron deposit at
Tjårrojåkka is similar to the Kiirunavaara apatite-iron ore with magnetite as
almost the only iron oxide and a breccia developed along the wall rock contacts
(Martinsson, 2003). However, it differs from most other Kiruna type apatiteiron ores in Norrbotten in the higher sulphide content of the breccia
surrounding the massive magnetite body and the spatial relation to a copper (gold) deposit. The Tjårrojåkka copper (-gold) deposit can be considered as a
copper dominated end-member in the IOCG spectrum of deposits. It is
characterised by strong sodic and potassic alteration comparable to those
surrounding the apatite-iron ore, but show a stronger structural control. The
common spatial relationship between apatite-iron and copper ores has also been
noted between more recent IOCG deposits, for example the Candelaria-Punta
del Cobre deposits (Marschik and Fontboté, 2001) and Carmen-Sierra Aspera
district (Gelcich et al., 2005) that shear many features with the Tjårrojåkka
deposits.
The dominant magnetite association at Tjårrojåkka indicate a higher
temperature and a lower oxidation state than for example at the Olympic Dam
deposit where hematite is the dominant Fe-oxide (Oreskes and Einaudi, 1990,
1992). Mark et al. (2000) suggested that there is a spectrum of deposit within
the Fe-oxide Cu-Au group ranging from relatively lower gO2, hotter and
deeper deposits (e.g. Ernest Henry) to those forming at higher levels from more
oxidized lower temperature fluids (e.g. Olympic Dam) and that fluid mixing
could be the cause of the diversity. The continuum is also seen in the copper
sulphide association with chalcopyrite being the most dominant copper
sulphide in the first mentioned and chalcocite-bornite-chalcopyrite in the
other. In the suggested model, the Tjårrojåkka deposits would represent a
deposit formed at deeper levels.
Analyses of apatite performed during this PhD project indicate that there
is a fundamental difference in the apatite chemistry between Kiruna type
apatite-iron ores and IOCG deposits, and that some apatite-rich iron ores form
associated with fluids similar to those creating copper-rich IOCG deposits.
These data could potentially be used as a tool for distinguishing copper
mineralising apatite-iron systems from barren. The results also allow the
discussion whether some of the apatite-iron ores should be considered as IOCG
deposits and not apatite-iron ores of Kiruna type, and if typical Kiruna type
apatite-iron ores should be included in the IOCG group of deposits at all.
17
CONCLUSIONS
From the studies completed during this PhD project, it can be concluded that:
1. The intermediate volcanic rocks and related intrusions in the
Tjårrojåkka area formed at around 1880 Ma in a volcanic arc
environment close to the Archaean continental margin. Later extension
in a back-arc subaquatic setting resulted in eruption of basaltic lavas and
the formation of basic dykes and sills. The area was subsequently
affected by epidote-amphibolite metamorphism and regional as well as
local albite, scapolite, and K-feldspar alteration.
2. The Tjårrojåkka apatite-iron and copper (-gold) deposits are spatially
and genetically related and can be considered representing two endmembers of the IOCG group of deposits.
3. The two Tjårrojåkka deposits show the same alteration paragenesis
with early albite alteration, overprinted by scapolite and thereafter Kfeldspar + amphibole alteration.
4. The apatite-iron ore (stage I) formed around 500-650qC followed by
the main copper mineralisation (stage II) at approximately 400-450qC.
Late stage copper mineralisation (stage III) occurred at 150-200qC.
5. The ore forming fluids were CO2-bearing, moderately to highly saline
CaCl2-NaCl-rich fluids with a relatively high oxidation state and
probably of a magmatic origin.
6. Cooling along with a decrease in salinity were important factors for
metal precipitation at Tjårrojåkka. A NE trending shear zone in the
area acted as a fluid channel and a structurally favourable location for
the copper (-gold) mineralisation.
7. The ore deposition occurred during a relatively short-lived event at
around 1780 Ma followed by an extended period of hydrothermal
activity that ended at around 1700 Ma. This demonstrates the presence
of another younger, previously unknown, 1780 Ma generation of
apatite-iron ores in Northern Sweden.
8. There is a fundamental difference in the apatite chemistry between
Kiruna type apatite-iron ores and IOCG deposits implying that some
apatite-rich iron ores formed associated with fluids similar to those
creating copper-rich IOCG deposits. These data could potentially be
used as a tool for distinguishing copper mineralising apatite-iron
systems from barren.
18
SIGNIFICANCE FOR EXPLORATION AND
FUTURE WORK
Significant amounts of both scientific and exploration work have been
accomplished on IOCG deposits since I started my PhD studies in 2001. Nevertheless,
there are still many questions, regarding their genesis and which deposits should be
included in the class, unanswered. I think we will have to be prepared to change our
ore genetic models as research progresses and accept that most likely the genesis of this
very diverse family of ore deposits cannot be explained by a single model.
From this study, the main implication for exploration is the fact that we have
been able to show that there is a genetic link between at least some apatite-iron and
copper deposits in Norrbotten. If we could further be able to distinguish between
copper bearing and barren systems (using for example apatite chemistry), it would be a
big improvement from an exploration point of view.
Based on the regional mapping that was done in the Tjårrojåkka area, we can
conclude that copper mineralisation occurred in all types of rocks (andesites, basalts,
and intrusive rocks). Hence, all these lithologies have to be considered when exploring
for IOCG deposits in Norrbotten. Other characteristics useful for exploration are the
intense Na-K-Ca alteration and vicinity of structures.
The integrated geophysical-geological approach of the project have shown that
there is a good spatial correlation between copper occurrences and high K/Th values
in the area (Sandrin, 2003). Due to the glacial deposits covering the area, geophysics is
crucial for the geological interpretations and detection of geological structures, which
are important for locating structurally controlled IOCG deposits.
The increased interest in U exploration in Sweden could also include IOCG
deposits. Many IOCG deposits have anomalous U grades (Hitzman and Valenta,
2005), but it has seldom been systematically analysed for. Hitzman and Valenta (2005)
suggest that exploration for these types of deposits should be focused on areas where
the host rock contains anomalous amounts of uranium.
Further research is clearly needed to determine the Kiruna type apatite-iron
ores’ position in the IOCG spectrum of deposits. As indicated from apatite chemistry
there might be an essential difference between copper bearing apatite-iron ores and
barren. Therefore, it would be of interest to compile a substantial amount of apatite
chemistry data from both Kiruna type and IOCG deposits to test the proposed theory.
Another matter that needs to be confirmed is the presence of a younger
generation of apatite-iron ores in Norrbotten. However, it is generally difficult to date
the massive iron-oxide ores in Norrbotten due to the lack of datable minerals. Gelcich
et al. (2005) used U-Pb geochronology on apatite-magnetite from the Cretaceous
Carmen deposit to constrain the age of mineralisation and pointed out that the
method could potentially be used for older deposits as well. Another possible method
for constraining the age of apatite-iron ores in the area could be Re-Os dating of
magnetite, but this method still needs to be developed.
Finally, in my opinion new methods need to be considered to take the debate
19
forward concerning the origin of Kiruna type apatite-iron ores. According to Markl et
al. (2006) the use of iron isotopes is a potential technique to interpret ore formation
and hydrothermal processes and might hence also be useful in the genetic
interpretations of Kiruna type deposits.
20
ACKNOWLEDGEMENTS
Since the project started in 2001, I have worked in close cooperation
with The Natural History Museum in London (The ACCORD Marie Curie
funded PhD training site), USGS (United States Geological Survey) in Denver,
The Swedish Museum of Natural History in Stockholm (Dr. Kjell Billström),
and Stockholm University (Dr. Curt Broman). The project was funded by
GEORANGE and also received financial support from Phelps Dodge
Exploration Sweden AB and Stiftelsen Längmanska kulturfonden.
Writing a thesis is nothing you do alone. It requires many and long
discussions with colleagues and it involves family and friends to manage life
outside university. I would like to take this opportunity to thank a few people,
without whose support, help, and love, I would not have accomplished what I
have today.
First, I would like to thank my supervisor Dr. Olof Martinsson who
initiated the project and unrestrained shared his knowledge on the geology and
metallogeny of Norrbotten with me. My supervisors during my time at the
Marie Curie PhD training site at The Natural History Museum in London, Dr.
Robin Armstrong and Dr. Martin Smith, are greatly thanked for their patience
and support in both scientific and personal matters. Dr. Bob Rye at USGS in
Denver is acknowledged for showing interest in the project and giving advice
and constructive comments on the stable isotope interpretations. Dr. Kjell
Billström and Dr. Curt Broman are thanked for all the help with the dating and
fluid inclusion work. My colleagues at the division (Kicki, Christina, Denis,
Glenn, Robert, and Cecilia) deserve a big acknowledgement for always
listening and helping me. Special thanks go to Alessandro who left me halfway
through for a better life in Copenhagen -, but kept on sending me
encouraging e-mails and photos. I am also grateful to all the scientists I have
met in different parts of the world, who contributed with their specific
knowledge.
Furthermore, I want to thank my mum, dad, and sister with family, for
supporting me through the years and for encouraging me to travel and take
chances. Big thanks to my aunt Gun-Maj, as well as my friends Lene and
Malin, who helped me tremendously by looking after Adina when I was home
on my own. I am also very grateful to my family in South Africa who have
supported and prayed for us during difficult times.
Finally, I want to thank my gorgeous daughter Adina for being such a
patient big girl during the last couple of months when mum, most of the time,
was sitting in front of the computer and you had to play by yourself. And
Lionel – for loving me. Without your love, support, and endless cups of tea,
this would not have been possible.
21
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igneous-related Fe oxide-(REE-Cu-Au-U) mineralization: Geology, v.
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Bergman, S., Kübler, L., and Martinsson, O., 2001, Description of regional
geological and geophysical maps of northern Norrbotten County (east
of the Caledonian orogen): Geological Survey of Sweden, Ba 56, p.
110.
Broman, C., Nyström, J. O., Henríquez, F., and Elfman, M., 1999, Fluid
inclusions in magnetite-apatite ore from a cooling magmatic system at
El Laco, Chile: GFF, v. 121, p. 253-267.
Clayton, R. N., and Mayeda, T. K., 1963, The use of bromine pentafluoride in
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Paper I
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Paper II
Mineralium Deposita (2005) 40: 409–434
DOI 10.1007/s00126-005-0005-y
ARTICLE
Åsa Edfelt Æ Robin N. Armstrong Æ Martin Smith
Olof Martinsson
Alteration paragenesis and mineral chemistry of the Tjårrojåkka
apatite–iron and Cu (-Au) occurrences, Kiruna area, northern Sweden
Received: 25 May 2005 / Accepted: 10 June 2005 / Published online: 25 August 2005
Springer-Verlag 2005
Abstract The northern Norrbotten area in northern
Sweden, is an important mining district and hosts several deposits of Fe-oxide Cu-Au-type. One of the best
examples of spatially, and possibly genetically, related
apatite–iron and copper–gold deposits in the region is at
Tjårrojåkka, 50 km WSW of Kiruna. The deposits are
hosted by strongly sheared and metamorphosed intermediate volcanic rocks and dolerites and show a structural control. The Tjårrojåkka iron deposit is a typical
apatite–iron ore of Kiruna-type and the Tjårrojåkka
copper occurrence shows the same characteristics as
most other epigenetic deposits in Norrbotten. The host
rock has been affected by strong albite and K-feldspar
alteration related to mineralisation, resulting in an
enrichment of Na, K, and Ba. Fe and V were depleted in
the altered zones and added in mineralised samples.
REE were enriched in the system, with the greatest
addition related to mineralisation. Y was also mobile
associated with albite alteration and copper mineralisation. The Tjårrojåkka iron and copper deposits show
comparable hydrothermal alteration minerals and
paragenesis, which might be a product of common host
rock and similarities in ore fluid composition, or overprinting by successive alteration stages. Mineralogy and
mineral chemistry of the alteration minerals (apatite,
scapolite, feldspars, amphiboles, and biotite) indicate a
higher salinity and Ba/K ratio in the fluid related to the
Editorial handling: P. Williams
Å. Edfelt (&) Æ O. Martinsson
Division of Ore Geology and Applied Geophysics,
Luleå University of Technology, 971 87 Luleå, Sweden
E-mail: [email protected]
R. N. Armstrong
Department of Mineralogy, The Natural History Museum,
Cromwell Road, London, SW3 5BD, UK
M. Smith
Cockcroft Building, University of Brighton, Lewes Road,
Brighton, BN2 4GJ, UK
alterations in the apatite–iron occurrence than in the
copper deposit, where the minerals are enriched in F and
S. The presence of hematite, barite, and in SO4 in
scapolite suggests more oxidising-rich conditions during
the emplacement of the Tjårrojåkka-Cu deposit. From
existing data it might be suggested that one evolving
system created the two occurrences, with the copper
mineralisation representing a slightly later product.
Keywords Sweden Æ Proterozoic Æ IOCG Æ
Hydrothermal alteration Æ Mineral chemistry
Introduction
The northern Norrbotten area, northern Sweden
(Fig. 1), hosts several economic and subeconomic Feoxide and Cu (-Au) deposits and has been described as
an Fe-oxide Cu–Au (IOCG) district (Hitzman et al.
1992). The most economically significant deposits of the
region are the Kiruna and Malmberget apatite–iron and
the Aitik Cu-Au ores. The Tjårrojåkka area is located
about 50 km WSW of Kiruna and hosts one of the best
examples in Norrbotten of spatially related apatite–iron
and copper deposits (Fig. 1). Following an extensive
exploration program in 1967–1975, a large number of
drill cores are available from the area, but no scientific
results on the Tjårrojåkka occurrences have been published to date. The geology of the deposits is briefly
described in Ros and Rönnbäck (1971), Grip and
Frietsch (1973), Quezada and Ros (1975), Ekström
(1978) and Ros (1979). More recently short descriptions
of the Tjårrojåkka area have been published in Bergman
et al. (2001), Edfelt and Martinsson (2003), Edfelt and
Martinsson (2004), and Edfelt et al. (2004).
The geological settings, hydrothermal alteration systematics and mineralising fluid compositions among
deposits classified as IOCG-type show a great variation
(e.g. Porter 2001; Sillitoe 2003; Hitzman et al. 1992).
Detailed descriptions of specific parageneses and mineral
associations are important in order to understand the
410
Fig. 1 Geological map of
northern Norrbotten showing
the location of major Fe and Cu
(-Au) deposits, and the
Tjårrojåkka study area (after
Bergman et al. 2001). Inset map:
map of the Fennoscandian
Shield with the location of the
northern Norrbotten area.
KNDZ Kiruna-Naimakka
deformation zone; KADZ
Karesuando-Arjeplog
deformation zone; NDZ
Nautanen deformation zone;
PSH Pajala shear zone
possible genetic relationships between different deposit
types within this broad classification. This paper will
describe the alteration characteristics of the Tjårrojåkka
apatite–iron and Cu (-Au) occurrences in terms of
whole-rock geochemistry, mineral chemistry and paragenesis. The mineral chemical data are also used as an
indicator of the nature of the hydrothermal fluids involved in the formation of the deposits. These data will
be used to examine the relationship between the two
occurrences and compare them to other deposits in the
region and elsewhere in the world.
Regional geological setting and metallogeny
The Precambrian bedrock in the northern Norrbotten
region includes a ca. 2.8 Ga Archaean granitoid-gneiss
basement, which is unconformably overlain by a meta-
volcanic sequence of Palaeoproterozoic age (Fig. 1).
Stratigraphically lowest in the metavolcanic sequence
are rift related 2.5–2.0 Ga Karelian units that are followed by ca. 1.9 Ga Svecofennian successions including
several units of metavolcanic and epiclastic rocks. In the
central Kiruna area the Svecofennian successions comprise, from the oldest to youngest, the Porphyrite
Group, the Kurravaara Conglomerate, the Kiirunavaara Group and the Hauki Quartzite (Allen et al. 2004).
Equivalent Palaeoproterozoic units are also found outside the Kiruna area. The calc-alkaline andesite-dominated Porphyrite Group is suggested to be subduction
related, while the Kiirunavaara Group has a bimodal
character and a geochemical signature resembling
within-plate volcanic rocks (Martinsson and Perdahl
1994).
The approximately 10-km thick pile of Palaeoproterozoic volcanic and sedimentary rocks was deformed
411
and metamorphosed contemporaneously with intrusion
of the Haparanda (1.89–1.87 Ga) and Perthite monzonite (1.88–1.86 Ga) granitoid suites (Bergman et al.
2001). These plutonic rocks have a calc-alkaline to alkali-calcic character and are comagmatic with the
Svecofennian volcanic rocks (Witschard 1984; Bergman
et al. 2001). The Lina Suite comprises ca. 1.79 Ga
granites and pegmatites (Skiöld et al. 1988), which are
temporally related to Trans-Scandinavian Igneous Belt
(TIB) 1 intrusions in the Kiruna-Narvik area (Romer
et al. 1994; Romer et al. 1992). A second phase of
metamorphism and deformation occurred at least locally at this time (Bergman et al. 2001).
Northern Norrbotten is an important mining province dominated by Fe- and Cu-deposits, with Au as a
minor constituent in some of the Cu-occurrences. The
main occurrences and their characteristics are summarised in Table 1. The economically most important
deposits are the iron ores with an annual production of
ca. 31 Mt of ore from the Kiirunavaara and Malmberget
deposits (Fig. 1), and a total production of about
1,600 Mt from 10 mines during the last 100 years. Besides magnetite and hematite, most of the iron ores
contain significant amounts of apatite. This class of
deposits has been named ‘‘apatite–iron ores’’ or ‘‘Kiruna
type’’ with the Kiirunavaara deposit being the largest
and best-known example. Kiirunavaara contains more
than 2,000 Mt of high-grade ore and was first described
in detail by Geijer (1910). About 40 apatite–iron ores are
known from northern Norrbotten. Individual deposits
have an average content of Fe and P varying between
30–65 and 0.05–5%, respectively. Their spatial distribution coincides with that of the Kiirunavaara Group
and they are almost exclusively hosted by metavolcanic
rocks belonging either to the Kiirunavaara Group or the
underlying Porphyrite Group (Martinsson 2003). Oreelated alteration minerals include albite, scapolite,
amphibole, K-feldspar, quartz, and sericite.
Copper was produced intermittently during the seventeenth and eighteenth centuries and recently on a
larger scale in the Kiruna area. Sweden’s largest sulphide
mine, Aitik, is situated in the Gällivare area (Fig. 1).
With an annual production of 18 Mt of ore, it is one of
the major Cu and Au producers in Western Europe.
Although only a few economic sulphide deposits have
been found in the northern Norrbotten ore province, a
large number of epigenetic Cu–Au occurrences exist in
the area. They exhibit large variation in mineralisation
style, host rock composition and ore-related hydrothermal alteration.
Most copper deposits are hosted by tuffitic units of
the Karelian greenstones and mafic to intermediate
volcanic rocks within the Svecofennian porphyries (i.e.
the Porphyrite Group and the Kiirunavaara Group).
Table 1 Summary of characteristics of Fe-oxide and Cu–Au deposits in northern Norrbotten
Deposit
Grade and size
Ore minerals and
gangue minerals
Host rocks–wall
rocks
Alteration minerals
References
Kiirunavaara
>2,000 Mt at >60%
Fe, ca. 1% P
20 Mt at 33%
Fe, 3.5% P
660 Mt at 51- 61%
Fe, <0.8% P
166 Mt at 35% Fe
Mag, (Hem),
Ap, Am
Hem, Mag, Ap,
Qtz, Carb
Mag, Hem, Ap
Trachyandesite,
rhyodacite
Rhyodacite,
rhyolite
Trachyandesite,
rhyodacitea
Trachyandesite
Am, Ab, Bt
Aitik
606 Mt at 0.38%
Cu, 0.21g/ton Au
1.68 Mt at 1.89% Cu,
0.88 ppm Au
Andesitic
volcaniclastica,
Qtz-monzodiorite
Basaltic tuffite,
graphite schist,
mafic sill
Bt, Ser, Kfs, Ep, Grt
Pahtohavare
Ccp, Py, Po,
(Bn, Mag, Mo),
Brt, Bt, Qtz, Grt
Ccp, Py, Po, Ab,
Carb, Scp
Bergman et al.
(2001)
Bergman et al.
(2001)
Bergman et al.
(2001)
Lundberg and
Smellie (1979)
Bergman et al.
(2001)
Wanhainen et al.
(2003)
Gruvberget
0.2 Mt at 0.5–1% Cu
(production)
0.07 Mt at 1–1.5% Cu
(production)
Ccp, Bn, Mag,
(Mo), Kfs, Ep, Carb
Ccp, Bn, Mag,
(Mo), Kfs, Ser,
Tur, Grt, Qtz, Am
Ccp, Bn, Mag,
(Mo), Kfs, Tur, Scp
Py, Ccp, Mag,
Hem, (Mo), Kfs
Andesitea
Andesitic
volcaniclastica
Ab, Kfs, Scp, Ep,
Am, Grt, Px
Kfs, Bt, Scp, Grt,
Ser, Tur, Qtz
Basalt,
Qtz-monzonite
Andesite
Kfs, Ser, Scp, Bt, (Tur)
Rektorn
Malmberget
Mertainen
Nautanen
Pikkujärvi
5 Mt at 0.61% Cu
Kiskamavaara
3.4 Mt at 0.37%
Cu, 0.09% Co
Mag, Am
Ab Albite; Am amphibole; Ap apatite; Brt barite; Bt biotite; Carb
carbonate; Chl chlorite; Ep epidote; Grt garnet; Kfs K-feldspar; Px
pyroxene; Qtz quartz; Scp scapolite; Ser sericite; Tur tourmaline;
Bn bornite; Ccp chalcopyrite; Hem hematite; Mag magnetite; Mo
molybdenite; Po pyrrhotite; Py pyrite
a
Kfs, Qtz, Ser, Chl, Bt, Tur
Ab, Kfs, Bt, Am, Scp
Ab, Scp, Am
Ab, Scp, Bt, Carb
Kfs, Bt, Scp, Tur
Lindblom et al.
(1996)
Bergman et al.
(2001)
Frietsch (1966)
Lindskog (2001)
Bergman et al.
(2001)
Bergman et al.
(2001)
Bergman et al.
(2001)
Suggested precursor of strongly altered/metamorphosed rock
Mineral in brackets less common
412
Some of them display a close genetic and/or spatial
relationship to intrusive rocks varying in composition
from monzodiorite to granite represented by plutons
belonging to the Haparanda and Perthite monzonite
suites. Magnetite is a common minor component in
many of the deposits and in two cases (Gruvberget and
Tjårrojåkka) the copper deposits occur adjacent to major magnetite deposits (Allen et al. 2004; Bergman et al.
2001). Besides structural traps, chemical traps may also
be important, with redox reactions involving graphitic
schists triggering sulphide precipitation. In addition to
Cu, several occurrences also contain Co and/or Au in
economic to subeconomic amounts (Martinsson 2000;
Bergman et al. 2001).
Ore-related alteration is dominated by K-feldspar,
albite, biotite, and scapolite with amphibole, carbonate,
tourmaline, garnet, and sericite as locally important
minerals. In most deposits the paragenetic sequence
from oldest to youngest is: scapolite + biotite fi albite fi carbonate, or: scapolite + biotite fi K-feldspar fi sericite ± tourmaline. Stilbite and chabazite
may be late phases occurring in druses and veins together with calcite. Ore minerals formed mainly at the
intermediate or late stages of alteration. GeochronoFig. 2 Generalised geology of the Tjårrojåkka area with location
of the Tjårrojåkka iron and copper deposits and minor occurrences. Inset map: drill holes at the Tjårrojåkka deposits with the
investigated profiles indicated. Sections 400W and 320E shown in
Figs. 3 and 4, respectively
logical data from Cu–Au deposits and hydrothermal
alteration in the northern Norrbotten ore province
demonstrates two major events of ore formation at ca.
1.87 and 1.77 Ga, respectively (Billström and Martinsson 2000; Edfelt 2003). The importance of saline
hydrothermal fluids in the genesis of regional albite–
scapolite alteration and the nature of the ore deposits in
the northern Norrbotten ore province and adjacent
Karelian areas in northern Finland and Norway has
been emphasised by Frietsch et al. (1997). Highly saline
fluid inclusions with 30–45 eq.wt% NaCl and depositional temperatures of 500–300C are recorded for the
Cu–Au deposits in this region (Ettner et al. 1993;
Lindblom et al. 1996; Broman and Martinsson 2000).
High Ca contents characterise ore fluids from most Cu–
Au occurrences, which might be an expression of added
components from evaporitic sediments within the Karelian greenstones that contributed to the salinity of the
mineralising fluids (Wanhainen et al. 2003).
Geology of the Tjårrojåkka area
The geology in the Tjårrojåkka area is dominated by
metamorphosed mafic to intermediate extrusive and
intrusive rocks (Fig. 2). The stratigraphically lowest unit
comprises metaandesites and metadolerites that are
overlain by metabasalts. The metabasalts and metadolerites in the area have the same chemical signature
413
and have been interpreted to have formed from the same
magma with the dolerites acting as feeder dykes for the
overlying basaltic unit (Edfelt 2003). Intrusions of gabbroic to quartz-monzodioritic composition crosscut the
andesites and basalts. The rocks are metamorphosed in
epidote-amphibolite facies, based on mineral assemblages (hornblende + plagioclase ± epidote ± quartz)
(Spear 1993) of non-mineralised basic rocks (metabasalt
and -dolerite). They have been strongly affected by albite, scapolite, and K-feldspar alteration that is more
intense in the vicinity of deformation zones and mineralisation. From textural relationships (scapolite porphyroblasts growing over the metamorphic foliation in
metabasalts and -dolerites) the regional alterations are
interpreted as being temporally later than the metamorphism. Based on geochemistry the metaandesites
resemble the intermediate rocks of the Svecofennian
Porphyrite Group, while the metadolerites and -basalts
have a more primitive signature and cannot be correlated with any known volcanic sequence in Norrbotten
(Edfelt 2003).
Rocks of the area, which are located within a splay
off of a regional NW–SE trending deformation zone
(Fig. 1), have undergone at least three stages of deformation including two compressional events (Edfelt
2003). The first compressional episode created NE–SW
striking foliation parallel to the strike of the Tjårrojåkka
deposits. It was followed by the development of an E–W
trending deformation zone identified from aeromagnetic
data showing a low magnetic anomaly and parallel
foliation (shearing) in outcrops. The third deformation
stage is characterised by ENE–WSW compression seen
in folding in the central part of the area. The compressional stages can also be correlated with the regional
tectonics in Norrbotten (cf. Bergman et al. 2001). Several structurally controlled Fe- and Cu-occurrences occur in the area (Sandrin and Elming 2003) of which the
largest are the Tjårrojåkka magnetite–apatite (Tjårrojåkka-Fe) and the Tjårrojåkka copper-gold (Tjårrojåkka-Cu) occurrences located 750 m apart.
The Tjårrojåkka-Fe deposit, comprising massive
magnetite with minor disseminated copper, was discovered through airborne magnetic measurements in 1963
by the Geological Survey of Sweden. A drilling program
was initiated in 1967 and continued for 3 years during
which some copper-bearing boulders and outcrops were
found, and the Tjårrojåkka-Cu prospect was discovered.
Between 1970 and 1975, 62 drill holes were drilled into
the copper deposit. The Tjårrojåkka-Fe deposit is hosted
by strongly sheared intermediate metavolcanic rocks
and less deformed metadolerites. It consists of a massive
magnetite core surrounded by a fractured host rock with
apatite–magnetite veins filling the fractures (breccia)
known to a depth of 400 m. The calculated tonnage for
the apatite–iron deposit is 52.6 Mt at 51.5% Fe (Quezada and Ros 1975) with locally up to 3% Cu in some
sections. The Tjårrojåkka-Cu occurrence, which is
characterised by copper sulphides with minor quantities
of magnetite, is hosted by the same rocks, localised in a
30 m wide and 700 m long zone, striking NE and dipping approximately 85 towards north. The deposit is
estimated to contain 3.23 Mt at 0.87% Cu (cut-off
0.4%) (Ros 1979).
Sampling and analytical methods
Four drill sections, one in the apatite–iron ore and
three in the copper deposit (Fig. 2), were logged and
sampled. Seventy-six thin sections representing different
rock and alteration types were initially examined in
transmitted and reflected light at Luleå University of
Technology and subsequently at the Natural History
Museum, London using a Jeol 5900LV scanning electron microscope (SEM). SEM observations were made
using a back-scattered electron detector (BSE), with an
accelerating voltage of 20 kV and a beam current of
1 nA measured specimen current in pure cobalt metal.
Mineral analyses were performed using a Cameca
SX50 WDS electron microprobe at the Natural History
Museum, London, with the technique described in Potts
et al. (1995). The analytical conditions and standards
used for different minerals are available in Edfelt (2003)
and the samples analysed are described in Appendix.
Silicate analyses were carried out using an accelerating
voltage of 15 or 20 kV, a beam current of 20 nA, and a
5-lm beam diameter. Apatites were analysed using an
accelerating voltage of 15 kV, a beam current of 20 nA,
and a 5-lm beam diameter. For sulphides and oxides a
1-lm beam diameter, an accelerating voltage of 15 or
20 kV, and a beam current of 20 nA were used, except
for one set of sulphide analyses for which a 60 nA beam
current was used. Different pure metals, natural minerals and synthetic glasses were used as standards. Interferences between X-ray peaks for Ba/Ti, Ce/Ti, Ce/Ba,
Nd/Ce, Co/Fe, F/Ce, Mo/S and V/Ti were corrected
empirically using previously collected data from standards.
Whole-rock analyses for major and trace elements
were carried out on 89 drill core samples at Activation
Laboratories Ltd in Canada. The major elements were
analysed using the inductively coupled plasma method
(ICCP-OES), while trace elements were analysed by
inductively coupled plasma mass spectrometry (ICCPMS) and instrumental neutron activation analysis
(INAA).
Mineralisation and hydrothermal alteration
The main ore and alteration minerals and styles are
summarised in Table 2. Cross sections through the
Tjårrojåkka-Fe (400W) and Tjårrojåkka-Cu deposits
(320E) (cf. Fig. 2), showing the relationships between
mineralisation and main alteration types, are presented
in Figs. 3 and 4, respectively. The apatite–iron ore
(Tjårrojåkka-Fe) consists of a massive core (60–67%
Fe and 0.5–1.3% P) surrounded by a breccia (25–60%
414
Table 2 Main ore and alteration minerals and styles in the Tjårrojåkka-Fe and Tjårrojåkka-Cu occurrences
Mineral
Associated minerals
Style
Location
Spatial relation
Relative time relationship
to Cu-mineralis-ation to main magnetite and
copper ore-forming stages
Magnetite
Ab, Scp, Pl, Bt,
Ap, Py, Ccp
Massive, veins
and disseminated
In breccia surrounding the
massive magnetite ore at
Tjårojåkka-Fe; footwall of Tjårrojåkka-Cu;
disseminated with Ab alteration
Close to none
Hematite
Mag
Bn, Py, Mag,
Ap, Kfs, Am, Qtz
Bornite
Ccp
Veins and
disseminated
Pyrite
Ccp, Carb, Zeol
Veins and disseminated
In and around the massive magnetite ore of
Tjårrojåkka-Fe; footwall of Tjårrojåkka-Cu
In the massive magnetite ore and in the surrounding
breccia at Tjårrojåkka-Fe; mineralised part
of Tjårrojåkka-Cu
In the massive magnetite ore and in the surrounding
breccia at Tjårrojåkka-Fe; mineralised part
In the breccia at Tjårrojåkka-Fe; mineralised part
Some
Chalcopyrite
Veins and
disseminated
Veins and
disseminated
Albite
Mag
Pervasive
Tremolite
Ap, (Carb)
Fracture filling, veinlets
Close
Massive Mag ore pre
Cu-mineralisation,
veins mostly pre
Cu-mineralisation,
in places syn
Cu-mineralisation
(intergrown with Ccp)
Post massive Mag, pre
(-syn) Cu-mineralisation
Post massive Mag, syn
Cu-mineralisation
Close
Post massive Mag, syn
Cu-mineralisation
Close
Post massive Mag,
syn-post
Cu-mineralisation
Syn-post massive Mag,
pre Cu-mineralisation
Around the massive magnetite ore of Tjårrojåkka-Fe; None
footwall of Tjårrojåkka-Cu; between the copper
and iron deposits
In massive magnetite ore at Tjårojåkka-Fe
None
Mg-hornblende Kfs, Ccp, Py, Mag
Disseminated, porphyroblasts, Everywhere in wall rock
and veinlets
Close to none
Tschermakite
Kfs, Ccp, Py, Mag
Disseminated, porphyroblasts, Everywhere in wall rock
and veinlets
Close to none
Actinolite
Kfs, Ttn
Veins, veinlets
Everywhere in wall rock
Close
Apatite
Mag, Am, Ccp, Bn,
Py, Carb
Veins, disseminated
Some
Biotite
Scp, Mag, (Kfs), Pl
Pervasive
Scapolite
Mag, Bt, Am
Porphyroblasts, veins
K-feldspar
Titanite
Act, Mg-Hbl, Ts, Ep,
Pervasive and in veins
Ccp, Bn, Mag, Qtz, Ttn
Kfs, Am
In veins with Am + Kfs
Quartz
Kfs, Am, Ccp, Bn, Carb Veins
Inside and around the magnetite ore
at Tjårojåkka-Fe;
footwall of Tjårrojåkka-Cu
Related to scapolite and K-feldspar alteration
in both deposits
In dolerites; locally in wall rock around massive
magnetite ore at Tjårojåkka-Fe; in hanging
wall of Tjårrojåkka-Cu
Locally in the wall rock around at Tjårojåkka-Fe;
in the mineralised zone of Tjårrojåkka-Cu
In K alteration around magnetite
ore at Tjårojåkka-Fe;
hanging wall of Tjårrojåkka-Cu
Some
Some
Close
Close
Some
Syn-post massive Mag,
pre Cu-mineralisation
Post massive Mag,
syn-post
Cu-mineralisation
Post massive Mag,
syn-post
Cu-mineralisation
Post massive Mag,
syn-post
Cu-mineralisation
Syn-post massive
Mag, pre- main
Cu-mineralisation
Mainly pre (-syn)
Cu-mineralisation
Post massive
Mag, pre-main
Cu-mineralisation
Post massive Mag,
syn Cu-mineralisation
Post massive
Mag, syn-post
Cu-mineralisation
Syn-post main
ore stages
None
Am, Qtz, Ccp, Zeol
Py, (Ccp), Am,
Ep, Kfs, Carb
Carbonates
Zeolites
Fracture-contolled,
often in reactivated veins
Musc
Fluorite
Ab Albite; Act actinolite; Ap apatite; Bt biotite; Carb carbonate; Chl chlorite; Ccp chalcopyrite; Ep epidote; Kfs K-feldspar; Mag magnetite; Mg-Hbl magnesium-hornblende; Musc
muscovite; Pl plagioclase; Py pyrite; Qtz quartz; Scp scapolite; Ttn titanite; Tr tremolite; Ts tschermakite; Zeol zeolite
Post main ore stages
Kfs, Am, Qtz, Carb
Epidote
Patches, porphyroblasts,
and veinlets (often
fracture-controlled)
Infilling in vugs, along
foliation plane
Veinlets, veins
None
None
Footwall of Tjårrojåkka-Cu, in periphery
of main mineralised zone
Both in the breccia and in the massive magnetite ore
at Tjårojåkka-Fe; in the footwall of Tjårrojåkka-Cu
(more abundant to E)
In the breccia around the massive magnetite ore
at Tjårojåkka-Fe; in mineralised zone
n the Tjårrojåkka-Cu (more abundant to E)
None
Spatial relation
to Cu-mineralis-ation
Associated minerals
Mineral
Table 2 (Contd.)
Style
Location
Relative time relationship
to main magnetite and
copper ore-forming stages
415
Fe and 0.4–3% P) with low-grade copper mineralisation
(Bergman et al. 2001), whereas the Tjårrojåkka-Cu
consists of an elongated body of disseminated copper
mineralisation with magnetite–apatite veining in the
footwall. Albite, scapolite, and K-feldspar alteration has
strongly affected the host rock to both deposits.
Mineralisation
Tjårrojåkka-Fe
Outcrop and drill core investigations indicate that the
Tjårrojåkka-Fe deposit was the first of the occurrences
to form since copper sulphides occur in fractures and
veins crosscutting the massive magnetite. Magnetite is
by far the most common ore mineral in the TjårrojåkkaFe deposit with minor hematite occurring as veins cutting the magnetite or as partly hematite-altered magnetite grains. Within the massive magnetite ore, veinlets of
red or green apatite, tremolite, and carbonate fill fractures (Fig. 5a). Chalcopyrite, bornite, pyrite and minor
molybdenite occur as veins and disseminations in the
breccia and more rarely in fractures in the massive
magnetite body. Gold (electrum) and silver telluride are
trace minerals found in chalcopyrite (Fig. 5b). Based on
textural relationships the sulphides in general post-date
the massive magnetite, but do in some cases occur intergrown with magnetite in the massive ore and in veins
in the breccia.
Tjårrojåkka-Cu
The Tjårrojåkka-Cu deposit essentially consists of
chalcopyrite, bornite, pyrite, and magnetite as disseminations, patches and in veinlets, locally with disseminated molybdenite. Magnetite occurs in footwall and is
cut by later chalcopyrite (Fig. 5c) and carbonate veinlets. The magnetite in some cases exhibits martite
replacement textures (Fig. 5d). Chalcopyrite and bornite
occur as single grains or intergrown and are mainly
associated with pervasive K-feldspar alteration and
veins of amphibole ± K-feldspar ± quartz ± magnetite
± carbonate in both metaandesites and metadolerites.
Chalcopyrite has also been identified intergrown with
pyrite and magnetite. Bornite occurs in the part of the
mineralisation richest in copper, while pyrite is more
abundant in the eastern part of the deposit and at deeper
levels. Silver telluride, silver sulphide, and native gold
occur as micron-sized minor phases. Gold has been
observed in quartz in a vein together with amphibole
and chalcopyrite. Ekström (1978) also observed gold as
inclusions in silicates associated with chalcocite and
bornite. Chalcocite and covellite have been observed as
secondary minerals replacing chalcopyrite and bornite
(Ekström 1978) and locally oxidation of copper sulphides has resulted in the formation of malachite and
chrysocolla.
416
Fig. 3 Cross section through
Tjårrojåkka apatite–iron ore
(profile 400W) showing the
relation between the magnetite
body, breccia, and alteration
types. Alteration zones
established based on
geochemistry and visible
appearance of alteration
minerals. Ccp chalcopyrite; Bn
bornite
Fig. 4 Cross section through the Tjårrojåkka-Cu deposit (profile
320E) showing the relationships between copper mineralisation and
main alteration types. Alteration zones established based on
geochemistry and visible appearance of alteration minerals.
a Albite (Ab) altered footwall with overprinting magnetite (Mag)apatite (Ap) veins. b Scapolite (Scp) altered hanging wall. c Intense
K-feldspar (Kfs) alteration
copper-bearing sulphides. Several different types and
generations of amphibole occur, both associated with
magnetite and copper mineralisation and in post-mineralisation assemblages. Epidote and zeolites were the
last phases to form from post main-ore stage low-temperature fluids.
Tjårrojåkka-Fe
Hydrothermal alteration
The hydrothermal alteration assemblages at Tjårrojåkka
are highly variable with several of the alteration minerals
occurring in numerous generations and settings, overlapping alteration stages, and with reactivation of already pre-existing veins, indicating a complex, long
history of fluid activity in the area. The most widespread
alteration minerals are albite, magnetite, apatite, scapolite, biotite, K-feldspar, and clinoamphiboles (tremolite, actinolite, Mg-hornblende, and tschermakite). The
paragenetic evolution of the Tjårrojåkka deposits is
illustrated in Fig. 6a, b. The alteration paragenesis in the
two occurrences is similar, with albite forming at an
early stage associated with magnetite and apatite.
Scapolite was formed mainly before the main Cu-sulphide stage and is generally accompanied by biotite. The
albitised and scapolitised rocks are overprinted by later
K-feldspar alteration, which is spatially associated with
The wall rock adjacent to the Tjårrojåkka apatite–iron
deposit has been affected by extensive and pervasive
albite alteration giving the rock a light grey or reddish
colour due to hematite staining. Albite + magnetite
alteration is particularly well developed in the area between the apatite–magnetite and the copper deposit.
Scapolite occurs locally as porphyroblasts and later
veinlets. The albitised and scapolitised rocks are overprinted by locally pervasive K-feldspar alteration and
veins of K-feldspar + Mg-hornblende ± titanite ±
quartz ± magnetite ± sulphides. Epidote is common
together with K-feldspar, as late veinlets (Fig. 5e) and as
an alteration of amphibole (Mg-hornblende). Amphibole (principally actinolite) also occurs in late veins
cutting epidote. Allanite occasionally occurs in the matrix associated with epidote. Quartz veins have been
observed in two generations. Carbonate veins (usually
calcite), sometimes with zeolites ± pyrite, generally
417
Fig. 5 Photographs of alteration and mineralisation types and
textures. a Typical massive magnetite ore with apatite, amphibole
(tremolite) and carbonate infill from the Tjårrojåkka-Fe deposit.
b Chalcopyrite with gold and hematite as late infill in fractures in
massive magnetite in the Tjårrojåkka-Fe deposit (BSE image).
c Chalcopyrite crosscutting magnetite in the footwall of the
Tjårrojåkka-Cu deposit. d Martite (light grey) replacing magnetite
(darker grey) in a vein in the footwall of the Tjårrojåkka-Cu
deposit. e Epidote veinlets crosscutting K-feldspar-amphibole
alteration in porphyritic andesite in the Tjårrojåkka-Cu deposit.
f Albite altered to K-feldspar in the Tjårrojåkka-Cu deposit (BSE
image). Ab albite; Am amphibole; Ap apatite; Bt biotite; Carb
carbonate; Ep epidote; Kfs K-feldspar; Ttn titanite; Ccp chalcopyrite; Hem hematite; Mag magnetite
represent the final stage of infill in existing veins and
vugs, or have exploited pre-existing fractures.
Tjårrojåkka-Cu
The footwall to the copper deposit is characterised by
pervasive albite alteration overprinted by veins of mag-
netite and red, green, white or rare blue apatite (Fig. 4a).
K-feldspar post-dates the albite alteration (Fig. 5f).
Scapolite (porphyroblasts and veins) was formed at an
early stage in the hanging wall (Fig. 4b), subsequently
overprinted by pervasive K-feldspar alteration, and has
affected the metadolerites to a greater extent than the
metaandesites. Amphibole occurs in several generations
as porphyroblasts, in monomineralic veins, or together
with K-feldspar ± titanite ± quartz ± carbonate ±
chalcopyrite ± bornite. The porphyroblasts contain
inclusions of quartz, K-feldspar, plagioclase and iron
oxide. Biotite occurs together with scapolite and is
commonly affected by later chlorite alteration. Epidote
occurs as patches in the matrix, together with K-feldspar
± amphibole ± carbonate ± quartz in veins or as a late
mineral phase cutting all the earlier phases in thin veinlets. Zeolites (stilbite and chabazite) are fracture-controlled post-ore stage minerals sometimes occurring in
earlier formed veins of amphibole ± epidote ± car-
418
Fig. 6 Simplified paragenetic
sequence of main ore and
alteration minerals in the
Tjårrojåkka apatite–iron (a)
and Tjårrojåkka copper (b)
occurrences
A TJÅRROJÅKKA-Fe
Magnetite stage
Magnetite
Hematite
Chalcopyrite
Bornite
Pyrite
Molybdenite
Gold
Apatite
Scapolite
Albite
Plagioclase
K-feldspar
Tremolite
Mg-hornblende/Tschermakite
Biotite
Titanite
Quartz
Epidote
Carbonate
Zeolites
B TJÅRROJÅKKA-Cu
M
Copper sulphide stage
VL
V+D
V+D
V+D
F
Loc
Loc
VL
V
P+V
P
P?
P+V
VL
P+V
P+V
V
V
F+VL
VL
VL
F
Magnetite stage
Magnetite
Hematite
Chalcopyrite
Bornite
Pyrite
Molybdenite
Gold
Apatite
Scapolite
Albite
K-feldspar
Mg-hornblende/Tschermakite
Actinolite
Biotite
Titanite
Quartz
Epidote
Carbonate
Zeolites
Post main ore stage
V
M
Copper sulphide stage
Post main ore stage
V
VL
V+D
V+D
V+D
F
Loc
Loc
V
?
P+V
P
P+V
P+V
V
P
V
V
F+VL
VL
F
M massive; V in veins; VL veinlets; P pervasive; F fracture filling; D disseminated; Loc locally occurring; ? uncertain
Solid line = major mineral forming event
Hatched line = minor mineral forming event
The length of the line is not in exact proportion with the time interval of the alteration.
bonate ± chalcopyrite ± pyrite. Fluorite has been observed in profile 600E in association with sericite and
pyrite. REE minerals comprise allanite, occurring as rims
on epidote, and late REE-carbonates in the magnetite–
apatite altered footwall. Barite (associated with Cusulphides and in K-feldspar), thorite (intergrown with
chalcopyrite or epidote), and zircon (in apatite and veins
of chalcopyrite + feldspar + quartz) are minor hydrothermal constituents also observed in the copper deposit.
Whole-rock geochemistry
Geochemical analyses were performed on drill core
samples to characterise the mass transfer during mineralisation and different types of alteration. Although attempts were made to sample least altered rocks, all
samples exhibit some effect of alteration and/or meta-
morphism; hence the geochemical data do not record
pristine magmatic features of the rock which in turn
makes the mobile element interpretation difficult.
Major and minor elements
The host rocks to the Tjårrojåkka deposits show large
variation in many of the major and minor elements due
to the intense hydrothermal alteration (Table 3). The
SiO2 content of the intermediate rocks varies between
50.16 and 67.86 wt% with total alkalis (Na2O + K2O)
from 6.11 to 11.26 wt%. The Fe2O3(tot) contents range
between 3.19 and 17.84 with TiO2 reaching a maximum
of 0.92 wt%. The Zr content shows large variation from
67 to 439 ppm. The widespread potassic alteration is
characterised by elevated values of K2O (max.
8.96 wt%) and BaO (max. 0.5 wt%), and the sodic
419
Table 3 Major and trace element whole-rock geochemical data for representative rocks
Rock type
Alteration
Drill hole
andesite
Least altered
Reference
sample
andesite
Ab altered
68301
andesite
Ab altered
70309
andesite
Kfs altered
68313
andesite
Kfs altered
74319
andesite
mineralised
74319
dolerite
unmineralised
69306
dolerite
mineralised
74320
123.8–124.05
21.35–21.57
76.60–76.85
79.74–80.02
200–208
155.0–162.0
153–156
57.09
0.697
17.56
9.32
0.107
2.2
4.13
3.41
4.07
0.35
1.19
100.14
57.63
0.699
16.73
9.42
0.046
3.25
1.7
6.97
2.46
0.31
0.99
100.20
61.58
0.596
16.20
4.46
0.073
2.05
3.64
7.15
1.13
0.76
2.08
99.72
53.72
0.705
16.06
10.60
0.099
3.21
4.01
3.65
5.02
0.30
2.54
99.92
58.80
0.658
16.16
6.93
0.097
2.37
3.95
3.63
6.19
0.26
0.96
100.00
59.82
0.915
15.93
5.29
0.100
1.64
2.56
2.11
8.06
0.32
1.49
98.23
47.68
1.882
15.08
14.67
0.053
7.33
2.59
4.84
2.63
0.62
2.42
99.79
46.71
1.759
15.40
14.01
0.328
6.21
7.53
2.92
2.53
0.52
2.05
99.96
<0.5
1502
<0.4
1.8
<10
19
1.2
5.1
<0.2
9
21
6
157
<1
403
0.5
0.6
7.3
0.4
1.9
116
<1
16
38
201
35.4
79.0
9.3
35.6
6.1
1.45
4.3
2.9
0.6
1.6
0.22
1.4
0.22
71
23
2.0
<1
<1
<2
3.9
NA
<0.5
456
<0.4
1.6
146
20
1
4.3
<0.2
7
47
6
97
1
269
0.4
0.5
5.3
0.5
6.9
143
<1
15
34
171
60.4
115.4
11.9
43.2
6.5
1.83
4.4
0.5
2.7
1.5
0.21
1.3
0.21
50
27
4.2
46
0.4
<2
<0.5
NA
<0.5
644
<0.4
<0.5
51
21
0.8
9.1
<0.2
9
<20
30
24
1
207
1.0
1.2
15.3
<0.1
3.2
46
<1
37
52
359
65.8
168.0
20.7
74.0
14.5
2.77
9.1
6.9
1.4
3.5
0.45
3.0
0.49
50
16
3.4
<1
0.6
<2
4.5
NA
<0.5
3564
<0.4
1.0
385
18
<1
4.4
<0.2
7
<20
<5
106
<1
399
0.3
0.5
4.0
0.2
1.7
139
3
13
430
150
30.1
63.7
7.37
30.0
5.1
1.64
3.8
0.5
2.6
1.4
0.20
1.3
0.20
23
61
2
<1
<2
<2
<1
NA
<0.5
2280
<0.4
0.5
ND
21
1.1
8.8
<0.2
14
64
15
135
1
295
1.0
0.9
11.2
0.3
3.4
134
<1
23
44
303
86.4
159.0
17.2
66.4
11.3
2.10
5.8
4.9
0.8
2.1
0.33
2.1
0.30
75
14
2.0
<1
<1
<2
6.3
NA
0.7
5790
3.8
1.4
8240
20
0.9
7.2
<0.2
11
<20
<5
177
3
310
0.7
0.8
8.5
0.5
4.8
128
2
24
36
275
81.6
144.0
15.0
55.3
7.5
2.10
5.5
4.3
0.9
2.5
0.34
2.2
0.34
77
15
1.8
36.0
0.9
193.0
7.2
0.936
<0.5
190
<0.4
1.4
ND
19
2.00
3.2
<0.2
7
48
6
117
4
129
0.2
1.7
2.5
0.2
3.9
215
<1
47
37
114
93.5
305.0
36.2
145.0
21.8
5.55
14.9
9.5
1.6
4.8
0.66
4.0
0.54
24
26
5.8
<1
<1
4.0
<0.5
NA
<0.5
807
<0.4
1.2
1020
20
1.3
2.6
<0.2
4
74
<5
85
<1
325
0.1
0.8
0.5
0.3
0.8
235
<1
26
82
87
19.0
41.0
5.25
23.7
4.7
1.90
5.4
4.7
1.0
2.9
0.37
2.4
0.38
102
51
3.0
<1
0.5
6.0
2.0
0.069
m along hole
wt%
SiO2
TiO2
Al2O3
Fe2O3 (tot.)
MnO
MgO
CaO
Na2O
K2O
P2O5
LOI
Total
ppm
Ag
Ba
Bi
Cs
Cu
Ga
Ge
Hf
In
Nb
Ni
Pb
Rb
Sn
Sr
Ta
Tb
Th
Tl
U
V
W
Y
Zn
Zr
La
Ce
Pr
Nd
Sm
Eu
Gd
Dy
Ho
Er
Tm
Yb
Lu
Cra
Coa
Asa
Moa
Sba
Aua (ppb)
Bra
Sb(wt%)
Major elements analysed with ICP and trace elements with ICP-MS
NA not available
a
Analysed by INAA
b
Analysed by XRF
420
alteration by Na2O contents reaching 9.57 wt%. This is
clearly being illustrated in the Na2O versus K2O plot
which also shows that Cu is correlated with potassic
alteration (Fig. 7a).
The metadolerites are characterised by a SiO2 range
between 35.8 and 50.78 wt%, a higher CaO content, up
to 9.16 wt%, compared to the metaandesites, and significantly lower Zr content (36–117 ppm). The metadolerites show the greatest variation in TiO2 with
concentrations varying from 0.64 to 2.37 wt%.
Rare earth elements (REE)
Compared to the K-feldspar altered metaandesites, the
albite altered metaandesites display a greater range in
Fig. 7 Whole-rock geochemistry plots of the host rocks to the
Tjårrojåkka deposits. a Na2O-K2O plot showing inverse relationship and correlation of Cu-mineralised samples to potassic
alteration. b REE patterns of representative rock samples.
Chondrite normalised after Boynton (1984). c Metaandesites and
metadolerites plotted on the igneous spectrum diagram after
Hughes (1973). d Rock classification diagram after Winchester
and Floyd (1977) revised by Pearce (1996)
c
Fig. 8 Immobile element plots for metaandesites and metadolerites
at Tjårrojåkka
REE content. The La content of the K-feldspar altered
samples varies between 26 and 86 ppm, with a mean of
51 ppm, while the La content of the albite altered samples varies between 15 and 208 ppm, with a mean of
58 ppm. The highest total REE content of the albite
altered samples is comparable to the highest concentration observed in the mineralised samples.
The REE patterns of representative samples exhibiting different types of alteration and mineralisation,
normalised after Boynton (1984), show LREE-enrichment and a negative Eu anomaly (Fig. 7b). The albite
altered and Cu-mineralised samples show the greatest
enrichment in REE compared to the least altered reference sample.
Element mobility during alteration and mineralisation
Element mobility was identified by plotting elements
normally considered to be immobile (Al, Zr, Ti, Y, and
421
500
B 20,00
450
18,00
400
16,00
350
14,00
Al2O3 (wt%)
A
Zr (ppm)
300
250
200
150
10,00
8,00
6,00
100
4,00
50
2,00
0
0,000
0,500
1,000
1,500
2,000
0,00
0,000
2,500
TiO2 (wt%)
0,500
1,000
1,500
2,000
2,500
400
500
TiO2 (wt%)
80,00
C
12,00
D
70,00
35
30
60,00
Nb (ppm)
SiO2 (wt%)
25
50,00
40,00
20
15
30,00
10
20,00
5
10,00
0
0,00
0
100
200
300
400
0
500
100
200
E
F
50
45
45
40
40
35
35
30
30
Y (ppm)
Y (ppm)
50
25
300
Zr (ppm)
Zr (ppm)
25
20
20
15
15
10
10
5
5
0
0
0
100
200
300
400
500
0
5
Zr (ppm)
Metaandesite - least altered
Metaandesite - albite altered
10
15
20
25
Nb (ppm)
Metaandesite - K-feldspar altered
Metaandesite - visible Cu
Metadolerite
Reference sample
30
35
422
Nb) against each other and other selected elements, and
using isocon plots that compare concentrations of elements in altered relative to least altered samples (Grant
1986). The samples were divided into metadolerites and
metaandesites, with the latter grouped as least altered,
albite altered, K-feldspar altered and mineralised. The
K-feldspar altered samples did not in most cases, show
evidences of previous albitisation, which makes the
comparison of element behaviour in the different alterations possible. The least altered sample used in the
isocon plots was collected from an outcrop distal to the
deposits and has a chemical composition similar to an
unaltered Andean arc andesite (Raymond 1995).
A large number of samples plot outside the igneous
spectrum in the diagram after Hughes (1973), and have
higher total alkalis that expected, suggesting alkali
mobility (Fig. 7c). In Fig. 7d the samples are plotted in
the rock classification diagram Zr/TiO2-Nb/Y after
Winchester and Floyd (1977) (revised by Pearce [1996]),
which shows that most samples retain andesitic and
basaltic affinity even after metamorphism and intense
hydrothermal alteration. Most of the samples affected
by K-feldspar alteration cluster relatively well (with one
exception), while the albite altered and mineralised
samples show a greater spread.
The behaviour of elements normally considered
immobile is illustrated in Fig. 8. The two clear trends
that can be distinguished in the TiO2-Zr plot indicate
different origins of the intermediate and basic rocks and
are in agreement with what has been observed in regional studies (Edfelt 2003). The roughly straight trends
and clusters of Zr, TiO2, Al2O3, and SiO2, (Fig. 8a–c)
suggest that these elements were, for the most part,
conserved in the system and that the large variation of
Zr in the andesites probably is a primary fractionation.
Y, however, is more scattered and can be considered to
have been mobile (Fig. 8e, f). The plot of Zr–Nb
(Fig. 8d) show that albite altered and mineralised samples scatter most, while the K-feldspar altered are well
clustered, which might indicate some degree of Nb
mobility in these systems. Fig. 8f also demonstrates that
Y was least mobile associated with K-feldspar alteration, but was mobile in the dolerites and related to
albite alteration and mineralised samples. This also explains the spread of the dolerite samples in the classification diagram (Fig. 7d).
In the isocon diagrams TiO2, Al2O3, SiO2 and Zr lie
very close to the ideal isocon for all three groups of
samples (albite altered, K-feldspar altered, and mineralised), suggesting that they were relatively immobile in
all systems (Fig. 9). However, in the K-feldspar altered
samples Zr show a slight enrichment compared to the
reference sample. Albite alteration caused significant
addition of Na2O and some addition of P2O5, resulting
in the formation apatite, and a depletion of K2O, MnO,
and Fe2O3. In the isocon diagram for K-feldspar altered
samples, K2O, MnO, and P2O5 show the inverse relationship compared to the albite altered samples. K2O,
MnO, P2O5, and Fe2O3 have been added in the min-
c
Fig. 9 Isocon diagrams for metaandesites showing elemental
changes associated with alteration and mineralisation. Average
values for groups of altered samples are compared with least
altered reference sample; n(albite altered)=22, n(K-feldspar
altered)=28, n(mineralised)=15. Major oxides plotted in wt%
and trace elements in ppm. For composition of reference sample see
Fig. 7 and Table 3
eralised samples whilst CaO is depleted in all three
groups compared to the reference sample.
Barium enrichment characterises K-feldspar altered
and mineralised rocks and is greatest in the latter. A
slight enrichment of Fe2O3 and V occurs in the mineralised samples, probably due to formation of magnetite. All REE elements are enriched in the altered and
mineralised samples compared to the reference sample,
which is in agreement with the results form the REEpatterns (cf. Fig. 7b). The greatest addition of REE is
observed in the mineralised samples.
Mineral chemistry
Silicates
Representative chemical compositions of feldspars are
shown in Table 4. Feldspars are among the most
abundant alteration minerals in the two deposits and
can be divided into three groups: potassium feldspar (Or
>90%), albite (Ab >90), and plagioclase (An 75–45).
Albitisation is restricted to the host rock surrounding
the Tjårrojåkka-Fe deposit and the footwall of the
Tjårrojåkka-Cu deposit, whereas K-feldspar alteration
is locally developed in the Tjårrojåkka-Fe deposit
associated with Cu-mineralisation and in the hanging
wall of the Tjårrojåkka-Cu deposit. Plagioclase occurs in
parts of the Tjårrojåkka-Fe deposit. The potassium
feldspars have a varying content of Ba substituted for K,
but there does not seem to be a systematic variation
within individual grains. However, Cu-mineralised
samples and pervasive K-feldspar alteration tend to be
richer in Ba than non-mineralised samples and K-feldspar occurring in veins. Some samples from the apatite–
iron occurrence contain more than 2 wt% BaO (Fig. 10)
and can be considered as hyalophane (Deer et al. 1992).
Scapolite has a meionite (Ca4Al6Si6O24CO3) content
(Me=100·Ca/(Ca + Na + K) between 30 and 55
(Fig. 11a). The Cl content varies between 0.9 and
2.9 wt% and CO2 between 1.2 and 2.8 wt% while the F
content is less than 0.2 wt% (Table 5). The SO3 contents
show wide variation from 0 to 1.5 wt%. The scapolite in
the Tjårrojåkka-Fe deposit has higher Cl (2.3–2.9 wt%)
and lower S content than samples from Tjårrojåkka-Cu
deposit (Fig. 11b). Scapolite from unmineralised wall
rock has a distinct character in being richer in CO2 than
scapolite related to mineralisation.
The composition of biotites, shown in Table 6, is between phlogopite/annite and eastonite. The Ti content
varies from 1 to 3 wt% TiO2, with the highest contents in
biotite associated with the Tjårrojåkka-Cu deposit. The
423
100
1000
SiO2
Albite altered metaandesite
Albite altered metaandesite
P2O5*100
K2O*10
Al2O3
10
MnO*100
Fe 2O3
Na2O
TiO2*10
CaO
Sr
Zr
Ba*0,1
Ce
100
V
La
Lu*100
Y
Nb
Th
10
MgO
1
1
1
10
100
1
10
100
1000
Least altered (reference sample)
1000
100
K-feldspar altered metaandesite
K-feldspar altered metaandesite
K2O*10
P2O5*100
SiO2
Al2O3
MnO*100
10
Fe2O3
TiO2*10
Na2O
MgO
CaO
Sr
Zr
Ba*0,1
Ce
100
V
La
Lu*100
Nb
Th
10
Y
1
1
1
10
1
100
10
100
1000
1000
100
K2O*10
Ba*0,1
Mineralised metaandesite
Mineralised metaandesite
P2O5*100
SiO2
MnO*100
Al2O3
Fe2O3
10
TiO2*10
Na2O
MgO
Ce
Zr
V
100
La
Lu*100
Y
Nb
Th
10
CaO
1
1
1
10
100
1
10
100
1000
424
Table 4 Representative results of electron-microprobe analyses of feldspars
Sample
Deposit
67306:250.61
Tj–Fe
74319:200.0
Tj–Cu
SiO2
63.42
63.08
TiO2
ND
ND
18.78
18.67
Al2O3
FeOa
ND
0.05
MgO
ND
ND
BaO
2.60
1.37
CaO
ND
ND
Na2O
1.22
1.09
14.50
15.64
K2O
Total
100.51
99.89
Or
79.17
86.43
Ab
6.65
6.01
An
0.00
0.00
Celsian
14.19
7.56
Number of cations on the basis of 32O
Si
11.83
11.82
Ti
0.00
0.00
Al
4.13
4.12
0.00
0.01
Fe2+a
Mg
0.00
0.00
Ba
0.19
0.10
Ca
0.00
0.00
Na
0.44
0.40
K
3.45
3.74
75316:75.10
Tj–Cu
71305:166.62
Tj–Cu
71305:392.4
Tj–Cu
67306:250.61
Tj–Fe
67306:279.0
Tj–Fe
64.32
ND
17.82
0.04
0.03
0.74
ND
0.61
16.28
99.83
92.35
3.45
0.00
4.20
64.91
0.02
18.23
0.09
ND
0.26
ND
0.20
16.75
100.45
97.35
1.15
0.00
1.50
69.09
ND
19.44
ND
0.02
ND
0.05
11.24
ND
99.85
0.14
99.39
0.47
0.00
64.15
0.02
22.86
0.07
ND
ND
4.00
9.38
0.13
100.61
0.96
69.45
29.59
0.00
56.64
0.05
27.45
0.32
0.12
ND
8.90
6.42
0.18
100.06
1.17
41.42
57.40
0.00
12.00
0.00
3.92
0.01
0.01
0.05
0.00
0.22
3.87
12.00
0.00
3.97
0.01
0.00
0.02
0.00
0.07
3.95
12.04
0.00
3.99
0.00
0.01
0.00
0.01
3.80
0.00
11.26
0.00
4.73
0.01
0.00
0.00
0.75
3.19
0.03
10.17
0.01
5.81
0.05
0.03
0.00
1.71
2.23
0.04
ND Not detected
All Fe as Fe2+
a
4
K-feldspar
Tjårrojåkka-Fe
Cu-mineralised
BaO (%)
3
Tjårrojåkka-Cu
Non-mineralised
Cu-mineralised
2
1
0
14
15
16
17
18
K2O (%)
Fig. 10 Variation in BaO content in K-feldspar
Ba content is higher in Cu-mineralised samples than in
non-mineralised samples. The amount of Cl varies between 0.2 and 0.5 wt% and F between 0 and 0.8 wt%.
The biotites from the apatite–iron ore plot in two distinct
groups with respect to the Mg/Fe and F contents
(Fig. 12a). In, or close to the breccia, the Mg content is
higher and the F content lower, than in the samples
outside. The sample that shows the highest F values is also
richest in Cl (0.5–0.6 wt%). The biotites from the Tjårrojåkka-Cu deposit show less variation in Mg/Fe ratio,
but Cu-mineralised samples are generally more Mg-rich
(Fig. 12a, b). In Fig. 12b three linear trends can be distinguished with the amount of Cl increasing with Fe.
The amphiboles in the Tjårrojåkka-Fe and -Cu
deposits are Ca-rich and range from tschermakite to
magnesio-hornblende to actinolite and tremolite (Table 7 and Fig. 13a). The most widespread types are
tschermakite and Mg-hornblende occurring in the matrix, often together with pervasive K-feldspar alteration,
or in fractures together with chalcopyrite or bornite.
Actinolite is found in veins where it generally is paragenetically later the other amphiboles, in the breccia
surrounding the apatite–iron body, and in the Tjårrojåkka-Cu deposit. Tremolite only occurs as veinlets in
the massive magnetite ore in the Tjårrojåkka-Fe deposit.
The amount of Cl in the amphiboles increases with the
Fe content and is highest in the tschermakites (Fig. 13b).
F is present in the amphiboles in the Tjårrojåkka-Cu
deposit (0.1–0.2 F per formula unit) but it is below
detection limit in the amphiboles from the Tjårrojåkka
apatite–iron ore.
Chlorite, titanite, epidote and allanite are minor constituents among the rock-forming and hydrothermal
alteration mineral assemblages and their chemistry will
not be discussed in detail. Titanite is more common in the
alteration assemblages in the copper deposit and contains
between 0.2 and 1.2 wt% F, around 1–2 wt% Fe2O3 and
traces of Ce. The Fe2O3 content in the epidote varies
between 15.5 and 17.2 wt%. REE were not detected.
Apatite
The analysed apatites classify as fluor-apatites with F
contents between 1.6 and 3.4 wt% (Table 8). The apatites in the copper occurrence have higher F than those
A
0.8
Si/(Si+Al)
425
0.7
Tjårrojåkka-Cu deposit have significant Co contents of
up to 1.8 wt%. Cr, Mn, Ni, Sb, Te, Hg, Pb, and Bi were
also analysed, but were below detection limits.
The V2O5 content in magnetite and hematite range
from 0.1 to 0.9 wt%, with the highest values in hematite
from the Tjårrojåkka-Cu deposit. Mn, Co, and Ni were
also detected in some of the samples, but are generally
below the detection limit. There do not seem to be any
systematic variations in minor element compositions of
iron oxides (Al, Ti, V, and Mn), except for Cr which is
slightly enriched in magnetite associated with copper
sulphides.
Scapolite
0.6
Tjårrojåkka-Fe
Non-mineralised
Cu-mineralised
Tjårrojåkka-Cu
Non-mineralised
Related to Cu-mineralisation
Discussion
0.5
Element mobilisation and chemical variations
20
30
40
50
60
Me
Cl
B
C
10xS
Fig. 11 Variation in scapolite composition. a Diagram showing
variation in meionite (Me) content. Me=100·Ca/(Ca + Na
+ K). b Cl-C-S diagram. All atoms per formula unit
in the iron ore. Apatites from an unmineralised outcrop
of metaandesite, located about 1 km WNW of the
Tjårrojåkka deposits, are the most F-rich (Fig. 14).
The apatites in the massive magnetite ore in Tjårrojåkka-Fe are the most Cl-rich (0.9–1.6 wt%), with a few
exceptions that show Cl values around 0.3 wt% probably due to zoning with the rims being Cl-poorer. The
slightly high totals in the analyses may be a result of
either the breakdown of the mineral under the electron
beam or a calibration problem due to partial breakdown
of the standards with time.
Sulphides and oxides
Representative analyses for sulphides (chalcopyrite,
pyrite and bornite) and oxides (magnetite and hematite)
are presented in Table 9. The sulphides do not show
large compositional variations between the two deposits.
In a few samples, chalcopyrite shows traces of Se,
Ag and Au and some pyrites associated with the
Element mobilisation and redistribution is common
during hydrothermal alteration, however, in terrains
that have been subject to extensive regional alteration,
metamorphism and/or metasomatism the quantification
of element mobility is difficult. In the case of the Tjårrojåkka occurrences, the degree of element mobility and
transport is best illustrated by considering the geochemical systematics of the metaandesitic rocks. Thirtynine percent of the samples plot outside the igneous
spectrum in the diagram after Hughes (1973) as a result
of potassic and sodic alteration (cf. Fig. 7c). The data
show that the albite altered metaandesites (mainly in the
footwall of the Tjårrojåkka-Cu deposit and the host
rock of the Tjårrojåkka-Fe deposit) have been subject to
a relative enrichment in Na, while the hanging wall of
the Tjårrojåkka-Cu and the copper mineralised zones
are characterised by a relative enrichment in K.
The distributions of both the major, minor and trace
elements suggest that the degree of mobility within the
K-enriched and Na-enriched samples is systematically
different. This is particularly well illustrated by the distribution of Na2O, K2O, P2O5, Ba, Y, and REE. Albite
altered and mineralised samples scatter in Y and REE
plots, indicating that the elements were mobile in these
systems, while the K-feldspar altered samples cluster.
The variation of Y in the dolerites could be due to the
intense scapolite alteration breaking down primary
mafic minerals.
Mobility of Zr, Ti and REE during hydrothermal
processes has been noted by many authors, including
Gieré (1990) and Rubin et al. (1993), in fluids where P,
F, and K and/or Na were important components along
with high activity of CO2. However, the variation of Zr
and Ti in the andesites is most probably a result of
primary fractionation although Zr shows a slight
enrichment in the K-feldspar altered samples and
hydrothermal zircons and titanites have been observed.
On the other hand, the enrichment of REEs in altered
and mineralised samples, relative to least altered, and
the presence of allanite and late REE-carbonates indicate that REE were mobile at Tjårrojåkka.
426
Table 5 Representative results of electron-microprobe analyses of scapolite
Sample
Deposit
67306: 279.0
Tj–Fe
75311: 255.96
Tj–Cu
SiO2
54.43
55.29
Al2O3
23.20
23.37
0.28
0.18
FeOa
CaO
8.46
9.03
Na2O
8.82
7.53
K2O
0.89
0.70
Cl
2.66
2.60
F
ND
ND
0.39
NA
SO3
COb2
1.48
1.84
Total
100.60
100.53
Cl=O
0.59
0.58
F=O
0.00
0.00
Total
100.01
99.95
Number of cations on the basis of 12(Si, Al)
Si
7.99
8.01
Al
4.01
3.99
0.03
0.02
Fe2+a
Ca
1.33
1.40
Na
2.51
2.11
K
0.17
0.13
Cl
0.66
0.64
F
0.00
0.00
S
0.04
0.00
0.29
0.36
Cb
75311: 13.0
Tj–Cu
71305: 392.40
Tj–Cu
73311: 91.40
Tj–Cu
75316: 226.49
Tj–Cu
53.72
23.45
ND
9.72
8.32
0.69
1.91
ND
0.05
2.59
100.44
0.42
0.00
100.01
53.39
22.84
0.08
10.73
6.94
1.08
1.96
0.07
1.09
1.73
99.90
0.44
0.03
99.43
51.78
23.95
0.12
11.23
7.71
0.75
1.55
ND
1.03
2.40
100.52
0.34
0.00
100.17
50.80
24.30
0.13
12.51
7.01
0.69
1.29
ND
1.35
2.36
100.43
0.29
0.00
100.14
7.92
4.08
0.00
1.54
2.38
0.13
0.48
0.00
0.01
0.52
7.98
4.02
0.01
1.72
2.01
0.21
0.50
0.03
0.12
0.35
7.77
4.23
0.02
1.81
2.24
0.14
0.39
0.00
0.12
0.49
7.67
4.33
0.02
2.02
2.05
0.13
0.33
0.00
0.15
0.48
74319: 200.0
Tj–Cu
75311: 255.96
Tj–Cu
73311: 91.40
Tj–Cu
67306: 250.61
Tj–Fe
36.54
2.88
15.35
16.60
0.67
13.18
ND
0.20
10.00
0.09
0.32
0.19
3.77
99.78
0.01
0.06
99.71
37.12
2.73
13.12
17.85
0.55
13.91
0.10
0.11
9.79
0.08
0.33
0.44
3.67
99.80
0.03
0.07
99.70
36.52
2.10
14.10
17.14
0.80
14.23
ND
0.16
9.62
0.04
0.73
0.30
3.53
99.28
0.02
0.15
99.11
37.98
0.99
14.55
15.37
0.15
16.18
0.04
0.21
9.71
0.07
0.42
0.50
3.69
99.87
0.03
0.08
99.76
5.54
0.33
2.74
2.10
0.09
2.98
0.00
0.01
1.93
0.03
0.15
5.67
0.31
2.36
2.28
0.07
3.16
0.02
0.01
1.91
0.02
0.16
5.59
0.24
2.55
2.20
0.10
3.25
0.00
0.01
1.88
0.01
0.35
5.70
0.11
2.57
1.93
0.02
3.62
0.01
0.01
1.86
0.02
0.20
NA Not available; ND not detected
a
All Fe as Fe2+
b
CO2 and C calculated by difference
Table 6 Representative results of electron-microprobe analyses of biotite
Sample
Deposit
69304: 45.53
Tj–Fe
71305: 449.15
Tj–Cu
SiO2
34.25
36.65
TiO2
2.03
2.40
17.48
16.22
Al2O3
a
FeO
22.24
18.45
MnO
0.21
0.43
MgO
8.35
11.47
CaO
ND
ND
BaO
0.07
0.06
9.89
9.80
K2O
Na2O
0.17
0.15
F
0.77
0.18
Cl
0.58
0.56
3.34
3.73
H2Ob
Total
99.37
100.08
Cl=O
0.04
0.03
F=O
0.16
0.04
Total
99.17
100.02
Si
5.38
5.56
Ti
0.24
0.27
Al
3.23
2.90
2+a
Fe
2.92
2.34
Mn
0.03
0.06
Mg
1.95
2.60
Ca
0.00
0.00
Ba
0.00
0.00
K
1.98
1.90
Na
0.05
0.04
F
0.38
0.09
427
Table 6 (Contd.)
Sample
Deposit
69,304: 45.53
Tj–Fe
71,305: 449.15
Tj–Cu
74,319: 200.0
Tj–Cu
75,311: 255.96
Tj–Cu
73,311: 91.40
Tj–Cu
67,306: 250.61
Tj–Fe
Cl
OHb
0.16
3.46
0.14
3.77
0.05
3.80
0.11
3.72
0.08
3.57
0.13
3.67
ND Not detected
All Fe as Fe2+
b
OH and H2O calculated by difference
a
Alteration paragenesis and the evolution
of fluid chemistry
Similarity in alteration minerals and paragenesis may
partly be a product of the common host rock to the
A
0.7
Biotite
Mg/(Mg+Fe 2+)
0.6
0.5
0.4
0.3
0
0.2
0.4
0.6
F in formula
B
0.7
Mg/(Mg+Fe2+)
0.6
0.5
Tjårrojåkka-Fe
Non-mineralised
Cu-mineralised
Tjårrojåkka-Cu
Non-mineralised
Cu-mineralised
0.4
0.3
0
0.04
0.08
0.12
0.16
0.2
Cl in formula
Fig. 12 Diagrams showing compositional variation in biotite.
a Plot of F against Mg/(Mg+Fe2+). b Plot of Cl against Mg/
(Mg+Fe2+)
Tjårrojåkka-Fe and Tjårrojåkka-Cu occurrences, but is
also an indication of similarities in fluid compositions
and depositional conditions. Ba, Cl, F and S are elements enriched in the alteration minerals in the Tjårrojåkka occurrences and can be used as indicators of the
nature of the hydrothermal fluids. Variation in the
content of these elements in K-feldspar, scapolite, apatite, biotite and amphibole clearly suggests differences in
the physical and/or chemical environment during alteration and mineralisation in the two deposits.
Barium feldspars commonly occur associated with
manganese deposits (Deer et al. 1992), but have also
been noted in, for example, the galena deposit at Korsnäs
(Mäkipää 1976) and the Pikkuharju Cu–Zn mineralisation (Lahtinen and Johanson 1987) in Finland, the Rosh
Pinah Pb–Zn deposit in Namibia (Page and Watson
1976), and the Ernest Henry IOCG-deposit in Australia
(Mark et al. 2000). At Tjårrojåkka the Ba content in Kfeldspar varies between the two deposits. In TjårrojåkkaFe deposit K-feldspar with a celsian component
(BaAl2Si2O8) occurs in the Cu-mineralised breccia surrounding the massive magnetite body indicating a high
Ba/K ratio in the hydrothermal fluids responsible for this
K-feldspar alteration. The amount of Ba in K-feldspar is
lower in samples from the Tjårrojåkka-Cu deposit and
lowest in the non-mineralised samples.
Scapolite is in some districts a common mineral in
metamorphic and metsomatic rocks and can be used as
an indicator of volatile activities and the Cl content of the
fluid salinity (e.g. Shaw 1960; Vanko and Bishop 1982).
The occurrence of marialite (Na4Al3Si9O24Cl)-rich
scapolite indicates high activities of NaCl in the rock or
fluid (Orville 1975) and regional occurrences of scapolite
rich in Cl possibly indicate the presence of metamorphosed evaporitic sequences (Ellis 1978). The scapolite at
Tjårrojåkka shows a trend with more Cl-rich varieties
around the magnetite body trending towards higher SO3and CO2-contents in the Tjårrojåkka-Cu deposit. The
same compositional variation has been observed in the
Malmberget apatite–iron ore (Fig. 1) where the scapolite
is Cl-rich (3.8 wt%) and in the nearby Nautanen Cu–Au
mineralisation (Fig. 1) scapolite is dominated by SO3and
CO2 (Frietsch et al. 1997). At Tjårrojåkka the scapolite
most distal to the copper deposit is more CO2-rich and
SO3-poor than scapolite from the mineralised part, and
can hence be interpreted as having formed from a SO3depleted hydrothermal fluid.
Apatite is a common mineral in the Tjårrojåkka
occurrences and since the three solid-solution end-
428
Table 7 Representative results of electron-microprobe analyses of amphiboles
Sample
Ampibole
Deposit
73311: 91.40
Tschermakite
Tj–Cu
40.75
SiO2
0.89
TiO2
Al2O3
10.27
Cr2O3
ND
a
Fe2O3
7.17
a
13.16
FeO
MnO
1.17
MgO
9.31
CaO
11.62
Na2O
1.56
K2O
1.73
Cl
0.61
F
0.22
1.70
H2Ob
Total
100.16
Cl=O
0.14
F=O
0.09
Total
99.93
Si
6.25
Ti
0.10
Al
1.86
Fe3+a
0.83
1.69
Fe2+a
Mn
0.15
Mg
2.13
Cr
0.00
Ca
1.91
Na
0.46
K
0.34
Cl
0.16
F
0.11
b
1.74
OH
68313: 263.75
Mg-hornblende
Tj–Fe
71305: 199.46
Mg-hornblende
Tj–Cu
71305:166.62
Actinolite
Tj–Cu
68313: 182.80
Tremolite
Tj–Fe
43.70
0.34
8.98
0.04
6.64
11.10
0.30
11.69
11.99
1.26
1.14
0.51
ND
1.88
99.58
0.11
0.00
99.47
50.06
0.43
4.84
0.03
3.71
10.72
0.67
14.23
12.20
0.94
0.52
0.17
ND
1.87
100.37
0.04
0.00
100.34
53.76
0.06
2.18
0.02
2.43
9.67
0.74
16.06
12.56
0.33
0.19
0.05
0.10
2.03
100.20
0.01
0.04
100.14
57.23
ND
0.38
0.05
0.47
3.55
0.05
22.21
13.70
0.13
0.02
0.02
ND
2.17
99.99
0.00
0.00
99.99
6.56
0.04
1.59
0.75
1.39
0.04
2.62
0.00
1.93
0.37
0.22
0.13
0.00
1.87
7.26
0.05
0.83
0.40
1.30
0.08
3.08
0.00
1.90
0.26
0.10
0.04
0.14
1.82
7.69
0.01
0.37
0.26
1.16
0.09
3.42
0.00
1.93
0.09
0.03
0.01
0.05
1.94
7.90
0.00
0.06
0.05
0.41
0.01
4.57
0.01
2.02
0.03
0.00
0.00
0.00
2.00
ND Not detected
Fe2+ and Fe3+ calculated using the method of Droop (1987) assuming 13 cations and 23(O,OH,F,Cl)
Calculated assuming the (Cl,F,OH) site is filled
a
b
members constitute Cl-, F- and OH-apatites, these elements can be used as indicators of the composition of
the hydrothermal fluids (Korzhinskiy 1982). Korzhinskiy (1982) also showed that the Cl/F ratio in apatite
increases with temperature and that the pressure effects
are negligible. The apatites analysed from an outcrop
sample, located approximately one km WNW of the
Tjårrojåkka deposits, have the highest F while those
clearly related to the mineralising processes from the
copper deposit are more Cl-rich. The outcrop apatites
are clearly distinct from the apatites from the deposits
and imply lower Cl activities during formation, reflecting either primary magmatic conditions or subsequent
metamorphism of apatite in the presence of relatively
low salinity fluids. Compared to apatite from the Kiirunavaara apatite–magnetite ore (Harlov et al. 2002)
the apatites at Tjårrojåkka are richer in Cl and H2O and
poorer in F. La and Ce are generally lower while Nd
shows similar values to the apatites in Kiirunavaara.
The interpretation of the halogen contents of silicate
minerals is complicated by crystal chemical effects between the hydroxyl site and cation sites within the
minerals, generally termed the Fe–F avoidance principle
(e.g. Ekström 1972; Rosenberg and Foit 1977). The
halogen composition of biotite (assuming no post-crystallisation re-equilibration) will be a function of the
Mg:Fe ratio of the biotite as well as P-T conditions at
the time of crystallisation, and the fluid chemistry (Zhu
and Sverjensky 1991; Munoz 1984). Biotites from different parts of the systems do not show great variation in
chemistry, except biotite from a distal part of the iron
ore that differs from the others in being the most Fe-rich
and showing the highest content of F. However, in a plot
of Cl against Mg/(Mg+Fe2+) (Fig. 8b), three linear
trends can be distinguished originating from differences
in temperature or salinity of the fluids, or representing
different generations of biotite.
Previous studies have also suggested that the F and Cl
contents of amphiboles are influenced by mineral structure and crystal chemistry (including the Fe–F and Mg–
Cl avoidance effects) as well as the P-T conditions and
halogen activity in the co-existing fluid (e.g. Oberti et al.
1993). All amphiboles at Tjårrojåkka are Ca-rich with
the highest F content in the amphiboles in the Tjårro-
429
Amphiboles
A
1
Tremolite
Mg-Hornblende
Mg/(Mg+Fe 2+)
0.8
Tschermakite
Actinolite
0.6
0.4
FeActinolite
0.2
Fe Hornblende
Fe Tschermakite
0
8
7.5
7
6.5
6
5.5
Si in formula
B
1
Mg/(Mg+Fe 2+)
0.8
0.6
0.4
0.2
Tjårrojåkka-Fe
Tjårrojåkka-Cu
Massive magnetite ore
Non-mineralised
Cu-mineralised
Cu-mineralised
0
0
0.04
0.08
0.12
0.16
0.2
Cl in formula
Fig. 13 Composition of amphiboles (cf. Table 7). a Classification
of amphibole composition after Leake et al. (1997). b Variation in
Cl content in amphiboles
jåkka-Cu deposit, and the highest Cl in the tschermakites. Oberti et al. (1993) showed that an increase in Cl
content would require increasing Fe2+, K, and Al which
is consistent with the trends in the amphiboles from
Tjårrojåkka. A more extensive interpretation of fluid
composition from halogen chemistry in biotite, amphiboles and apatite would, however, require temperature
and pressure data, which are currently not available.
Magnetite and hematite have similar geochemistry to
magnetite from Kiirunavaara and El Laco in Chile
(Nyström and Henrı́quez 1994) in being rich in V
(average 2,860 ppm) and low in Ti (average 240 ppm)
and Cr (average 340 ppm).
The fact that late REE-carbonates occur in the
footwall of the copper deposit and that allanite rims on
epidote are common indicate late infiltration of REE
enriched fluids. Previous studies have shown that allanite and apatite may form as replacement products of
monazite during hydrothermal alteration (Finger et al.
1998; Wing et al. 2003), which could explain the low
content of REE in apatite (cf. Table 8) and the absence
of monazite. Another possibility could be REE leaching
from apatite during late stage alteration and metamorphism, which has been suggested to account for REE
depleted apatite rims and the development of late stage
monazite and allanite in the Kiirunavaara magnetite
body (Harlov et al. 2002).
Overall, the alteration minerals (K-feldspar, scapolite, and apatite) related to the Tjårrojåkka apatite–iron
ore are more Cl- and Ba-rich compared to the alteration
minerals in the copper deposit that have higher contents
of F and SO3. Higher Ba in K-feldspar near the iron
deposit could reflect lower fluid sulphate concentrations
associated with a high Ba/K ratio, which is supported by
higher Ba contents in whole-rock analyses of K-feldspar
altered samples from Tjårrojåkka-Fe. The presence of in
scapolite and the existence of minor barite and late
hematite in the copper deposit point towards more oxidising conditions during the formation of the Tjårrojåkka copper deposit.
The mineral chemical and paragenetic results can be
interpreted in two ways; either (a) there were two different hydrothermal systems; one reduced fluid with a
high Ba/K ratio, high salinity and low sulphate concentration forming the Tjårrojåkka-Fe deposit, and another one more oxidised and F-SO4-CO2-rich forming
the Tjårrojåkka-Cu deposit, or (b) there was one
evolving system. An evolving system would require
lowering of Cl contents of the fluid, which could be
achieved either by fluid mixing or by loss of Cl to minerals, with the latter being a common feature in Cu–Au
deposits in the Cloncurry district, Australia (Baker
1998). There, the loss of Cl from the fluids gave rise to
hornblende and biotites with Cl contents up to 3.5 wt%
and other Cl-bearing phases such as scapolite and apatite. However, at Tjårrojåkka the Cl content in the
biotites and amphiboles is much lower (<0.6 wt%), but
scapolite and apatite in the apatite iron-body are more
Cl-rich than in the copper deposit and could have
influenced the reduction of salinity. Some preliminary
fluid inclusion work on the Tjårrojåkka occurrences
indicates moderately to highly saline (15–32 eq.wt%
CaCl2 + NaCl) systems (Broman and Martinsson 2000;
Edfelt et al. 2004), which is in accordance with data
from other copper deposits in the region (Wanhainen
et al. 2003; Broman and Martinsson 2000; Lindblom
et al. 1996). Edfelt et al. (2004) also noted an increase in
salinity and the appearance of carbonate daughter
minerals going from the apatite-forming stage to the Cusulphide stage, with a likely cause being fluid mixing.
The Tjårrojåkka occurrences as IOCG type deposits
The Tjårrojåkka Fe-oxide Cu–Au occurrences share
many characteristics (structural control, abundance of
iron oxides, anomalous concentrations of REE, albitescapolite-K-feldspar alteration) with deposits classified
as IOCG-type (e.g. Hitzman et al. 1992; Marschik and
Fontboté 2001; Porter 2001). The common spatial relationship between apatite–iron and copper ores has also
been noted between more recent deposits of Fe-oxide
Cu-Au-type in Cretaceous iron belt (Naslund et al.
2002) and Candelaria-Punta del Cobre deposits
(Marschik and Fontboté 2001) in Chile, which show
many similar features with the Tjårrojåkka occurrences.
430
Table 8 Representative results of electron-microprobe analyses of apatite
Sample
Deposit
75311: 255.96
Tj–Cu
75316: 328.50
Tj–Cu
CaO
56.13
55.81
MgO
ND
ND
SrO
0.11
0.09
MnO
0.19
0.09
a
ND
ND
FeO
La2O3
0.07
ND
0.14
ND
Ce2O3
Nd2O3
0.20
ND
41.31
42.23
P2O5
SO3
0.12
0.08
Cl
0.84
0.37
F
2.09
2.41
0.76
0.75
H2Ob
Total
101.95
101.82
Cl=O
0.05
0.02
F=O
0.46
0.52
Total
101.43
101.27
Number of cations on the basis of 26(O,OH,F,Cl)
Ca
9.89
9.73
Mg
0.00
0.00
Sr
0.01
0.01
Mn
0.03
0.01
2+a
Fe
0.00
0.00
La
0.00
0.00
Ce
0.01
0.00
Nd
0.01
0.00
P
5.75
5.82
Cl
0.23
0.10
F
1.09
1.24
b
0.68
0.66
OH
29IAE215
Outcrop
68313: 120.20
Tj–Fe
67306: 250.61
Tj–Fe
56.28
ND
0.05
0.16
0.07
ND
0.08
0.09
42.23
0.05
0.09
3.29
0.37
102.74
0.01
0.70
102.04
55.43
ND
0.09
ND
ND
0.09
0.15
0.16
41.42
0.11
1.57
1.54
0.84
101.38
0.10
0.34
100.94
54.98
ND
0.08
ND
ND
ND
0.09
0.09
41.64
0.10
0.99
1.96
0.79
100.71
0.06
0.43
100.21
9.59
0.00
0.00
0.02
0.01
0.00
0.00
0.01
5.68
0.02
1.66
0.32
9.85
0.00
0.01
0.00
0.00
0.01
0.01
0.01
5.81
0.44
0.81
0.75
9.74
0.00
0.01
0.00
0.01
0.00
0.01
0.01
5.83
0.28
1.02
0.70
ND Not detected
a
All Fe as Fe2+
b
Calculated assuming the (Cl,F,OH) site is filled
F
Apatite
Cl
OH
(calc)
Tjårrojåkka-Fe
Tjårrojåkka-Cu
Ap+Mag vein in footwall
Ap+Mag+Ccp vein in breccia
Cu-mineralised
Outcrop
Fig. 14 F-Cl-OH diagram showing compositional variation in
apatite (atoms per formula unit)
The magnetite–apatite occurrence at Tjårrojåkka has
similar characteristics to the Kiirunavaara apatite–iron
ore with magnetite as almost the only iron oxide and a
breccia developed along the wall rock contacts (Martinsson 2003). The Tjårrojåkka apatite–iron deposit
differs from the Kiruna type apatite–iron ores in Norrbotten only in the higher sulphide content of the breccia
surrounding the massive magnetite body. Both magmatic and hydrothermal replacement models have been
suggested for the formation of the apatite–iron ores of
Kiruna-type (e.g. Hitzman et al. 1992; Nyström and
Henrı́quez 1994), but from the existing data it is not
possible to prove either of these models for the Tjårrojåkka iron ore. However, the extensive hydrothermal
alteration and veining around the massive magnetite
body indicate that hydrothermal processes were definitely active at least at a later stage during the ore formation.
The Tjårrojåkka-Cu deposit might be related to this
late stage hydrothermal activity and considered as a
copper dominated end-member in the IOCG spectrum
of deposits. It is characterised by strong sodic and
431
Table 9 Representative results of electron-microprobe analyses of sulphides and oxides
Mineral
Sample
Deposit
Ccp
68313:166.4
Tj–Fe
Ccp
69304:45.53
Tj–Fe
Py
69304:45.53
Tj–Fe
Bn
68,313:29.0
Tj–Fe
Ccp
75311:255.96
Tj–Cu
Py
75311:255.96
Tj–Cu
Bn
75316:226.49
Tj–Cu
Wt%
S
Fea
Co
Cu
Zn
As
Se
Mo
Ag
Au
Total
34.82
31.12
ND
33.86
ND
ND
0.07
NA
ND
0.19
100.06
34.63
31.14
ND
33.74
0.15
ND
0.06
NA
0.11
ND
99.82
52.89
48.26
0.05
ND
ND
0.05
0.04
NA
ND
ND
101.29
25.27
11.80
ND
62.96
ND
0.05
ND
NA
ND
ND
100.07
37.19
30.53
ND
31.97
0.04
0.09
0.02
0.09
0.05
ND
99.99
50.02
47.21
1.67
ND
ND
0.09
0.03
0.06
ND
ND
99.08
26.19
11.77
ND
61.82
0.04
ND
ND
NA
ND
ND
99.82
Mineral
Sample
Deposit
Mag
68313:166.4
Tj–Fe
Mag
69304:218.16
Tj–Fe
Mag
68313:263.75
Tj–Fe
Hem
75316:328.50
Tj–Cu
Hem
75316:226.49
Tj–Cu
Mag
74319:335.50
Tj–Cu
Mag
75316:328.50
Tj–Cu
V2O5
SiO2
TiO2
Al2O3
Cr2O3
Fe2O3
FeO
MnO
MgO
ZnO
NiO
CaO
Total
0.34
0.03
0.03
0.22
ND
52.06
46.96
0.046
ND
ND
ND
ND
99.69
0.55
0.02
ND
0.12
ND
51.99
46.90
ND
0.02
ND
0.16
0.03
99.79
0.47
0.04
ND
0.04
0.04
52.19
47.08
ND
ND
ND
ND
ND
99.86
0.37
0.02
ND
0.04
ND
99.41
0.92
0.05
0.03
0.04
0.07
97.21
0.42
NA
0.13
0.06
NA
52.11
47.01
0.13
NA
0.05
ND
0.09
100.00
0.56
0.05
ND
0.03
0.04
52.11
47.01
0.10
ND
ND
ND
NA
99.90
b
b
0.07
ND
0.05
0.05
NA
100.00
0.05
ND
ND
ND
NA
98.36
ND not detected; NA not available. Ccp chalcopyrite; Py pyrite; Bn bornite; Mag magnetite; Hem hematite
a
Fe as Fe2+
b
All Fe as Fe3+
potassic alteration comparable to those surrounding the
apatite–iron ore, but show a stronger structural control.
The presence of metadolerites in the mineralised zone in
the Tjårrojåkka-Cu deposit could also have played and
important role for mineralisation as pathways for the
fluids.
Conclusions
The Tjårrojåkka occurrences can be considered as
belonging to the IOCG-group of deposits representing
two ‘‘end-members’’ of the class, with a spatial and
possibly also genetic relationship. The Tjårrojåkka
apatite–iron deposit has the typical characteristics of the
Kiruna-type iron ores, except the high concentrations of
sulphides in the surrounding ore breccia. The Tjårrojåkka-Cu occurrence is similar to epigenetic copper
deposits in the region and other Fe-oxide Cu–Au
deposits elsewhere in the world (e.g. Chile).
The whole-rock geochemistry indicates enrichment of
alkalis related to mineralisation due to the formation of
albite and K-feldspar. There was enrichment in Na and
P and depletion of K, Ba, and Mn related to albitisation,
with the inverse relationship of these elements associated
with K-feldspar alteration. Fe and V show depletion in
the altered zones and addition in mineralised samples.
REE were enriched in the system, with the greatest
addition related to mineralisation. Y mobility was
associated with albite alteration and copper mineralisation.
Several generations and overlapping hydrothermal
alteration stages indicate a long, complex history of
fluid activity related to the formation of the Tjårrojåkka deposits. The two occurrences at Tjårrojåkka
show a similar evolution in alteration paragenesis and
mineralogy, but with more oxidising, CO2-, F-, and rich fluids related to copper deposit, in contrast to the
Tjårrojåkka-Fe deposit where the fluids were more
reduced with a higher salinity and Ba/K ratio. This
might reflect one evolving system forming both
occurrences, with the copper deposit representing
slightly later products, but without geochronological
data and more detailed fluid inclusion and isotopic
studies we cannot rule out formation by two unrelated
mineralising events.
Acknowledgements We are grateful to GEORANGE and Phelps
Dodge Ltd who funded the study of the Tjårrojåkka Fe-oxide
Cu–Au occurrences. The SEM and electron microprobe work
432
was carried out at the Marie Curie ACCORD (Analytical and
Computational Centre for Ore Deposits) Ph.D. training site at
the Natural History Museum, London. We would like to thank
John Spratt, Anton Kearsley and Terry Greenwood for their
assistance with the analyses. Jan-Anders Perdahl, Roger Skirrow,
and Patrick Williams are thanked for their thoughtful reviews
and valuable comments, which substantially improved the manuscript.
Appendix
Appendix (Contd.)
74319:200.0
600E
Tj–Cu
74319:335.50
600E
Tj–Cu
75311:13.0
320E
Tj–Cu
75311:255.96
320E
Tj–Cu
75316:226.49
120E
Tj–Cu
75316:328.50
120E
Tj–Cu
75316:75.10
120E
Tj–Cu
Descriptions of drill core samples analysed for mineral chemistry
Sample no.
Profile
Occurrence
Description
29IAE215
67306:250.61
Outcrop
400W
Outcrop
Tj–Fe
67306:279.0
400W
Tj–Fe
68313:120.20
400W
Tj–Fe
68313:166.40
400W
Tj–Fe
68313:182.80
400W
Tj–Fe
68313:263.75
400W
Tj–Fe
68313:29.0
400W
Tj–Fe
68313:76.60
400W
Tj–Fe
69304:218.16
400W
Tj–Fe
69304:45.53
400W
Tj–Fe
71305:166.62
320E
Tj–Cu
71305:199.46
320E
Tj–Cu
71305:392.40
320E
Tj–Cu
71305:449.15
320E
Tj–Cu
73311:91.40
320E
Tj–Cu
Andesite, Kfs altered
Mag+Ap vein with
Ccp+Py in breccia,
Kfs altered
Scp+Bt alteration
with disseminated
Mag+Ap
Massive Mag with
Ap+Am+Carb
fracture infill
Massive Mag with
Ap+Carb+Ccp
+Au fracture infill
Massive Mag with
Hem vein and
Ap+Am+Carb
fracture infill
Mag+Am vein
with disseminated
Ccp in breccia,
Kfs altered
Disseminated Ccp+Bn
+Mag+Ap in Kfs
altered rock
Ccp+Py+Mag in
Am+Qtz vein in
Kfs+Bt altered
rock with
disseminated
Ccp+Py+Mag
Ccp+Py+Mag
in Pl+Bt
altered rock
Disseminated
Ccp+Py+Mag
in Kfs+Bt
altered rock
Am+Kfs+Ttn
vein cutting Mag
+Ap alteration
in footwall
Ab, Scp and Kfs
altered rock in
hanging wall
Kfs and Bt-altered
hanging wall
Kfs and Bt-altered
hanging wall
Ccp+Py+Mag
in veinlets of
Am, mineralised
zone
Ccp+Bn
disseminated
in Kfs, Bt,
Am-altered rock,
mineralised zone
Mag+Ap+Am
vein with Ccp
in footwall
Am+Ep+Qtz
vein in Kfs
and Scp-altered
hanging wall
Ccp+Py+Mag
in Am veinlets,
mineralised zone
Scp+Bt-altered
hanging wall
Mag+Ap+Am
vein in footwall
Kfs and Am altered
rock in hanging wall
Am amphibole; Ap apatite; Bt biotite; Carb carbonate; Ep epidote;
Kfs K-feldspar; Pl plagioclase; Qtz quartz; Scp scapolite; Ttn titanite; Au gold; Bn bornite; Ccp chalcopyrite; Hem hematite; Mag
magnetite; Py pyrite
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Paper III
Origin and fluid evolution of the Tjårrojåkka
apatite-iron and Cu (-Au) deposits, Kiruna area,
northern Sweden
Å. EDFELT1,*, K. BILLSTRÖM2, C. BROMAN3, R.O. RYE4,
M.P. SMITH5, AND O. MARTINSSON1
Division of Ore Geology and Applied Geophysics, Luleå University of
Technology, SE-971 87 Luleå, Sweden
2
Laboratory for Isotope Geology, Swedish Museum of Natural History,
Box 50 007, SE-104 05 Stockholm, Sweden
3
Department of Geology and Geochemistry, Stockholm University,
SE-106 91 Stockholm, Sweden
4
U.S. Geological Survey, Mail Stop 963, Denver Federal Center, Denver,
Colorado 80225, USA
5
School of the Environment, University of Brighton, Cockcroft Building, Lewes
Road, Brighton BN2 4GJ, UK
1
Corresponding author: [email protected]
*
_________________________________________________
Abstract
The Tjårrojåkka deposits are located in Northern Norrbotten, Sweden,
approximately 50 km WSW of the town of Kiruna, and consist of a spatially related
Kiruna type apatite-iron ore and a copper (-gold) deposit. This study presents fluid
inclusion, stable (oxygen, hydrogen, and sulfur) and radiogenic (U-Pb, Sm-Nd) isotope
data in an attempt to identify specific signatures of fluids related to different episodes of
ore deposition of the two deposits, establish hydrothermal temperatures, constrain the
time interval during which deposition took place, and finally investigate a possible
genetic link between the apatite-iron and copper (-gold) deposits at Tjårrojåkka.
From the available data, it is not obvious whether the massive part of the
apatite-iron ore formed from an iron rich melt or through hydrothermal replacement.
However, Sm-Nd data from the apatite-iron ore show that it has its origin in a source
with an Archean H-Nd isotopic composition. Moreover, the results show that a
hydrothermal system was active at least at a late stage during the deposition of the iron
ore, producing the apatite-magnetite-actinolite breccia, copper mineralization, as well
as extensive hydrothermal alterations.
The ore forming fluids were CO2-bearing, moderately to highly saline CaCl21
NaCl-rich fluids, with a relatively high oxidation state. The G18OH2O and GDH2O values
together with sulfur isotope data imply that magmatic fluids, or fluids that had
equilibrated with igneous rocks, played an important role in the formation of the
Tjårrojåkka deposits. However, due to the Ca-rich character of the fluids it can not be
ruled out that the fluids incorporated seawater brines or evaporites. The lowtemperature assemblage (stage IV) shows a trend towards lower G18O values most likely
due to mixing with meteoric water.
Stable isotope and fluid inclusion data indicate that the magnetite ore-forming
stage (stage I) deposited at a minimum temperature of 500 to 650°C followed by the
main copper mineralization (stage II) at around 400-450°C. The post ore stage of
copper mineralization associated with quartz veining (stage III) occurred at around 150200°C. The heat required for the hydrothermal system was most likely provided by a
deep seated magma. Although at present, it is not possible to establish a genetic link
between the Tjårrojåkka deposits and a particular intrusion in the area; however,
regionally there was igneous activity at the time of mineralization.
Fluid inclusion data indicate that cooling, along with decrease in salinity (from
stage II to III), were important factors for metal precipitation at Tjårrojåkka. A NE
trending shear zone in the area acted as a major fluid channel and a structurally
favorable location for the deposition of the copper (-gold) mineralization. U-Pb ages of
titanites and indications from Sm-Nd analyses of magnetite, apatite, and amphibole,
point to an age of the mineralization close to 1780 Ma. The ore deposition was a
relatively short-lived event, while the low-temperature assemblages (stage IV) formed
during several phases for a long period with the youngest indicated age of about 1700
Ma.
Similarities in stable isotope values, fluid composition, temperature of ore
deposition, and age of alterations and mineralization imply that the Tjårrojåkka apatiteiron and copper (-gold) deposits formed during the same ore-forming event around
1780 Ma as one continuous system. This study also indicates the presence of a,
previously unknown, generation of 1780 Ma apatite-iron ores in Northern Sweden.
Keywords IOCG deposit, apatite-iron ore, Kiruna type, Sweden, Paleoproterozoic, fluid
inclusions, stable isotopes, U-Pb dating, Sm-Nd dating.
_____________________________________________________________________
2
Introduction
The Tjårrojåkka apatite-iron and copper (-gold) deposits are
situated in the northwestern part of the Norrbotten County, Sweden
(Fig. 1). They are located about 50 km WSW of the town of Kiruna and
the prominent Kiirunavaara apatite-iron ore. The Tjårrojåkka apatiteiron deposit was discovered by the Geological Survey of Sweden in 1963
through airborne magnetic measurements and a few years later the
adjacent copper (-gold) prospect was found. The Tjårrojåkka deposits are
the best example of spatially related apatite-iron and copper (-gold)
deposits in Sweden, but so far only a few descriptions of the deposits
have been published. The geology and mineralization is briefly presented
in Ros and Rönnbäck (1971), Quezada and Ros (1975), Grip and
Frietsch (1973), Ros (1979), and Ekström (1978). More recent
descriptions of the Tjårrojåkka deposits have been published in Bergman
et al. (2001), Edfelt and Martinsson (2003), Edfelt and Martinsson
(2004), and Edfelt et al. (2004; 2006). The most detailed description of
the deposits deals with the alteration and mineral chemistry (Edfelt et al.,
2005).
Since Hitzman et al. (1992) defined iron oxide-rich Cu-Au
deposits (IOCG), including the great Olympic Dam deposit, as an
independent group of ore deposits, there has been a growing exploration
and research interest for these types of deposits. However, it is still
questioned whether apatite-iron ores of Kiruna type should be
incorporated in this group of deposits (Hitzman, 2000). It also remains
unclear if there is a genetic link between them and copper dominated
IOCG-systems, even if a clear spatial relation has been observed in e.g.
the Cretaceous iron belt (Naslund et al., 2002) and Candelaria-Punta del
Cobre deposits in Chile (Marschik and Fontboté, 2001), and the
Tjårrojåkka (Edfelt et al., 2005) and Gruvberget deposits in Sweden
(Lindskog, 2001; Martinsson and Virkkunen, 2004).
The aim of the present paper is to characterize the ore-forming
fluids and timing of mineralization at Tjårrojåkka through fluid
inclusion, stable (oxygen, hydrogen, and sulfur) and radiogenic (U-Pb,
Sm-Nd) isotope studies. The data are used to identify specific signatures
and temperatures of fluids related to different episodes of ore deposition
of the two deposits, constrain the time interval during which deposition
took place, and finally investigate a possible genetic link between the
apatite-iron and copper (-gold) deposits at Tjårrojåkka.
3
FIG. 1. Regional geology of northern Norrbotten with the location of the Kiruna,
Malmberget, and Aitik mines, as well as the Tjårrojåkka area (after Bergman et al.,
2001). Inset map: Map of the Fennoscandian shield with location of the northern Norrbotten area. KNDZ = Kiruna-Naimakka deformation zone, KADZ = KaresuandoArjeplog deformation zone, NDZ = Nautanen deformation zone, PSH = Pajala shear
zone.
Geology of the Tjårrojåkka area
Regional geology
The bedrock in northern Norrbotten is dominated by
Paleoproterozoic metavolcanic and intrusive rocks (Fig. 1).
Stratigraphically lowest is the Archean granitoid-gneiss basement, which
is unconformably overlain by Paleoproterozoic supracrustal units. Lowest
in this sequence are rift-related 2.5-2.0 Ga Karelian rocks followed by ca.
1.9 Ga Svecofennian metavolcanic, intrusive, and sedimentary rocks
formed in an compressional regime (Bergman et al., 2001). The lowest
part of the Svecofennian unit consists of arc-related volcanic rocks
(Porphyrite Group) and associated sediments (Kurravaara conglomerate).
These units are overlain by the Kiirunavaara Group metavolcanic rocks
and finally the Hauki Quartzite (Martinsson, 2004).
The roughly 10 km thick Paleoproterozoic unit was deformed and
metamorphosed at around 1.88 Ga, contemporaneously with intrusion
of Haparanda and Perthite monzonite granitoid suites, as well as at 1.811.78 Ga in conjunction with the Lina and TIB suites (Martinsson, 2004).
4
The metamorphic grade varies between upper greenschist and upper
amphibolite facies (Bergman et al., 2001). According to Bergman et al.
(2001) several major ductile shear zones were active at ca. 1.8 Ga and
resulted in various NNW to NNE-trending deformation and shear zones
(Fig. 1).
Northern Norrbotten is an important mining region hosting the
giant Kiirunavaara and Malmberget apatite-iron ores, and the Aitik CuAu deposit (Fig. 1). Kiirunavaara contains more than 2000 Mt of highgrade (60-68% Fe) magnetite ore and is the type locality for the “Kiruna
type” apatite-iron ores (Geijer 1931). The Malmberget deposit is
estimated to contain about 660 Mt ore at 51-61% Fe (Grip and Frietsch,
1973). More than 40 apatite-iron deposits are known from this area and
these are almost exclusively hosted by metavolcanic rocks of either the
Porphyrite or Kiirunavaara Group (Martinsson, 2004). Sweden’s largest
sulfide mine, Aitik, is located 20 km from Malmberget and is one of the
major copper and gold producers of Western Europe. It has an annual
production of 18 Mt of ore and is hosted by andesitic metavolcanic rocks
and a quartz-monzodiorite (Wanhainen, 2005). A large number of
epigenetic copper-gold deposits are found in the northern Norrbotten
area, but only a few of them have been proven to be economic up to
now. They exhibit large variations in mineralization style, host rock, as
well as ore-related alteration. The dominant hydrothermal alteration
minerals include albite, scapolite, K-feldspar, and biotite with amphibole,
carbonates, tourmaline, garnet, and sericite as locally important minerals.
Local geology
The geology in the Tjårrojåkka area is dominated by
metamorphosed intermediate and basic volcanic rocks (Fig. 2). Lowest in
the stratigraphy are the 1878±7 Ma porphyritic to aphyric metaandesites
classified as belonging to the Porphyrite Group volcanic rocks (Edfelt et
al., 2006). The metaandesites are cut by metadiabases that acted as feeder
dykes for the overlying metabasaltic unit. The intrusive rocks in the area
range from gabbro to quartz-monzodiorite in composition. The
intermediate rocks have been interpreted to have formed in a volcanic
arc setting on the Archean continental margin, while the basaltic unit
represents a later extensional event in a subaquatic back arc environment
(Edfelt et al., 2006).
The metamorphic grade in the area has been determined as
epidote-amphibolite facies (Edfelt et al., 2006; Ros, 1979). Widespread
alteration has been recognized in the area and is more intense in the
vicinity of deformation zones and mineralization. The most common
alteration types involve the formation of albite, scapolite, biotite, Kfeldspar, and epidote. Three deformation events have been distinguished
5
FIG. 2. Generalized geology of the Tjårrojåkka area with location of the Tjårrojåkka
apatite-iron and copper (-gold) deposits, and some minor occurrences. Coordinates in
Swedish national grid RT 90.
in the Tjårrojåkka area. The first event created NE-SW-striking steep
foliation corresponding with the strike of the Tjårrojåkka deposits and
was followed by the formation of an E-W deformation zone (Fig. 2). A
subsequent NNE-SSW compressional event, possible related to thrusting
from SW, resulted in folding, deformation of the Tjårrojåkka apatiteiron ore (Sandrin and Elming, 2005) and the formation of a NNW-SSE
deformation zone (Edfelt et al., 2006).
Mineralization and alteration
The Tjårrojåkka deposits consist of a Kiruna type apatite-iron ore
(Tjårrojåkka-Fe) and a copper (-gold) deposit (Tjårrojåkka-Cu). The
apatite-iron ore is characterized by a strong magnetic anomaly, which
continues along the footwall of the copper (-gold) deposit (Fig. 3A). The
Tjårrojåkka deposits are hosted in a 1.88 Ga metaandesite that have been
affected by widespread alteration during a prolonged history of
hydrothermal activity described in detail by Edfelt et al. (2005).
The alteration and mineralization assemblages are comparable in
the two deposits and the analyzed samples are referred to either of the
following stages; (I) magnetite ore stage, (II) copper (chalcopyrite) ore
6
stage, (III) post-ore stage, and (IV) low T stage (cf. Fig. 9). Stage I
represents the formation of the massive magnetite ore and the late stage
magnetite ± apatite ± amphibole ± quartz ± chalcopyrite veins. Stage II
overlaps with stage I and includes the main copper ore forming event
characterized by chalcopyrite and bornite. Stage III (post ore stage) involved
the formation of lower temperature veins with quartz ± amphibole and
some minor copper sulfides. The low temperature stage (IV) did not
involve mineralization and is characterized by low temperature assemblages.
FIG. 3. A. Magnetic map of the Tjårrojåkka deposits with location of drill holes
(circles), sample locations, and section A-A’ (modified after Sandrin, 2003). B. Schematic illustration of section A-A’ showing the distribution of alteration and mineralization as well as sample locations (modified after Edfelt et al., 2005). Mineral abbreviations: Ap = apatite, Bn = bornite, Ccp = chalcopyrite, Mag = magnetite.
7
Tjårrojåkka-Fe
The apatite-iron deposit at Tjårrojåkka consists of a massive
magnetite body surrounded by magnetite-apatite veins, here referred to
as breccia (Fig. 3B). It is known to a depth of about 400 m with an
estimated tonnage of 52.6 Mt at 51.5% Fe (Quezada and Ros, 1975).
Magnetite is the dominant ore mineral with hematite only occurring as
veins cutting the magnetite or as partly altered magnetite grains (Edfelt et
al., 2005). Apatite, tremolite, and carbonate fill fractures within the
massive magnetite ore. Sulfides (chalcopyrite, bornite, and pyrite) occur
as disseminations and veins mainly around the massive magnetite core
with electrum and silver tellurides found as inclusions in chalcopyrite.
Textural evidence from relations between magnetite and sulfides
indicates that the sulfides for the most part post-date the massive
magnetite (Edfelt et al., 2005).
The earliest alteration related to the genesis of the apatite-iron ore
is expressed by the formation of albite. The albite altered zone extends
around the entire magnetite body and into the footwall of the copper
(-gold) deposit (Fig. 3B). It is overprinted by subsequent scapolite and
K-feldspar alteration. K-feldspar also occurs in cross-cutting veins
together with Mg-hornblende ± titanite ± quartz ± magnetite ±
sulfides. Late stage veins comprise epidote, actinolite, and quartz, while
carbonate and zeolites ± pyrite veins represent the final stage of the
hydrothermal activity (Edfelt et al., 2005).
Edfelt et al. (2005) showed that the hydrothermal alteration
resulted in enrichment of Na related to albitization, and K, Ba, and Mn
associated with potassic alteration. Also REE are enriched in altered and
mineralized samples compared to non-mineralized. The same study
demonstrates that the Cl and Ba content of apatite, scapolite, feldspars,
amphiboles, and biotite are higher in alteration minerals related to the
apatite-iron ore compared to the copper (-gold) deposit.
Tjårrojåkka-Cu
The Tjårrojåkka copper (-gold) deposit, an elongated body about
700 m long and 30 m wide, shows a structural control (Sandrin and
Elming, 2005) and has a calculated tonnage of 3.23 Mt at 0.87% Cu
(Ros, 1979) . The ore mineralogy is dominated by chalcopyrite, bornite,
pyrite, and magnetite occurring as disseminations and veins in a NE
striking zone dipping about 85° towards N. Minor ore phases include
gold, silver tellurides, and silver sulfides.
The alteration pattern surrounding the copper deposit can be
divided into three zones on basis of alteration mineralogy (Fig. 3B): (1)
early pervasive albite alteration in the footwall overprinted by magnetiteapatite veins; (2) scapolitization and associated biotite alteration in the
8
hanging wall; and (3) potassic alteration mainly defined by the formation
of K-feldspar in and around the ore zone. Copper sulfides are associated
with pervasive K-feldspar alteration and veins of amphibole ± K-feldspar
± quartz ± magnetite ± carbonate (Edfelt et al., 2005). Late alteration
minerals include epidote, carbonates, zeolites, and some minor fluorite.
The whole-rock chemistry of altered and mineralized samples from the
copper (-gold) deposit shows the same pattern as the ones from the
apatite-iron ore (see previous section), whereas apatite, scapolite,
amphiboles, and biotite are enriched in F and S compared to the apatiteiron deposit.
Sampling and methods
Thirty-four samples were collected for fluid inclusion, stable and
radiogenic isotope studies (Fig. 3). In Table 1, they are described with
regard to location, mineralogy, paragenesis, and the type of analysis
conducted on them. Fluid inclusions were studied at the Fluid Research
Laboratory at the Department of Geology and Geochemistry, Stockholm
University and at the University of Brighton, by optical microscopy,
microthermometry, and Raman microspectrometry in doubly polished
thin sections obtained from drill cores. Fluid inclusions in quartz, calcite,
apatite, and actinolite were analyzed in 8 samples from 5 different drill
cores.
A conventional microscope was first used to study the petrography
and distribution of fluid inclusions. At the Stockholm University the
microthermometric low temperature measurements, 180 to +35RC,
were made on a Linkam THM 600 stage with a reproducibility of ±0.1RC.
The cooling was obtained by a flow of liquid nitrogen through the stage.
The high temperature measurements, +35 to +600RC, were done with a
Chaixmeca heating/freezing stage with a reproducibility of ±2RC. At the
University of Brighton, a Linkam MDS600 heating/freezing system was
used with similar precision. The instruments were calibrated with
synthetic fluid inclusion standards and small amounts of high-purity
melting-point standards. In order to identify solid phases and check for
the presence of gases in the inclusions, Raman analyses were made with
a multichannel Dilor XY Raman spectrometer on some of the samples.
Exciting radiation was provided by the green line (514.5 nm) of an
Innova 70 argon laser. The laser beam was focused on the sample with a
100 X objective in an optical microscope. Calibration was made with
respect to wave number using a neon laser and a silicon standard.
Stable isotope analyses were carried out at the isotope laboratory at
the U.S. Geological Survey in Denver, USA. Oxygen isotope data were
9
TABLE 1. Location and Description of Samples Used for Fluid Inclusion and Isotope Analyses
Swdish grid RT90
Type of
Easting Northing
Sample description
Paragenesis
Sample1
analysis
Tjårrojåkka-Fe
67306:122.95 7514927 1642889 Ap-Am-Ccp in massive Mag ore
I
SI
67306:156.45 7514927 1642889 Mag-Ap with Am-Qtz-Ccp-Carb in
IMag-Ap
SI, FI
massive Mag ore
IIIAm-Qtz-Ccp-Carb
67306:284.00
67306:62.20
7514927
7514927
1642889 Mag-Am-Qtz-Ccp vein in breccia
I
1642889 Massive Mag-Ap-Am with later Qtz-Carb IMag-Ap
IIQtz-Carb
SI
SI, FI
68305:202.65
68305:204.71
7514870
7514870
1642959 Qtz-Kfs-Py vein cutting Mag ore
1642959 Am-Py-Zeol as later infill in Mag vein
III
IMag
IIIAm-Py-Zeol
SI, FI
SI
68313:199.70
68313:20.57
69304:93.03
69304:214.00
69304:229.83
Tjårrojåkka-Cu
71305:149.01
7515044
7515044
7515104
7515104
7515104
1642746
1642746
1642672
1642672
1642672
I
IV
III
I
I
SI
SI, Dat
Dat
SI, FI
SI
7514957
1642238 Qtz-Carb vein in Am-Ap altered footwall IIIAp-Am
IVQtz-Carb
SI, FI
71305:168.50
71305:272.70
7514957
7514957
I
II
SI
SI
71305:416.14
72303:138.92
72303:145.75
72303:180.00
73303:99.61
74313:83.4
74319:301.77
74320:134.37
74325:179.80
75311:165.45
75311:205.15
75311:220.65
7514957
7515173
7515173
7515173
7515222
7514943
7515309
7515046
7515362
7515208
7515208
7515208
IV
III
III
II
III
I
I
II
IV
III
III
II
SI
SI, Dat
SI, Dat
SI
SI, Dat
Dat
SI
SI
SI
Dat
FI
SI
75311:247.76
7515208
1642238 Mag-Ap-Ccp vein in footwall
1642238 Am-Kfs-Qtz-Carb-Ccp vein in Cumineralization
1642238 Qtz-vein cutting Kfs alteration
1642117 Kfs-Am-Ttn vein
1642117 Kfs-Am-Ttn vein
1642117 Disseminated Kfs-Am-Mag-Ap-Ccp
1642410 Am-Fds-Ttn vein
1641970 Mag-Ap-Ccp-Ttn vein
1642362 Mag-Ap-Am vein in footwall
1641959 Ccp-Bn vein cutting Scp alteration
1642333 Qtz(-Ep-Zeol) vein cutting Am-Mag vein
1642098 Qtz-Ttn vein cuting Am-Ep alteration
1642098 Qtz-vein with Bn
1642098 Am-Mag-Ccp vein and dissemination
overprinting Scp alteration
1642098 Disseminated Ccp-Mag in Am+Kfs(±Ep)
alteration
II
SI
75311:262.02
75311:283.30
7515208
7515208
1642098 Qtz-vein with Bn±Ccp
III
1642098 Mag-Ap-Am vein with later Carb in foot- IMag-Ap-Am
wall
IVCarb
FI
SI, FI
75316:263.17
75316:268.91
75316:272.63
75316:328.50
Regional
TJ013
7515089
7515089
7515089
7515089
1641935
1641935
1641935
1641935
SI
SI
Dat
SI
7515103
1644124 Qtz-monzodiorite
Ap-Am in massive Mag ore
Kfs-Am-Ttn-Ep vein in breccia
Kfs-Am-Ttn alteration
Mag-Ap-Am-Qtz-Ccp vein in breccia
Mag-Am-Qtz-Ccp vein in breccia
Am-Mag-Ccp-Py-Zeol vein
Am-Mag-Ccp-Py dissemination
Am-Scap-Ttn alteration
Ap-Mag vein in footwall
IV
II
II
I
Dat
Drill hole number and depth; Abbreviations: Act = actinolite, Am = amphibole, Ap = apatite, Bn =
bornite, Carb = carbonate, Ccp = chalcopyrite, Ep = epidote, Fds = feldspar, Kfs = K-feldspar, Mag =
magnetite, Hbl = hornblende, Py = pyrite, Qtz = quartz, Scp = scapolite, Ttn = titanite, Zeol = zeolite.
FI = fluid inclusion, SI = stable isotope, Dat = dating.
For drill hole and sample locations see Fig. 3.
1
10
obtained from quartz, K-feldspar, magnetite, apatite, and amphiboles by
use of the BrF5 method described by Clayton and Mayeda (1963) and a
Finnigan 252 mass spectrometer. Reproducibility was generally ±0.2 per
mil or better. Hydrogen isotope data were collected by continuous flow
isotope ratio mass spectrometry using a Thermo Finnigan TC/EA
pyrolysis device coupled to a Thermo Delta Plus XL mass spectrometer
(Sharp et al., 2001). Reproducibility was generally ±4 per mil or better
for GD. Oxygen and hydrogen isotopic compositions are reported
relative to Vienna Standard Mean Ocean Water (VSMOW) in
conventional Gnotation. An analysis of the standard material that was
run along with the unknowns gave 96 per mil, which almost
matches within error the accepted value of 100 ±2 per mil (Coplen et al.,
2001). Sulfur isotope analyses were conducted on chalcopyrite, bornite, and
pyrite following the method of Giesemann et al. (1994) using a Carlo Erba
Elemental Analyzer coupled to a Micromass Optima mass spectrometer.
Reproducibility was ±0.2 per mil or better. The isotopic compositions are
expressed in G-notation relative to Cañon Diablo Troilite (CDT).
Titanites from different alteration parageneses were separated from
drill cores and handpicked under a binocular microscope. They were initially
treated in a clean laboratory, washed in acetone in an ultra-sonic bath, then
with diluted HNO3 on a hot plate, and finally rinsed in double distilled
water. Briefly, isotope dilution analysis was performed as follows. Each
sample was spiked with a 233-236U/205Pb solution and a mixture of HF and
HNO3 was added. Following this, it was dissolved in a Teflon bomb at ca.
200°C for 5 days. After evaporation and dissolution in HBr an initial ion
exchange step was carried out from which a purified Pb aliquot resulted.
The uranium fraction went through a second ion exchange procedure in
HCl where eventually remaining Fe was removed. Finally, the resulting Pb
fraction was loaded on a single filament, while the uranium was loaded using
a double-filament arrangement, and the appropriate isotopic ratios were
measured on a Finnigan MAT 261 spectrometer. The software packages
ISOPLOT and PBDAT from Ludwig (1991a; 1991b) was used to calculate
and plot relevant ages and associated errors.
Two samples taken from the massive part of the apatite-iron ore were
selected with the aim to derive a Sm-Nd mineral isochron. It was possible to
separate the same three minerals (amphibole, magnetite, and apatite) from each
of them, and these phases underwent conventional ion exchange techniques to
obtain Sm and Nd aliquots (Pin and Zalduegui, 1997), which subsequently
were analyzed on a Finnigan MAT 261 spectrometer (see Mellqvist et al. (1999)
for further analytical details). All the chemical procedures and mass spectrometry
related to radiogenic isotope work were carried out at the Laboratory for
isotope geology at the Swedish Museum of Natural History in Stockholm.
11
Fluid inclusions
Four types of fluid inclusions were found in apatite, actinolite,
quartz, and calcite in the samples from the Tjårrojåkka deposits (Table
2). Type AM fluid inclusions are aqueous multisolid inclusions with at
least three solid phases and a vapor bubble. Type A1 and A2 inclusions
contain an aqueous fluid, a vapor bubble, and one or two solid phases,
respectively. Type A inclusions consist of two phases, an aqueous liquid,
and a vapor bubble. Most measurements were made on primary (trapped
during primary growth of the host mineral) fluid inclusions. A few
secondary inclusions (type A) occurring in healed micro-fractures were
also analyzed with the purpose to get a full picture of all hydrothermal
fluids that have affected the deposits. No inclusion was larger than 30 Pm
and most were less than 10 Pm in their longest dimension.
Since the first melting temperature (Tfm) of fluid inclusions
indicates that the aqueous inclusions have a complex salt composition
with additional chlorides present alongside NaCl (among them
significant amounts of CaCl2), the salinity will be expressed as eq. wt. %
(CaCl2+NaCl), which gives the best approximation for the specific
composition. The salinity was estimated from the final melting of ice, Tm(ice),
using the data of Oakes et al. (1990) for CaCl2-rich compositions. The
TABLE 2. Description and Types of Inclusions Present in Samples Used
for Fluid Inclusion Studies
Sample1
Tjårrojåkka-Fe
68305:202.65
67306:62.20
67306:156.45
69304:214.00
Tjårrojåkka-Cu
75311:205.15
75311:262.02
75311:283.30
71305:149.01
Type of inclusions observed
AM
A2
A1
A
Host mineral
Quartz
Quartz
Actinolite
Apatite
Calcite
Quartz
-
+
+
+
+
+
+
+
+
Quartz
+
-
-
-
Quartz
Quartz
Calcite
Calcite
Quartz
-
-
-
+
+
-
-
+
+
+
+
+
Drill hole number and depth
AM = aqueous multisolid inclusion with a vapor bubble, A2 = aqueous
inclusion with two solid phase and a vapor bubble, A1 = aqueous inclusion
with one solid phase and a vapor bubble, A = aqueous inclusion with a
vapor bubble
For sample descriptions see Table 1 and for locations Fig. 3.
1
12
FIG. 4. Photomicrographs of the different types of fluid inclusions present at Tjårrojåkka. A. Type AM fluid inclusion in quartz (69304:214.00). B. A1 fluid inclusions in
quartz (67306:156.50). C. Fluid inclusion (type A) in apatite (67306:156.50). D. Type
A fluid inclusions in calcite (67306:156.50).
temperature obtained from fluid inclusion studies is a minimum estimate
of the trapping temperature (no pressure correction has been added).
Tjårrojåkka-Fe
Multisolid aqueous fluid inclusions (type AM) are the earliest
inclusions found in quartz (stage I) and contain at least three solid phases;
hematite, calcite, and halite (Table 2; Fig. 4A). The presence of hematite
and calcite was identified by their characteristic Raman spectra in the
multiphase inclusions; hematite bands at 612, 413 and 295 cm-1, and
calcite bands at 1087, 714 and 283 cm-1 (Griffith, 1987). The very low
first observed melting temperatures (Tfm), from around -65º to ñ70ºC,
indicate a complex CaCl2+NaCl dominated composition of the fluid
(Table 3), probably with high concentrations of other divalent cations.
Upon heating, hematite and calcite remained unchanged. Type AM
inclusions underwent decrepitation before final halite melting, and
homogenization of the inclusion content, was achieved; therefore, the
salinity could not be obtained from the melting temperature of halite.
Instead the salinity must be determined from volume estimates of the size
of the halite cube in the inclusions (Roedder, 1984) and by using this
13
FIG. 5. Salinity vs. homogenization temperature for primary inclusion types A1 and A.
Grey symbols represent samples from the Tjårrojåkka apatite-iron deposit and white
symbols samples from the copper (-gold) deposit.
method an approximate salinity of 40-60 eq. wt. % NaCl is indicated. It
is difficult to establish the salinity more accurately due the complex
nature and variable phase ratios of the inclusions. Total homogenization
could not be measured, but the temperature of decrepitation provides
minimum values and show that homogenization temperatures should be
at least 300º to >500ºC.
Aqueous inclusions with one solid phase, halite or calcite, (type
A1; Fig. 4B) or two solid phases, halite and calcite, (type A2) in addition
to liquid and vapor in quartz are often found associated with chalcopyrite
and are interpreted as representing the fluid composition during the main
stage of copper deposition (stage II) and post ore stage (stage III) (Table
2). For both types of inclusions first melting (Tfm) took place between
ñ62º and ñ70ºC, which suggests that the aqueous liquid has a
composition dominated by CaCl2 and NaCl (Table 3). Total
homogenization (to liquid) was possible solely for those with halite as the
solid phase (A1Hl) (Fig. 5). For A1Hl total homogenization by dissolution
of the halite was measured between 193º to 282ºC (to liquid). The
salinity calculated from these temperatures varies between 22 and 37 eq.
wt. % CaCl2+NaCl. Inclusions with calcite as the solid phase (A1Cal)
displayed final ice melting around ñ24ºC, which corresponds to a
salinity of approximately 22 eq. wt. % CaCl2+NaCl (Table 3).
Homogenization of the vapor and the liquid in the presence of calcite
occurred at 128º to 134ºC. Halite dissolution in inclusions with both
halite and calcite as solid phases (A2) occurred within the same
temperature interval as for A1Hl.
Type A inclusions are found in apatite, actinolite, quartz, and
calcite and represent stages I to III (Table 2: Fig. 4D). In apatite-hosted
14
inclusions, the vapor bubble is relatively large and occupies about 20-30
volume % of the total inclusion volume (Fig. 4C). Such inclusions are
situated in the center of the apatite grains. A few inclusions, at the
margin of the grains, have a smaller (~5 vol. %) vapor phase. The
analyses show that the fluid inclusions are composed of an aqueous
CaCl2-NaCl solution (Tfm = ñ50º to ñ55ºC) with a salt content of
between 15 and 17 eq. wt. % CaCl2+NaCl (Tm = ñ11º to ñ14ºC).
Homogenization of the inclusions in the center of the apatite occurred at
temperatures of 370º to 380ºC. One inclusion on the margin of an
apatite grain homogenized at 180ºC. In actinolite the vapor phase
occupies 5-10 volume % of the inclusions. Actinolite occurs intergrown
with chalcopyrite in veins and many crystals contain solid inclusions of
chalcopyrite. Analyses of the few measurable fluid inclusions in actinolite
with Tfm = ñ35ºC indicate a MgCl2 composition of the aqueous solution
(Davis et al., 1990) and a salinity of around 15 eq. wt. % MgCl2 (Tm =
ñ11º to ñ13ºC). Homogenization temperature (to liquid) was between
121º and 129 ºC. Analyses of the fluid inclusions in quartz and calcite
show that the fluid at this stage still had a CaCl2-NaCl composition (Tfm
= ñ53º to ñ70oC). The salinity of the two-phase inclusions is between
18 and 28 eq. wt. % CaCl2+NaCl (Tm = from ñ15º to ñ40ºC) and a
homogenization temperature between 113º and 270ºC.
Tjårrojåkka-Cu
The main part of inclusions observed from samples from the
Tjårrojåkka copper (-gold) deposit represent stages III and IV. Type AM
inclusions in quartz are probably the earliest inclusions, however, only
one inclusion was observed. It consists of an aqueous liquid, a vapor
bubble and three solid phases. Unfortunately, the inclusion decrepitated
at around 150ºC, before any temperature measurements were obtained.
The size of the halite cube indicates a salinity of approximately 40 eq.
wt. % NaCl (Roedder, 1984).
Inclusions of type A1 are observed in quartz and calcite with halite
as a solid phase. Total homogenization occurred by halite melting
between 196ºC and 292ºC to liquid (Table 3; Fig. 5). These
temperatures give a salinity between 32 and 37 eq. wt % CaCl2+NaCl
(Tfm = from ñ70º to ñ76ºC).
Type A inclusions are the most common and occur randomly in
quartz and calcite. One inclusion was different than the others; it
contained a number of dark solid phases, probably bornite. A few twophase inclusions with similar shape and size appear in a healed
microfracture that cross-cuts the random-occurring inclusions. First
melting (Tfm) of the random-occurring inclusions was observed between
15
TABLE 3. Fluid Inclusion Microthermometry Results
Sample1
Type of
Mineral
inclusion
Tfm(ice)
Tm(ice)
eq. wt. %
T
T
CaCl2+NaCl h(l+v) h(l+h)
Notes
Tjårrojåkka-Fe
68305:202.65
A
Qtz
ñ68
ñ34.9
26.5
135
--
68305:202.65
A
Qtz
--
ñ18.8
19.9
192
--
68305:202.65
A
Qtz
--
ñ31.4
25.4
130
--
68305:202.65
A
Qtz
--
ñ18.4
19.8
177
--
68305:202.65
A
Qtz
--
ñ31.3
25.3
124
--
68305:202.65
A
Qtz
ñ58
ñ37.0
27.1
126
--
68305:202.65
A
Qtz
ñ58
ñ39.7
27.8
131
--
68305:202.65
A
Qtz
ñ58
ñ19.5
20.3
141
--
68305:202.65
A
Qtz
--
--
--
126
--
68305:202.65
A
Qtz
--
ñ28.9
24.4
128
--
68305:202.65
A
Qtz
ñ55
--
--
113
--
68305:202.65
A
Qtz
ñ69
ñ25.6
23.1
240
--
68305:202.65
A
Qtz
ñ69
ñ25.2
23.0
270
--
68305:202.65
A
Qtz
ñ70
ñ39.6
27.8
153
--
68305:202.65
A
Qtz
--
ñ31.7
25.4
136
--
68305:202.65
A
Qtz
--
ñ29.1
24.4
130
--
68305:202.65
A
Qtz
ñ70
ñ36.3
26.7
140
--
68305:202.65
A
Qtz
ñ52
ñ2.9
5.8
166
-- secondary inclusions
68305:202.65
A
Qtz
--
ñ3.6
6.9
156
68305:202.65
A
Qtz
ñ57
ñ8.9
13.2
154
67306:156.50
A
Cal
ñ55
ñ15.9
18.4
138
--
67306:156.50
A
Cal
ñ55
ñ15.6
18.2
128
--
67306:156.50
A
Cal
ñ54
ñ19.3
20.2
133
--
67306:156.50
A
Cal
ñ53
ñ19.6
20.3
136
--
67306:156.50
A
Cal
ñ54
ñ19.9
20.5
133
--
67306:156.50
A
Cal
ñ54
ñ18.4
19.7
137
--
67306:156.50
A
Cal
ñ55
ñ17.9
19.0
137
--
67306:156.50
A
Cal
ñ55
ñ18.7
19.9
132
--
67306:156.50
A1
Qtz
ñ63
ñ24.3
22.7
128
-- Aq(l)+Aq(v)+Cal solid phase
67306:156.50
A1
Qtz
ñ62
ñ23.6
22.2
134
67306:156.50
A1
Qtz
ñ63
ñ23.6
22.2
133
67306:156.50
A1
Qtz
ñ65
ñ24.5
22.7
130
67306:156.50
A
Act
ñ35
ñ11.3
15.7
123
--
67306:156.50
A
Act
ñ35
ñ13.1
16.8
121
--
67306:156.50
A
Act
ñ35
ñ13.8
17.2
129
--
67306:156.50
A
Ap
ñ55
ñ14.2
17.4
370
--
67306:156.50
A
Ap
ñ50
ñ11.1
15.5
67306:156.50
A
Ap
ñ52
ñ12.5
16.4
375
--
67306:156.50
A
Ap
ñ54
ñ13.8
17.2
373
--
67306:156.50
A
Qtz
ñ62
ñ23.4
22.1
152
--
67306:156.50
A
Qtz
ñ62
ñ23.3
22.1
150
--
67306:156.50
A
Qtz
ñ63
ñ24.1
22.4
153
--
67306:156.50
A
Qtz
ñ61
ñ23.6
22.2
155
--
67306:156.50
A
Qtz
ñ62
ñ23.5
22.2
154
--
67306:156.50
A
Qtz
ñ63
ñ23.4
22.1
152
67306:62.50
A1
Qtz
ñ65 to ñ70
--
37.0
127
282 Salinity calculated from Tm(halite)
67306:62.50
A1
Qtz
ñ65 to ñ70
--
34.0
115
16
--
--
Table 3 cont.
67306:62.50
A1
Qtz
ñ65 to ñ70
--
37.0
123
67306:62.50
A1
Qtz
ñ65 to ñ70
--
33.0
128
67306:62.50
A1
Qtz
ñ65 to ñ70
--
32.0
135
67306:62.50
A1
Qtz
ñ65 to ñ70
--
31.0
132
67306:62.50
A1
Qtz
ñ65 to ñ70
--
32.0
125
67306:62.50
A1
Qtz
ñ65 to ñ70
--
33.0
120
67306:62.50
A1
Qtz
ñ65 to ñ70
--
34.0
130
75311:283.30
A
Cal
ñ65 to ñ70 ñ26.3
23.5
172
-- Random-occurring
75311:283.30
A
Cal
ñ65 to ñ70 ñ26.8
23.7
167
-- Random-occurring
75311:283.30
A
Cal
ñ65 to ñ70 ñ27.1
23.8
176
-- Random-occurring
75311:283.30
A
Cal
ñ65 to ñ70 ñ23.3
22.2
187
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70
--
--
178
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70
--
--
183
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70 ñ25.3
23.0
191
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70
--
179
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70 ñ38.5
27.5
156
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70 ñ36.5
26.9
183
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70 ñ36.5
26.9
185
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70 ñ27.8
24.0
187
-- Random-occurring
Tjårrojåkka-Cu
--
75311:262.02
A
Qtz
ñ65 to ñ70
--
185
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70 ñ37.0
--
27.1
187
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70 ñ26.0
23.3
173
-- Random-occurring
75311:262.02
A
Qtz
ñ65 to ñ70 ñ23.7
22.3
175
-- Random-occurring
75311:205.15
A
Qtz
ñ65 to ñ70 ñ36.3
26.9
136
-- Close to healed microfracture
75311:205.15
A
Qtz
ñ65 to ñ70 ñ36.7
27.0
162
75311:205.15
A
Qtz
ñ65 to ñ70 ñ36.0
26.8
119
75311:205.15
A
Qtz
ñ65 to ñ70 ñ30.0
24.8
--
75311:205.15
A
Qtz
ñ65 to ñ70 ñ30.8
25.1
111
75311:205.15
A
Qtz
ñ50
ñ3.7
7.1
145
-- In healed microfracture
75311:205.15
A
Qtz
ñ50
ñ9.2
14.4
143
75311:205.15
A
Qtz
ñ50
ñ2.3
5.0
--
75311:205.15
A
Qtz
ñ50
ñ2.8
5.7
--
71305:149.01
A1
Cal
ñ76
ñ37.8
--
208
-- Salinity calculated from Tm(halite)
71305:149.01
A1
Cal
--
--
33.3
155
71305:149.01
A1
Cal
--
ñ32.0
36.7
209
71305:149.01
A1
Cal
ñ75
--
--
--
71305:149.01
A1
Cal
--
ñ29.1
36.6
176
71305:149.01
A1
Qtz
--
ñ36.4
--
--
71305:149.01
A1
Qtz
ñ75
ñ35.5
31.7
181
71305:149.01
A1
Qtz
ñ72
--
--
--
71305:149.01
A1
Qtz
-70
-35.3
--
169
71305:149.01
A
Qtz
ñ73
ñ31.4
25.4
155
--
71305:149.01
A
Qtz
--
ñ32.4
25.7
150
--
71305:149.01
A
Qtz
ñ62
ñ36.0
26.8
150
--
71305:149.01
A
Qtz
--
ñ37.6
27.2
149
--
71305:149.01
A
Qtz
ñ69
ñ37.8
27.3
--
--
Drill hole number and depth. For sample descriptions see Table 1.
Mineral abbreviations: Act = actinolite, Am = amfibole, Ap = apatite, Cal = Calcite, Kfs = K-feldspar, Mag = magnetite,
Hbl = hornblende, Qtz = quartz.
1
17
ñ65º to ñ73ºC and suggests melting of an aqueous solution containing
dissolved salts of mainly CaCl2 and NaCl (Table 3). Final melting of ice,
Tm(ice), for inclusions with a random appearance was observed between
ñ25º and ñ38ºC, which gives a salinity in the range 23 to 27 eq. wt. %
CaCl2+NaCl. The inclusions in the healed microfractures have much
lower melting temperatures with Tfm about ñ50ºC and Tm(ice) between
ñ2º and ñ9ºC. The melting temperatures suggest a CaCl2-rich solution
with a salinity of about 5 to 14 eq. wt. % CaCl2+NaCl. The
homogenization temperatures (to liquid) of the two groups were
measured in the range 111º to 191ºC.
Stable isotope geochemistry
Stable isotope data (oxygen, hydrogen, and sulfur) of different
alteration and ore minerals from the Tjårrojåkka apatite-iron and copper
(-gold) deposits were used to determine the type and source of the ore
forming fluids, as well as constrain temperatures of deposition. Sixtyseven samples of quartz, K-feldspar, apatite, amphibole, magnetite,
chalcopyrite, bornite, and pyrite were used in the study. The samples are
described in Table 1 and all data are listed in Tables 4 and 5.
Oxygen isotopes
The G18O values of amphibole, apatite, K-feldspar, magnetite, and
quartz range from ñ0.5 to 18.7 per mil (Table 4 and Fig. 6A). The
oxygen isotope fractionations between magnetite-quartz (Matthews et
al., 1983), magnetite-apatite (Valley, 2003), and magnetite-hornblende
(Bottinga and Javoy, 1975) were used to determine formation
temperatures of the magnetite-apatite and copper mineralization stages.
The calculated temperatures indicate that the magnetite ore stage (I)
took place between 410° and 660°C whereas the single determination
for the copper ore stage (II) indicated a temperature close to 470°C.
Using the calculated temperatures of the magnetite ore stage or an
estimated temperature of 550°C (based on the calculated temperatures
from oxygen isotope data) in the case where a calculated temperature
was not available, the G18OH2O values of the fluids for stage I show a
narrow range between 3.5 and 8.8 per mil (Table 4; Fig. 6A). Fluid
G18OH2O values for the copper ore stage (II) fall between 4.4 and 9.7 per
mil using the calculated temperature of the magnetite-hornblende pair
(469°C) for sample 72303:180.00 and an assumed temperature of 400°C,
for the other samples. The fluid G18OH2O values of the post-ore stage (III)
and the low-temperature quartz veins (stage IV) fall between 0.9 and 9.7
18
FIG. 6. Isotope signatures of minerals and fluids associated with ore and alteration
stages. A. Range of G18O values for amphibole, apatite, K-feldspar, magnetite, quartz
and calculated fluid compositions. Fluid compositions calculated using fractionation
factors of Zheng (1993b) for Am-H2O, Cole et al. (2004) for Mag-H2O, and Zheng
(1993a) for Qtz-H2O and K-feldspar-H2O. Arrow showing evolution of fluid composition. Data for temperatures in Table 2. B. Plot of calculated GDH2O vs. G18OH2O values for ore forming fluids. Fluid compositions calculated using fractionation factors of
Zheng (1993b) for G18OH2O and Graham et al. (1984) for GDH2O. Fields of different
waters and meteoric water line taken from Sheppard (1986). Grey symbols represent
samples from the Tjårrojåkka apatite-iron deposit and white symbols samples from the
copper (-gold) deposit. Mineral abbreviations: Ap = apatite, Am = amphibole, Kfs =
K-feldspar, Mag = magnetite, Qtz = quartz.
19
TABLE 4. Results of Oxygen and Hydrogen Isotope Analyses
GDmineral
G18Omineral(‰)
Sample1
Paragenesis
Tjårrojåkka-Fe
67306:122.95
I
Ammin
IMag-Ap
IIIAm-Qtz-Ccp-Carb
7.2Act
67306:284.00
I
5.7Hbl
67306:62.20
IMag-Ap
IIQtz-Carb
III
6.0Act
6.4Act
68313:199.70
IMag
IIIAm-Py-Zeol
I
68313:20.57
IV
6.5Act
20
68305:204.71
Kfs
Mag
Qtz
Am
0.3
67306:156.45
68305:202.65
Ap
(‰)
Am
Calc. G18OH2O(‰)
Am
Kfs
16.9
ñ73
409Ap-Mag/
250a
0.4
9.1
ñ57
564Qtz-Mag ñ33.9
3.5
5.7
1.0
ñ74
623Ap-Mag
ñ45
4.1
ñ38
7.5
ñ44.3
4.6
9.9
ñ44
8.3
ñ67
0.9
ñ66
8.4
550a/
150
489Ap-Mag
Qtz
7.9
8.7
7.9
7.8
6.7
6.3
7.9
250a
0.4
Mag
7.7
0.4
7.4
Ap
550a
8.4
8.6
6.3Tr
Calc. T
(°C)min pair
Calc.
GDH2O(‰)
2.8
250a
0.9
7.8
7.5
7.6
8.8
2.6
69304:214.00
I
0.1
8.0
606Qtz-Mag
7.1
5.9
69304:229.83
I
0.7
8.4
617Qtz-Mag
7.6
6.4
Tjårrojåkka-Cu
71305:149.01
IIIAp-Am
IVQtz-Carb
71305:168.50
I
71305:272.70
II
6.6Hbl
18.7
6.4
6.4Hbl
2.1
ñ66
250aAm/
150aQtz
ñ42.9
6.9
7.1
664Ap-Mag
400a
3.2
4.7
8.7
Table 4 cont.
71305:416.14
IV
72303:138.92
III
6.2Act
9.1
ñ71
250a
72303:145.75
III
6.3Act
8.8
ñ71
250a
ñ42
7.4
3.0
72303:180.00
II
6.4Hbl
9.5
ñ66
469Hbl-Mag
ñ42.9
4.4
8.1
73303:99.61
III
6.5Act
ñ60
250
ñ31
7.6
74319:301.77
I
10.7
6.6
1.7
150a
0.3
21
IV
II
75311:247.76
II
6.7Hbl
75311:283.30
IMag-Ap-Am
IVCarb
7.0Act
75316:328.50
I
150
1.3
9.3
6.7
0.2
6.5
ñ0.5
7.3
501Ap-Mag
11.4
74325:179.80
75311:220.65
a
ñ4.8
ñ42
3.3
6.7
9.7
8.1
a
ñ4.1
400a
9.6
ñ70
400a
ñ46.9
5.0
ñ70
489Ap-Mag
ñ41
5.4
466Ap-Mag
7.1
6.8
8.1
6.4
7.5
Mineral abbreviations: Act = actinolite, Am = amphibole, Ap = apatite, Kfs = K-feldspar, Mag = magnetite, Hbl = hornblende, Qtz = quartz, Tr =
tremolite. Temperatures for the mineral pair Ap-Mag was calculated using the fractionation factor of Valley (2003), for Qtz-Mag Matthews et al. (1983),
and for Hbl-Mag Bottinga and Javoy (1975). GDH2O(‰) calculated using fractionation equations of Graham et al. (1984). G18OH2O(‰) values computed using
fractionation equations of Zheng (1993b) for amphiboles, Zheng (1996) for apatite, Zheng (1993a) for K-feldspar and quartz, and Cole et al. (2004) for
magnetite.
a
For samples where a calculated temperature is not availabe, an estimated temperature for the assemblage was used.
1
per mil and ñ4.8 and 7.6 per mil G18O using an estimated temperature
of 250°C and 150°C (based on fluid inclusion data), respectively. The
trend of the G18OH2O values of the parent fluid for the different stages
shows a change towards lower values for the post-ore (stage III) and
low-temperature (stage IV) stages (Fig. 6A). However, the calculated G
18
OH2O values of the fluid have to be treated with caution. This is
demonstrated by the fact that minerals from the same sample and
paragenesis have different G18OH2O values. The observed variation could
be due to the fact that the minerals did not form exactly at the same
time, and that the minerals formed at slightly different temperatures and
from fluids of slightly different G18OH2O. According to Taylor (1968) long
cooling history promote retrograde oxygen isotope exchange; hence, the
higher temperatures are perhaps the most trustworthy.
Hydrogen isotopes
Hydrogen isotope analyses were performed on twelve amphiboles
(tremolite, hornblende, and actinolite) with GD values ranging from 57
to 74 per mil (Table 4). GDH2O values of the parent hydrothermal fluids,
calculated using the fractionation factors for tremolite-H2O, hornblendeH2O, and actinolite-H2O of Graham et al. (1984), lie between ñ31 and
ñ51.3 per mil. The temperatures used are based on calculated values
from oxygen isotope thermometers and fluid inclusions and are
stipulated in Table 4. The results plotted in Fig. 6B show that there is no
systematic difference in GDH2O and G18OH2O values of the fluids between
the apatite-iron and the copper (-gold) deposits, but they all overlap in a
relatively tight group in the primary magmatic and metamorphic water
fields.
Sulfur isotopes
Seventeen samples of chalcopyrite, pyrite, and bornite (seven from
the apatite-iron and ten from the copper (-gold) deposit) were analyzed for
their S isotopic compositions. The G34S values range from ñ4.9 to 0.1 per
mil (Table 5) showing a trend towards more positive values from stage I to
stage III (Fig. 7). A calculated temperature for a chalcopyrite-pyrite pair
from the copper ore stage (stage II) yields a temperature of 477°C using the
fractionation factor from Ohmoto and Rye (1979). This temperature is in
agreement with temperatures for stage II obtained from oxygen
fractionation between magnetite-hornblende (469°C).
22
TABLE 5. Results of Sulfur Isotope Analyses
Sample1
Paragenesis
G34SCcp(‰)
G34SPy(‰)
G34SBn(‰)
T (°C)
DPy-Ccp
Tjårrojåkka-Fe
67306:122.95
I
III
ñ4.0
67306:156.45
67306:284.00
I
ñ4.8
68305:202.65
68305:204.71
III
III
69304:214.00
I
ñ4.9
69304:229.83
I
ñ2.6
ñ2.2
71305:272.70
I
II
72303:180.00
II
ñ1.8
74320:134.37
75311:220.65
II
II
ñ0.1
75311:247.76
II
ñ0.6
75316:263.17
IV
ñ1.2
75316:268.91
II
ñ2.2
0.1
ñ0.3
ñ0.5
Tjårrojåkka-Cu
71305:168.50
ñ3.2
ñ4.2
ñ3.4
ñ1.4
477
Mineral abbreviations: Bn = bornite, Ccp = chalcopyrite, Py = pyrite. Temperatures for the mineral pair Py-Ccp was calculated using the fractionation factor
of Ohmoto and Rye (1979).
1
FIG. 7. Range of G34S values for chalcopyrite, pyrite, and bornite. Data for temperature in Table 2. Grey symbols represent samples from the Tjårrojåkka apatite-iron deposit and white symbols samples from the copper (-gold) deposit. Mineral abbreviations: Bn = bornite, Ccp = chalcopyrite, Py = pyrite.
23
Geochronology
The titanites used for geochronology represent different alteration
parageneses from the Tjårrojåkka apatite-iron and the Tjårrojåkka copper
(-gold) systems, respectively. In addition two titanite fractions from an
intrusive quartz-monzodiorite were analyzed. All the titanites from the
ore zones have the same appearance, being coarse-grained and are often
macroscopically recognizable. These titanites are typically dark brown,
show no obvious zonation, and are devoid of inclusions. The two
titanite fractions from the intrusive, occurring as anhedral grains in the
matrix, are brownish in color. Analytical data are nearly concordant and
display a significant range in ages (Table 6; Fig. 8A). Clearly, the U-Pb
data of the two titanite samples from the intrusive, although not giving
identical ages within error, are the oldest of the analyzed samples with
207
Pb/206Pb ages in the range of 1865-1846 Ma. Titanites from the
mineralized zones are considerably younger between 1773-1694 Ma.
Given that data are not fully concordant, it means that these ages are
minimum growth ages. Unpublished data from a Svecofennian
porphyritic rock of the Kiirunavaara Group, sampled close to the Kiruna
community and less than 30 km from the present border of the
Caledonian mountain range, includes a single grain with a relatively
precise age of ca. 400 Ma (personal communication, K. Billström). This
grain appeared to have grown during a metamorphic episode, and its age
is comparable with a Caledonian metamorphic event (e.g. Gee and Sturt,
1985 and references therein). This is suggesting that the bedrock at
Tjårrojåkka, situated even closer to the Caledonian front, has probably
suffered a similar Phanerozoic disturbance. Therefore, also a set of
207
Pb/206Pb titanite ages obtained from anchored regressions through
400±50 Ma are given in Table 6. The latter, being about 5-15 Ma older
than those directly defined from the analyzed Pb isotope compositions,
indicate three main stages of titanite growth; (1) a magmatic formation
at around 1.87-1.85 Ga, (2) an early hydrothermal episode at ca. 1.78
Ga, and (3) a subsequent stage between approximately 1.77 to 1.70 Ga.
Sm-Nd data are given in Table 7 and shown in Figure 8B. The
obtained spread in 147Sm/144Nd ratios is large, between ca 0.056 to 0.29,
which governs the construction of an isochron. However, the data
points of the six different specimens scatter considerably, and if the
magnetite from sample 68313:199.70 is excluded, this results in an
errorchron age of 1690±120 Ma (MSWD = 4.3). Initial H-Nd values
(calculated at 1800 Ma) range between –5.3 to –9.3, with the extreme
value of –12.3 for the magnetite from sample 68313:199.70.
24
TABLE 6. Conventional U–Pb Data from Titanite Occurring in Different Paragenetical Contexts at Tjårrojåkka (cf. Table 1)
207
U
Weight
Pb tot 206Pb/204Pb2 206Pb – 207Pb – 208Pb 206Pb/238U3 207Pb/235U3 207Pb/206Pb3
Pb/206Pb
3
(ppm) (ppm)
(mg)
meas.
age (Ma)4
radiog. Pb (at %)
Tjårrojåkka-Fe
69304:93.03
0.022
62.6
33.0
184
59.7 – 6.4 – 33.9
0.2978±12 4.408±20
0.1073
1755±4/1768
68313:20.57
0.175
75.1
31.0
621
64.2 – 6.7 – 29.1
0.2872±15 4.112±22
0.1039
1694±2/1707
Tjårrojåkka-Cu
74313:83.4
0.140
65.0
29.4
1016
61.9 – 6.7 – 31.4
0.3120±09 4.666±13
0.1084
1773±1/1777
75316:272.63
0.106
301
93.0
6075
84.4 – 9.2 – 6.4
0.3005±13 4.481±20
0.1082
1769±1/1782
72303:145.75
0.153
121
42.6
1546
75.4 – 8.1 – 16.5
0.2985±25 4.441±37
0.1079
1764±3/1778
72303:138.92
0.196
206
72.8
2555
73.7 – 8.0 – 18.3
0.2968±31 4.410±46
0.1078
1762±2/1778
75311:165.45
0.089
324
98.6
5911
87.5 – 9.4 – 3.1
0.3065±38 4.546±57
0.1076
1758±3/1765
73303:99.61
0.170
167
61.0
4427
71.5 – 7.6 – 20.9
0.3004±05 4.428±08
0.1069
1748±1/1758
Regional
TJ 013a
0.097
46.0
38.3
337
36.5 – 4.1 – 59.4
0.3274±17 5.094±31
0.1129
1846±5/1850
TJ 013b
0.171
81.4
65.3
383
37.7 – 4.3 – 58.0
0.3279±10 5.156±17
0.1140
1865±2/1871
Sample1
25
corrected for mass fractionation (0.10 % per a.m.u.)
1
2
corrected for mass fractionation, blank (10 pg Pb and 3 pg U), and common Pb (defined from the Stacey-Kramers model (1975) and individual, projected 207Pb/206Pb ages; see text)
4
the second, older age was calculated via an anchored regression through 400±50 Ma (see text)
Errors in the isotope ratios are given at the 95 % confidence level.
3
FIG. 8. Radiogenic isotope data for the Tjårrojåkka apatite-iron and copper (-gold)
deposits and a quartz-monzodioritic intrusion. A. 206Pb/238U vs. 207Pb/235U diagram for
titanites from alteration assemblages I-IV and a nearby intrusion. Samples 1 and 2 from
the apatite-iron deposit, 3 to 8 from the copper (-gold) deposit, and 9 and 10 from the
quartz-monzodiorite. Paragenetical order within parenthesis (I-IV). B. 143Nd/144Nd vs.
147
Sm/144Nd diagram for apatite-magnetite-amphibole assemblages for two samples
from the Tjårrojåkka apatite-iron ore.
26
TABLE 7. Sm-Nd Isotopic Compositions for Minerals Separated from Two Ore Samples Representing Paragenesis Stage I in the Apatite-Magnetite Ore at Tjårrojåkka
Sample1
Mineral
67306:62.20
67306:62.20
67306:62.20
68131:199.70
68131:199.70
68131:199.70
Ap (20)
Mag (21)
Act (22)
Ap (52)
Mag (53)
Tr (54)
Nd (ppm) Sm (ppm)
1111
55.3
1156
194
19.9
69.5
198
9.0
107
91.8
3.7
13.0
Sm/144Nd
147
Nd/144Nd
143
0.1078
0.0991
0.0560
0.2861
0.1136
0.1130
0.511216
0.511079
0.510700
0.513223
0.511027
0.511324
Errors2
ȯNd(t)
TDM3
7
6
9
8
11
13
7.3
7.9
5.3
9.3
12.3
6.3
2.65
2.63
2.27
0.34
3.11
2.62
errors are two sigma of the mean (given as the two last decimals)
3
Depleted mantle ages according to DePaolo (1981)
Mineral abbreviations: Act = actinolite, Ap = apatite, Mag = magnetite, Tr = tremolite.
1
2
Discussion
Comparison of data from the apatite-iron and copper (-gold) deposits
When comparing the data from the apatite-iron and copper (-gold)
deposits at Tjårrojåkka, it is evident that there are many similarities. The
fluid inclusion data indicate CaCl2-NaCl-dominated fluids and similar
temperatures for the different mineralization and alteration stages of the
two deposits (Fig. 5). The G18O, GD, and G34S values are within the same
range for the different stages of both deposits and the temperatures
obtained from oxygen data correlate well between the two deposits, as
well as with the temperatures obtained from fluid inclusion (Figs. 6 and
7). Also the calculated fluid compositions for stages I to III overlap (Fig.
6A). Unfortunately, no H isotope data from minerals in the late
paragenesis (stage IV) is available. Moreover, U-Pb titanite data indicate
similar ages for alteration processes related to both the apatite-iron and
copper (-gold) deposits, even though we were unable in this study to
determine the exact formation age of the massive magnetite ore due to
the lack of datable minerals.
Source and composition of ore fluids
The fluids involved in the deposition of the Tjårrojåkka apatiteiron and copper (-gold) deposits show comparable G18OH2O and GDH2O
values (Fig. 6). For stages I to III, theҏ G18OH2O values vary between 3.5
and 12.5 per mil, while stage IV shows a tendency towards lower values
most likely as a result of mixing with meteoric water. The GDH2O values
of the fluids from the two deposits overlap, implying the same origin for
the fluids involved in their formation. The G18OH2O and GDH2O data do
not exclusively determine the source of the fluids; however, they
indicate dominantly magmatic or metamorphic fluids without a
27
significant unexchanged meteoric water component for stages I to III.
Fluid inclusion data show that the ore forming fluids had moderate
to high salinities between 15 and 37 eq. wt. % CaCl2+NaCl. According
to Baker (1998) high salinity fluids can originate from magmas, through
retrograde metamorphism, or from dissolution of evaporites during
metamorphism. High-salinity (>60 wt. % salts), high-temperature (up to
800RC), “boiling” fluids of magmatic origin have been shown to be
associated with porphyry copper deposits (Roedder, 1984). Bennett and
Barker (1992) show that highly saline (up to 50 wt. %) fluid inclusions in
quartz are related to retrograde metamorphism in the Caledonian Thrust
Zones in Norway. However, the temperature of the infiltrating fluids
was determined to only 300-370RC, which is much lower than the initial
temperatures of the mineralizing fluids at Tjårrojåkka (up to 650RC for
stage I). Evaporites have been interpreted as the source for the highsalinity fluids associated with the Mary Kathleen zone in Australia
(Oliver, 1995) and for the majority of IOCG deposits in northern
Sweden (Frietsch et al., 1997). Also Barton and Johnson (1996)
considered evaporites to be an important factor for the formation of
many Fe-oxide-rich copper deposits. So far no evaporites have been
identified in Norrbotten, but intense albite-scapolite alteration and a
strong enrichment of Cl and Br in the Kiruna Greenstones have been
used as evidence for the occurrence of former evaporitic beds in the area
(Martinsson, 1997). The Ca in the fluid could have been derived from
such a sequence, through mixing with seawater derived brines, or if the
system was purely magmatic, from high temperature leaching of the wall
rock. The Ca-rich fluids responsible of mineralisation at the Aitik CuAu deposit were interpreted by Wanhainen et al. (2003) to be result of
interaction between a magmatic fluid and evaporites.
The slightly negative G34S values (ñ4.9 to 0.1 per mil) of sulfides at
Tjårrojåkka suggest that the sulfur was derived mainly from igneous
sources. These values fall within the same rage as for other deposits in
Norrbotten where the sulfur has been concluded to be of magmatic or
igneous origin (e.g. Gruvberget, Frietsch et al., 1995; Aitik, Wanhainen
and Martinsson, 2003). However, values as low as í5 for the magnetite
stage (stage I) indicate that the magma or its evolved fluid most likely
incorporated some sedimentary sulfides. There is no evidence of
sedimentary units in the Tjårrojåkka area that could have provided the
fluid with sulfides, but little is know about the deeper situated rock units.
It is unlikely that the sulfur was derived from evaporitic sources, as
suggested for other IOCG deposits (e.g. Barton and Johnson, 1996),
since the estimated isotopic composition of seawater sulfate in the
Paleoproterozoic range from +10 to +25 per mil (Strauss, 1993). At
28
temperatures >650RC, chalcopyrite and pyrite derived from fluids with a
Paleoproterozoic evaporitic signature would have positive G34S values
using the fractionation factor of Ohmoto and Rye (1979).
The trend of the G34S values becoming increasingly larger from stage I to
stage III of the paragenesis is highly significant and suggest that all of the
mineralization was related to a single evolving system. The cause of the
trend could be a result of loss of isotopically light sulfur either due to
degassing of H2S and/or precipitation of sulfides. Separation of H2S from
the fluid would leave the fluid enriched in 34S since H2S is depleted in
34
S relative to the bulk sulfur in the fluids (Ohmoto and Rye, 1979). The
presence of barite, hematite, and SO3 in scapolite at stage II and III
indicate that the conditions were becoming more oxidizing with time.
Consequently, the trend is not due to change in the oxidation state of
the fluids as a larger portion of SO4 in the system would have resulted in
the opposite trend for the sulfides, but is most likely due to some kind of
mixing or Raleigh effect on bulk sulfur in the magma.
When calculated for t=1.8 Ga, the resulting İ-Nd values vary between
–5.3 (amphibole from sample 67306:62.60) and –12.3 (magnetite from
sample 68313:199.7). This is a large range having the implication that the
hypothetical fluids involved in the formation of the studied minerals must
have İ-Nd values outside this range. In the Tjårrojåkka area, there are mainly
two groups of rocks, a suite of outcropping 1.88 Ga metavolcanic rocks and
most likely Archean rocks and/or rocks of the Kiruna Greenstone group in
the basement. On the average, Archean rocks at around 1.8 Ga would have
İ-Nd values around –12 to –13 (Mellqvist et al., 1999), whereas ca. 1.9 Ga
magmatic rocks (data mainly from granitoids believed to be co-magmatic
with rocks of the Porphyrite and of the Kiirunavaara Groups) typically have
İ-Nd values at crystallization covering a large range between –2 to –6
(Mellqvist et al., 1999), and with even more negative data, down to –8 in
the northern part of Norrbotten (Skiöld et al., 1988). 1.80 Ga granitoids
have H-Nd values between –3.1 and –5.8 Ga (n=6) listed in Öhlander et al.
(1999). These comparisons suggest that the Archean basement had a strong
impact on the isotopic composition of the apatite-iron system at Tjårrojåkka
and it is likely that the local 1.9 Ga rocks contributed to the Nd budget
during interaction between wall rocks and fluid(s) that penetrated the area.
Sample 68313:199.70 was collected from the centre of the massive
magnetite ore and would consequently have formed prior to sample
67306:62.60 that originates from the external part of the ore body. This
outer part of they system could have interacted with the surrounding rocks
and also inherited its İ-Nd values. Clearly, these values, which generally
become more negative by about one H-Nd unit if e.g. 1.7 Ga is used in the
calculations, argue that the analyzed mineral phases formed from fluids
29
dominated by Nd of Archean origin but evolved to less negative H-Nd
values by isotopic exchange with the wall rocks.
Evolution of ore forming fluids
The main magnetite ore-forming stage (stage I) formed at a
minimum temperature of 500-650oC. The earliest fluid inclusions occur
in apatite from the massive magnetite ore and were deposited from
moderately saline aqueous solutions with a salinity of 15-17 eq. wt. %
CaCl2+NaCl (Fig. 5), and represent a late stage of the apatite-magnetite
mineralization. This is the first time that this type of apatite-hosted fluid
inclusions, with high vapor-liquid homogenization temperature
(>370oC), have been observed in the Kiruna region. The calculated
temperature (409oC) from oxygen isotope data for the mineral pair
magnetite-apatite from the same sample confirms that the late stage of
magnetite-apatite mineralization occurred at around 400oC. The
presence of a parent hydrothermal aqueous fluid in the late magnetite
ore stage is significant in any discussion of whether the massive part of
the Tjårrojåkka ore crystallized directly from a magma or was formed by
hydrothermal processes.
Stage II followed shortly after or partly overlapped stage I, and
involved fluids with comparable G18OH2O and GDH2O values as stage I.
The main copper sulfide ore-forming stage is associated with highly
saline, carbonate-bearing fluids at temperatures >450oC, which is in
agreement with the temperature obtained from pyrite-chalcopyrite
thermometry (477oC). The reason for the increase in salinity between
stage I and II (Fig. 5) could be a result of mixing with a high salinity
fluid, boiling, or interaction with evaporitic beds in the bedrock. Mixing
would require a fluid with a higher salinity but the same G18OH2O and
GDH2O values (i.e. same origin) as the original fluid, since there is no
change in isotopic compositions between stages I and II. The second
alternative is boiling of the original moderately saline fluid to form a
fluid with higher salinity. The presence of relatively gas-rich and gaspoor inclusions in the stage I apatite could be an indication that the fluid
was boiling. However, too little fluid inclusion data is available from the
early stage of mineralization to prove that boiling really occurred. The
third option, that the fluid interacted with evaporites in the bedrock, is
somewhat speculative since no evaporites have been observed in the
area. On the other hand, the area is characterized by intense regional
scapolitization, which in other parts of Norrbotten has been used as an
evidence for the existence of former evaporitic beds (Martinsson, 1997).
Due to the occurrence of calcite in the fluid inclusions, it can also be
concluded that CO2 was present in the ore-forming fluids at stage II.
30
The main part of fluid inclusions in quartz reflects the fluid composition
at the end of the copper stage (stage II) or the post-ore stage (stage III)
that formed at temperatures between 150 and 200oC. The two-phase
inclusions are the most common type of inclusion in quartz and calcite
and reveal a trend with decreasing salinities from stage II to III probably
representing the final stage of copper mineralization of which bornite is
the dominating ore mineral.
From stage III to IV the G18OH2O of the fluid changed towards
lower values due to input of meteoric water (Fig. 6). The lack of
systematic change in the GDH2O towards values more similar to those of
meteoric water most likely reflects the similar įD of ambient meteoric
water with magmatic water. The inclusions that were trapped at this
stage also have a lower salinity and reduced iron content, with no
hematite present.
Age constraints for the different mineralizing stages
Overall, the available U-Pb data from the Tjårrojåkka area and adjacent
regions indicate an extended period of Early Proterozoic magmatic,
metamorphic, and hydrothermal activity between ca 1.9-1.7 Ga (Fig. 9).
This means that isotope systematics may have been disturbed to various
degrees and isotope data must be interpreted with caution. Previous UPb data for the andesitic host rock, and indirectly for the assumed basaltic
feeder dykes, indicated a minimum age of 1878±7 Ma (Edfelt et al.,
2006). The intruding quartz-monzodiorite is not likely to be much
younger if age correlations are made with other rocks occurring in
similar settings and with a similar chemistry (cf. Fig. 9 and references
therein). The titanite data presented here for the latter rock cannot be
used to derive a precise crystallization age since the indicated 207Pb/206Pb
ages scatter beyond analytical uncertainty. However, e.g. 206Pb/204Pb and
208
Pb/206Pb ratios are similar for the two fractions suggesting that these
share a similar origin, in consistency with the fact that they are optically
undistinguishable. We conclude that the indicated 1.87-1.85 Ga titanite
ages support that the quartz-monzodiorite did crystallize within a
relatively short time span after the emplacement of the extrusive rocks.
Furthermore, these titanite ages and the lack of any over-printing
hydrothermal mineral parageneses in the rock support a magmatic origin
for the matrix-related titanites and argue that no severe postcrystallization event has changed their ages. This is important since it
implies that neither the ages of the titanites, occurring in the ore zones,
have been resetted by e.g. a major metamorphic event. As a
consequence, the much younger U-Pb ages of ore-associated titanites
occurring in hydrothermal alteration parageneses must be considered as
real hydrothermal ages. Also, their much higher relative proportion of
31
32
FIG. 9. Relative age relationships of
regional tectonism, magmatism, metamorphism, and mineralizing events in
Norrbotten, and simplified paragenetic
sequence of the alteration and mineralization at Tjårrojåkka (modified after
Wanhainen, 2005 and Edfelt et al.,
2005). Shaded areas represent metamorphic events (data from Bergman et al.,
2001 and Martinsson, 2004). Solid lines
represent principal and dashed lines subsidiary events. Stars indicate regional age
determinations. Circles (TjårrojåkkaCu) and triangles (Tjårrojåkka-Fe) symbolize age determinations obtained in
this study. References for age determinations: 1Bergman et al. (2006), 2Weihed et al. (2005), 3Bergman et al.
(2001), 4Romer et al. (1992), 5Skiöld
(1988), 6Skiöld (1981a), 7Skiöld (1981b),
8
Martinsson et al. (1999), 9Lindroos and
Henkel (1978), 10Edfelt et al. (2006),
11
Wanhainen et al. (2006), 12Welin
(1987), 13 Skiöld and Cliff (1984),
14
Skiöld and Öhlander (1989), 15Wanhainen et al. (2005), 16Romer et al.
(1994), 17Lundmark et al. (2005), 18Cliff
et al. (1990), 19K. Billström (pers. commun., 2006), 20Billström and Martinsson
(2000), 21Martinsson and Virkkunen
(2004).
Pb clearly suggests that these are not magmatic crystals which became
partially reset at some later stage. The ore-associated titanites were taken
from four different assemblages, I to IV, which is likely to represent
successively younger parageneses based on textural evidence. Several
features, such as the fact that data are slightly discordant, that only one
data point represent paragenesis I and II, respectively, and that various
assemblages may grade into each other make it somewhat ambiguous to
conclusively assign specific ages for each paragenesis. Despite these
limitations, the indicated relative timing between different parageneses is
consistent with U-Pb titanite data. However, it appears that only short
time gaps, if any (ages are basically the same within error of each other),
exist between the first three parageneses (stages I to III) and these are
defining a short-lived event which took place close to 1780 Ma or
slightly later (Fig. 9). The fourth paragenesis (stage IV) did, apparently
form later and probably during several discrete stages. The youngest
indicated stage at ca 1.70 Ga compares well with ages obtained from
post-metamorphic, low temperature settings at Malmberget (Romer,
1996) and with data from TIB 2 granitoids (Romer et al., 1992).
Although the radiogenic isotope data are too sparse to really allow
a discussion about the possible presence of any systematic age differences
between the apatite-iron and the copper (-gold) systems, there is no
evidence to actually support such a possible difference. In other words,
the alteration assemblages may well have formed synchronously in the
two systems. There are no titanite data that can directly be used to date
the massive apatite-iron ore formation. However, it must be recalled that
certain of the alteration assemblages are likely to be synchronous with
late ore systems, such as apatite-magnetite veins and copper
disseminations. Titanites which represent these settings obviously formed
at around 1.78 Ga; therefore, there is radiometric evidence to argue that
ore-forming processes leading to the Tjårrojåkka copper (-gold) deposit
took place at about 100 Ma later than the original emplacement of the
magmatic host rocks.
The Sm-Nd errorchron shown in Fig. 8B does confirm an Early
Proterozoic age and the age is within error the same as the 1.78 Ga event
thought to be responsible for the formation of the Tjårrojåkka copper
system. This errorchron age is defined by phases that represent the
massive apatite-iron ore system, and although being imprecise it favours
a 1.78 Ga origin of the apatite-iron ore, rather than suggesting a genetic
model, which links magnetite ore formation with the 1.9 Ga magmatism
(cf. Fig.9 and references therein).
A poor fit to a line in an isochron diagram may be due to several
causes; either the system did not stay closed after crystallization, or the
samples are not coeval, or the samples crystallized with different initial
208
33
isotope ratios. Textural observations suggest that the three mineral phases
used for the purpose of constructing a Sm-Nd isochron formed within a
short time range considering that they are intergrown with each other,
and a difference in age is thus not likely to have caused the scatter in Fig.
8B. Judging from U-Pb data, ore formation took place at a stage postdating 1.80 Ga, when the main deformation and metamorphism had
declined and no later event capable of opening up the Sm-Nd system is
known. The remaining option to explore is that of a mineralizing system
characterized by a mix of fluids having different origins. If such fluids are
representing isotopically different end-members, this could be a
reasonable explanation to the scatter.
Ore genetic model for the Tjårrojåkka IOCG system
The genesis of Kiruna type apatite-iron ores have been subject of
discussion for more than 100 years, with the main focus on magmatic or
hydrothermal origins. The magmatic model explains the formation of
these types of deposits from high temperature, volatile-rich iron oxide
melts, mainly based on textural magmatic features like columnar and
dendritic magnetite, igneous structures, and the relation between the ores
and their host rocks (Henríquez et al., 2003; Henríquez and Nyström,
1998; Naslund et al., 2002; Nyström and Henríquez, 1994; Park, 1961).
Chemical data from magnetite and apatite is also used to support the
model (Frietsch and Perdahl, 1995; Naslund et al., 2002; Nyström and
Henríquez, 1994) and Broman et al. (1999) interpreted fluid inclusion
data from pyroxene and apatite at the Kiruna type apatite-iron ores at El
Laco, Chile, to have formed from late-magmatic remnant fluids gradually
becoming lower in temperature and salinity. The hydrothermal model,
on the other hand, favours metasomatic replacement from Fe-rich
hydrothermal hypersaline fluids for the formation of these types of
deposits (Hildebrand, 1986; Hitzman et al., 1992; Rhodes et al., 1999;
Sillitoe and Burrows, 2002). Based on theoretical grounds the existence
of iron oxide magmas was questioned by Hildebrand (1986), whereas
Rhodes and Oreskes (1999) used oxygen isotopes as an evidence to
support the replacement theory. Barton & Johnson (1996) proposed a
model for the formation of Fe-oxide-rich deposits by hydrothermal
processes involving evaporitic ligand sources. Although apatite-iron ores
have common characteristics there is a large variation in alteration and
mineralization style between deposits, which have led several authors to
the conclusion that all deposits of this type did not form by one and the
same process, but probably both magmatic and/or hydrothermal
mechanisms may be involved in the formation of them and the particular
mechanism probably varies from deposit to deposit (Barton and Johnson,
1996; Martinsson, 2004; Naslund et al., 2002).
34
As for the massive magnetite-apatite ore at Tjårrojåkka it is not
evident from the existing data whether it is of magmatic (melt) or
hydrothermal (replacement) origin. The formation from an iron-rich
melt would require either separation from a silica-rich melt or melting of
iron-rich crustal rocks. No clear textural evidence, that support a
magmatic model, has been observed. Yet, it should be noted that the ore
itself can only be studied in drill cores where such structures and textures
are not easily distinguishable. Due to the high temperatures of stage I
(>650oC), a hydrothermal model would require a fluid source relatively
close to the deposit itself (like in porphyry copper systems) or a major
fluid pathway capable of transporting the amount of fluids required
without lowering the temperature significantly. These fluids would
either have transported metals (iron and copper) from its source or
leached them from the surrounding rock. What can be concluded is that
the core of the massive magnetite ore originated from a source with a
dominant Archean H-Nd isotopic composition, and that a hydrothermal
system was active at least at a late stage during ore formation, creating
the apatite-magnetite-actinolite breccia, copper mineralization, as well as
the extensive Na and K alterations surrounding the massive ore body.
The main part of the copper (-gold) mineralization precipitated
between 150 and 480oC from highly to moderately saline CaCl2-NaClrich fluids, suggesting that copper and gold as well as iron were
transported as metal-chloride complexes. Highly saline fluids with
temperatures up to 400-500°C have also been noted in several other
IOCG systems in for example the 1.8 Ga IOCG stage at Aitik, Sweden
(Wanhainen, 2005; Wanhainen et al., 2003), Australia (Baker et al.,
2001; Skirrow et al., 2002), and Chile (Marschik and Fontboté, 2001).
The NE trending shear zone probably acted as a major fluid channel and
a structurally favorable location for the deposition of the copper (-gold)
mineralization. Fluid inclusion data indicate that a drop in temperature
most likely was an important factor for ore deposition together with
decreasing salinities from stage II to III.
The dominant magnetite association at Tjårrojåkka indicate a
higher temperature and a lower oxidation state than for example at the
Olympic Dam deposit where hematite is the dominant Fe-oxide
(Oreskes and Einaudi, 1990, 1992). However, according to Edfelt et al.
(2005) the presence of some hematite, barite, and SO4 in scapolite in the
copper (-gold) deposit implies that the conditions were more oxidising at
the deposition of stages II and III than at the formation of the massive
apatite-iron ore (stage I). Mark et al. (2000) suggested that there is a
spectrum of deposit within the Fe-oxide-Cu-Au group ranging from
relatively lower gO2, hotter and deeper deposits (e.g. Ernest Henry) to
those forming at a higher levels from more oxidized lower temperature
35
fluids (e.g. Olympic Dam) and that fluid mixing could be the cause of
the diversity. The continuum is also seen in the copper sulfide
association with chalcopyrite being the most dominant copper sulfide in
the first mentioned and chalcocite-bornite-chalcopyrite in the other.
The Tjårrojåkka deposits share many characteristics with the Ernest
Henry deposit and would in the suggested model represent a deeper
formed deposit.
The heat engine driving the hydrothermal system could have been
generated either through metamorphism or more likely by a nearby
intrusion. Regionally, there are Lina granite intrusions of the same age as
the Tjårrojåkka deposits (Fig.9) as well as diabases and basic sills (of
unknown age) ca. 10 km to the east of the area, that could have
generated the heat. The most likely option is, however, a magma at
depth, which have not been documented at surface. The metamorphic
grade of the Tjårrojåkka area has been determined to epidoteamphibolite facies (Edfelt et al., 2006; Ros, 1979), which according to
Apted and Liou (1983) takes place between 575 and 675oC (at 7 kb) and
could consequently have produced fluids hot enough for forming the
stage I mineralization. U-Pb dating of stage I shows that the late phase of
the magnetite-apatite mineralization took place at around 1770 Ma,
which is within the range of the regional metamorphism. However, a
metamorphic source of the fluids would require influence of evaporites
to produce the high-salinities observed at Tjårrojåkka.
Even if the results from this study cannot exclusively determine the
origin of the massive part of the apatite-iron ore, they indicate a
common origin for the apatite-iron and copper (-gold) deposits at
Tjårrojåkka and thus an age of the mineralization of about 1.78 Ga. The
apatite-iron ores in Norrbotten have previously been believed to have
formed at around 1.9 (cf. Fig. 9 and references therein) but the present
results indicate that apatite-iron ores also formed during another 100 Ma
younger ore forming event. Furthermore, dating of the Saivo deposit
also indicates the occurrence of a younger generation of apatite-iron
deposits in Norrbotten (Fig. 9; personal communication, K. Billström).
Conclusions
The Tjårrojåkka apatite-iron and a copper (-gold) deposits are the
best-known example in Sweden of spatially and genetically related
deposits of this type. From the available data, it is not obvious whether
the massive part of the apatite-iron ore formed from an iron rich melt or
through hydrothermal replacement. Sm-Nd data from the apatite-iron
ore show that, whether of magmatic melt or hydrothermal origin, it has
36
its origin in a source with an Archean H-Nd isotopic composition.
Moreover, the results show that a hydrothermal system was active at least at
a late stage during the deposition of the iron ore, producing the apatitemagnetite-actinolite breccia, copper mineralization, as well as extensive
hydrothermal alterations.
The ore-forming fluids were CO2-bearing, moderately to highly
saline CaCl2-NaCl-rich fluids, with the dominant magnetite and
chalcopyrite association indicating a relatively high oxidation state. The
source of the fluids and salts (magmatic or metamorphic) could not be
unequivocally determined from the available data; nevertheless, the G18O
and GD values together with sulfur isotope data imply that magmatic fluids,
or fluids that equilibrated with wall rocks, played an important role in the
formation of the Tjårrojåkka deposits and that all stages were part of a
single evolving system. Such fluids could have provided the system with
both ligands and metals needed for the mineralization, but the possibility of
incorporation of a formation water brine whose sulfate was removed by
prior reaction with wall rocks can not be ruled out. The low-temperature
assemblage (stage IV) shows a trend towards lower G18OH2O values due to
mixing with meteoric water.
Stable isotope and fluid inclusion data indicate that the magnetite
ore-forming stage (stage I) deposited at a minimum temperature of 500 to
650°C followed by the main copper mineralization (stage II) at around
400-450°C. The last stage of copper mineralization associated with quartz
veining (stage III) occurred at around 150-200°C. The heat required for
the hydrothermal system most likely was provided by an intrusion at depth.
Fluid inclusion data indicate that cooling, along with decrease in
salinity (from stage II to III), were important factors for iron and copper
precipitation at Tjårrojåkka. A NE trending shear zone in the area may
have acted as a major fluid channel and a structurally favorable location for
the deposition of the copper (-gold) mineralization. U-Pb ages of titanites
and indications from Sm-Nd analyses of magnetite, apatite, and amphibole,
point to an age of the mineralization close to 1780 Ma. The ore deposition
was a relatively short-lived event, while the low-temperature assemblages
(stage IV) most likely formed during several phases for a long period with
the youngest indicated age of about 1700 Ma.
Similarities in stable isotope and fluid composition, temperature of
ore deposition, and age of alterations and mineralization imply that the
Tjårrojåkka apatite-iron and copper (-gold) deposits formed during the
same ore-forming event around 1780 Ma, demonstrating a genetic link
between at least some apatite-iron and copper-gold deposits. This study
also shows the presence of a, previously unknown, 1780 Ma generation of
apatite-iron ores in Northern Sweden.
37
Acknowledgements
This paper is part of a doctoral study funded by GEORANGE. The
stable isotope work was financed by Stiftelsen Längmanska
Kulturfonden, Stockholm. All the involved staff at the isotope laboratory
at the U.S. Geological Survey in Denver is thanked for their assistance
with the laboratory work.
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45
Paper IV
Apatite chemistry – applications for characterising
apatite-iron and IOCG deposits
Å. Edfelt1,*, M. P. Smith2, R. N. Armstrong3, O. Martinsson1
Division of Ore Geology and Applied Geophysics, Luleå University of
Technology, SE-971 87 Luleå, Sweden
2
School of the Environment, University of Brighton, Cockcroft Building,
Lewes Road, Brighton BN2 4GJ, U.K.
3
The Natural History Museum, Cromwell Road, London SW3 5BD, U.K.
1
Corresponding author: [email protected]
__________________________________________________________
*
Abstract
Apatite-iron ores of Kiruna type and Fe-oxide Cu-Au (IOCG) deposits have
attracted a lot of interest the last decade, but several fundamental questions, regarding
their genesis and a possible genetic link between them, remain unanswered.
This study presents a preliminary study of the chemistry of apatite from Kiruna
type iron ores and IOCG deposits from northern Sweden, using transmitted light,
microprobe analysis (EMPA), and laser ablation inductively coupled plasma mass
spectrometry (LA-ICPMS). The content and distribution of halogens and REE in the
apatites were studied in an attempt to distinguish apatite-iron ores of Kiruna type from
IOCG deposits, and possibly make a distinction between copper bearing and barren
iron systems.
The results of this study suggest that there is a fundamental difference in the
apatite chemistry between Kiruna type apatite-iron ores and IOCG deposits. Apatites
from Kiruna type apatite-iron ores are F-dominated, enriched in LREEs and to some
extent S. Apatites from IOCG deposits show enrichment in Cl and depletion of LREE.
The variation in apatite chemistry might be the result of IOCG deposits forming from
fluids with a lower pH that enhance incorporation of Cl into apatite and LREE
complexion with Cl causing the depleted LREE pattern. Within the IOCG group of
deposits including the Tjårrojåkka apatite-iron ore, the trend of decreased Cl is
probably due to a decrease in temperature.
The available data indicate that some apatite-rich iron ores form associated with
fluids similar to those creating copper-rich IOCG deposits and that apatite chemistry
could be a potential tool for distinguishing copper mineralising apatite-iron systems
from barren.
Keywords Apatite-iron ore, Kiruna type, IOCG deposit, Sweden, apatite chemistry, microprobe,
LA-ICPMS.
_____________________________________________________________________
1
Introduction
There has been a growing exploration and research interest for Feoxide-Cu-Au (IOCG) deposits since Hitzman et al. (1992) characterized
the Olympic Dam and several other iron-oxide rich copper deposits as a
separate group of ore deposits. Despite a significant amount of research
on IOCG deposits during the last decade, several fundamental questions
remain unanswered. For example, it is still questioned whether apatiteiron ores (AIO) of Kiruna type should be incorporated in this group of
deposits (Hitzman 2000), if there is a genetic link between them and
copper dominated IOCG-systems (e.g. Marschik and Fontboté 2001;
Edfelt et al. 2005), and whether IOCG deposits are formed purely from
magmatic fluids or if evaporates play an important role in providing
ligands for the high salinity fluids (Pollard 2000; Barton and Johnson
1996; Barton and Johnson 2000).
Apatite chemistry, with the main focus on REEs, has been used in
numerous previous studies to investigate the source of the mineralising
fluids and the origin of deposits, as well as the use of apatite as an
indicator mineral for exploration. Several apatite-iron ores have been
studied with regard to their apatite chemistry. Parák (1973; 1985) and
Frietsch and Perdahl (1995) used apatite chemistry in their discussions on
the origin of the Kiruna deposits while Rhodes et al. (1999) studied the
REE geochemistry at El Laco to support a hydrothermal replacement
model for the deposit. Harlov et al. (2002) carried out detailed work on
the apatite-monazite relations in the Kiirunavaara ore and their
implications for post-emplacement fluid-rock interaction. Treloar and
Colley (1996) used the halogen contents in apatite in their ore-genetic
discussions of the Fresia and Carmen iron deposits in Chile and to
distinguish magmatic AIO from hydrothermal ones on grounds of
mineral chemistry.
A detailed review of REE behaviour during hydrothermal ore
formation was presented by Lottermoser (1992) focusing on intrusive
related hydrothermal deposits and VMS deposits. At the Bayan Obo FeREE-Nb deposit, apatite chemistry has been used in several studies to
investigate the different episodes of REE mineralisation as well as REE
fractionation during hydrothermal processes (Campbell and Henderson
1997; Smith et al. 2000). Layered igneous complexes have also been
studied for their apatite chemistry, with the focus on Cl and F contents,
to differentiate PGE bearing intrusions from barren (Boudreau 1993;
Boudreau et al. 1993). Belousova et. al. (2002) used multivariate
statistical analysis to distinguish apatite from different rock suits and to
recognise apatites from specific rock types or styles of mineralization.
The present paper presents a preliminary study of the chemistry of
2
Fig. 1. Geological map of northern Norrbotten (modified after Bergman et al. 2001)
with locations of the Kiirunavaara, Rektorn, Nukutus, Ekströmsberg, Tjårrojåkka, and
Nautanen deposits.
apatite from Kiruna type iron ores and IOCG deposits from northern
Sweden, using transmitted light, microprobe analysis (EMPA), and laser
ablation inductively coupled plasma mass spectrometry (LA-ICPMS).
The content and distribution of halogens and REE in the apatites were
studied in an attempt to distinguish apatite-iron ores of Kiruna type from
IOCG deposits, and possibly make a distinction between copper bearing
and barren iron systems.
3
Geological setting and metallogeny
The Norrbotten County is located in the northernmost part of
Sweden and is an important iron and copper producing region of
Europe. Palaeoproterozoic metavolcanic, metasedimentary, and intrusive
rocks dominate the geology in the area (Fig. 1). Metavolcanic rocks of
the 1.89-1.88 Ga Porphyrite and Kiirunavaara Groups, intruded by ca.
1.89-1.86 Ga intrusive rocks of the Haparanda and Perthite-monzonite
suites, overlie the Archaean basement and rift-related Karelian units. The
10 km thick pile of volcanic and sedimentary rocks were metamorphosed at
around 1.88 Ga and 1.81-1.78 Ga (Bergman et al. 2001; Martinsson
2004)
Northern Norrbotten hosts several IOCG and apatite-iron
deposits, including Kiirunavaara which is the type locality for the Kiruna
type iron ores (Fig. 1).The apatite-iron ores in the area are hosted in the
Porphyrite or Kiirunavaara metavolcanic sequences and have an average
content of Fe and P between 30-65% and 0.05-5%, respectively
(Martinsson 2003). The majority of apatite-iron ores in the area are
believed to have formed around 1.88 Ga (Cliff et al. 1990; Romer et al.
1994), but more recent studies show that they also occur as a younger
generation formed at around 1.78 Ga (Edfelt et al., 2007). The IOCG
deposits are generally hosted in the Svecofennian porphyries with some
of them showing a close genetic and/or spatial relation to intrusive
rocks. The epigenetic copper deposits in Norrbotten are believed to
have formed during two major mineralising events at ca. 1.87 and 1.77
Ga (Billström and Martinsson 2000). Magnetite is a common constituent
and in two cases, Gruvberget and Tjårrojåkka, a close spatial relation to
apatite-iron ores have been observed in the deposits (Lindskog 2001;
Edfelt et al. 2005). The host rock to the IOCG deposits is generally
intensively altered with albite, scapolite, K-feldspar, and amphibole as
the major alteration minerals (e.g. Edfelt et al. 2005; Martinsson and
Wanhainen 2004).
Sampling and analytical techniques
Apatite samples from five apatite-iron ores and two IOCG deposits
in northern Norrbotten were selected for the study (Table 1). Major
element data for samples 68313:120.20, 67306:250.61b, 75311:255.96,
and 75316:328.50 are from Edfelt et al (2005). The samples were initially
examined in transmitted light at the Luleå University of Technology to
identify textures and zoning as well as to locate areas suitable for mineral
4
Table 1. Descriptions of samples from apatite-iron and IOCG deposits in Norrbotten
used in the study.
Sample
number
66814 EKSTR
Ekströmsberg 2
Type
of deposit
Apatiteiron
Deposit,
Stratigraphic position
Ekströmsberg, Kiirunavaara group
Apatiteiron
Apatiteiron
Ekströmsberg, Kiirunavaara group
Rektorn, Kiirunavaara
group (above the
Kiirunavaara ore)
29JREK14
Apatiteiron
29JREK20
Apatiteiron
29JNuk1
Apatiteiron
KUJ5044 80.10m
Apatiteiron
Apatiteiron
Apatiteiron
Apatiteiron
group (above the
Kiirunavaara ore)
group (above the
Kiirunavaara ore)
Nukutus, Kiirunavaara
group (above the
Kiirunavaara ore)
Kiirunavaara, Kiirunavaara group
Tjårrojåkka-Fe, Porphyrite group
67306:250.61b
Apatiteiron
Tjårrojåkka-Fe, Porphyrite group
75316:328.50
IOCG
75311:255.96
IOCG
Tjårrojåkka-Cu, Porphyrite group
Tjårrojåkka-Cu, Porphyrite group
28KOM39A
IOCG
Nautanen, Porphyrite
group
28KOM39B
IOCG
Nautanen, Porphyrite
group
29JREK9
KUJ225 698.60m
KUJ 225 656.45
68313:120.20
5
Sample description
Coarse-grained apatite
vein (red) in massive magnetite
Fine-grained disseminated
apatite in magnetite
Coarse-grained apatite
with tabular martitealtered magnetite from the
middle of the ore
Fine-grained apatite with
hematite, banded, from
close the footwall contact
Red coarse-grained zoned
apatite from vein in the
ore
Red coarse-grained apatite
(some zoning)
Fine-grained apatite in
massive magnetite ore
Fine-grained banded magnetite ore white apatite
Fine-grained apatite in
massive magnetite
with carbonate, amphibole, and apatite veining
Apatite+chalcopyrite
+pyrite+magnetite-vein
from the surrounding ore
breccia
Magnetite+apaite vein in
footwall of copper deposit
Apatite in chalcopyrite
+amphibole-veins from
copper mineralisation
Fine-grained (white)
apatite+magnetite+
chalcopyrite vein in the N
part of the deposit
Round apatite
+magnetite+chalcopyrite
aggregates in the N part of
the deposit
analysis. Subsequently, mineral analyses were performed at the Natural
History Museum, London. Major element analyses were done using a
Cameca SX50 WDS electron microprobe with the technique described
in Potts et al. (1995). The apatites were analysed using an accelerating
voltage of 15 kV, a beam current of 20 nA, and a 5 Pm beam diameter.
Interferences between X-ray peaks for F/Ce and Nd/Ce were corrected
empirically using previously collected data from standards. LA-ICPMS
analyses were carried out using a UP-213 laser ablation system coupled
to a VG Plasmaquad 3 ICP-MS. The apatites were ablated at a laser
energy of 0.1 mJ/pulse and a rate of 20 Hz (10 Hz for samples
68313:120.20 and 6706:250.61b), resulting in a spot size of about 45 Pm.
National Institute of Science and Technology (NIST) standard glass
SRM612 was used as a calibration standard and isotope ratios were
converted to ppm concentrations using 43Ca as an internal standard, and
Ca concentrations previously determined by electron microprobe.
Accuracy was monitored using US Geological Survey (USGS) standard
SRM BCR-2G.
Apatite chemistry
Sixteen samples were analysed for major elements and, in addition,
nine of them for their REEs. The results are presented in Appendix 1
and 2. All apatites analysed are F-dominated with F abundances between
1.54 and 3.88 wt. % (Fig. 2a and b). The highest values are found in
apatites from “typical” Kiruna type iron ores. The lowest amounts are
recorded in the samples from the Tjårrojåkka apatite-iron (TjårrojåkkaFe) and the IOCG deposits (Tjårrojåkka-Cu and Nautanen) where the F
is substituted with Cl and to some extent OH. In Fig. 2a it is clear that
the samples from the Tjårrojåkka apatite-iron deposit differ in halogen
content to the other apatite-iron ores (Fig. 2a). The apatites from the
two IOCG deposits also show some enrichment in Cl and correlate well
with each other in the Cl-F-OH compositional diagram (Fig. 2b).
There is a clear trend in respect to F and Cl vs. S contents between
the apatite-iron and IOCG deposits (Figs. 2c and d). The apatite-iron
ores generally have higher concentrations of S than the IOCG deposits
with a maximum of 1 wt. % SO3 in the Rektorn ore. Also in these
diagrams the apatites from the Tjårrojåkka-Fe deposit follow the trend of
the IOCG deposits and not the one of the other apatite-iron ores.
According to Korzhinskiy (1981) the three solid-solution endmembers of apatite (Cl, F, and OH) can be used as indicators of the
composition of hydrothermal fluids. He also showed that the Cl/F ratio
in apatite increases with temperature and that the pressure effects on the
6
distribution for the components are
negligible at 500-700°C. Zhu and
Sverjensky (1991) also demonstrated
that partitioning of F and Cl
between minerals and hydrothermal
fluids is a strong function of
temperature, pressure, pH, and
fluid composition. According to
them the partitioning of Cl is a
strongly dependent of pressure
while the partitioning of F is not,
and that even in dominantly Clrich fluids the apatite would be Frich. Nevertheless, at higher
temperatures and pressures Cl-rich
apatite becomes more stable
relative to F-rich apatite.
The difference in Cl content
between the Tjårrojåkka-Fe and
the Kiirunavaara, Nukutus and
Rektorn deposits cannot be
explained by a temperature
difference. Both Tjårrojåkka-Fe
and Kiirunavaara formed at around
600°C (Edfelt et al., this volume;
Blake 1992) while the Per-Geijer
ores, to which Nukutus and
Rektorn belong, also formed at
approximately 550°C (O' Farrelly
1990). Within the IOCG group
(including the Tjårrojåkka-Fe),
temperature might be the cause of
the change in Cl content. The
sample with the highest Cl content
comes from the massive part of the
ore (i.e. highest temperature) while
the samples from the TjårrojåkkaCu deposit formed at lower
temperatures (Edfelt et al., 2007).
The other options for
explaining the trends are differences
in pressure, fluid composition, or
7
Fig. 2. Compositions of apatites from
selected apatite-iron and IOCG deposits
in northern Norrbotten. a and b F-ClOH diagram for apatite-iron and IOCG
deposits, respectively. c F-S variation
diagram. d Cl-S variation diagram. All
atoms per formula unit.
Fig. 3. a-i Chondrite-normalised REE patterns of apatite from apatite-iron and IOCG
deposits in Norrbotten. Data from this study. j Chondrite-normalised REE pattern for
apatite from selected iron ores. 1. Singhbhum, India; 2. Terra 1 and 2, Great Bear Lake,
USA; 3. Iron Springs Utah, USA; 4. Malmberget, Sweden; 5. El Laco, Chile. Data for
1-4 from Frietsch and Perdahl (1995) and for 5 from Rhodes et al. (1999). Chondrite
values after Anders and Grevesse (1989).
8
pH. No pressure data or estimates are available from any of the deposits;
hence, it is not feasible to conclude whether the pressure had an effect
on the Cl partitioning or not. The fluid compositions related to both
apatite-iron and IOCG deposits are similar. Fluid inclusion data from the
Tjårrojåkka-Fe and -Cu deposits suggest CaCl2-NaCl-dominated fluids
with salinities between 40-60 wt. % for the ore-forming event (Edfelt et
al., this volume), which is in agreement with fluid inclusion studies of
other epigenetic Fe-Cu-Au deposits in Norrbotten (Broman and
Martinsson 2000). Studies from the Kiruna type El Laco apatitemagnetite ore indicate that the fluids related to apatite formation were
NaCl-rich aqueous solutions with salinities up to 60 wt. % (Broman et
al. 1999). The difference seems to be that the IOCG deposits contain Ca
as an additional major component in the fluids, but what effect this has
on Cl partitioning into apatite could not be determined.
Rhodes and Oreskes (1999) showed when studying the El Laco deposit
that magnetite mineralisation is not very dependent on pH under low
activity of sulphur, but is mainly a function of oxygen fugacity.
However, at constant oxygen fugacity Fe solubility is very pH dependent
(Chou and Eugster 1977). The concentration of sulphur in the fluid can
also have an affect on the pH. In sulphur-rich hydrothermal fluids, H+ is
produced through oxidation of H2S:
H2S + 2O2 = HSO4í + H+
This type of reaction is commonly associated with porphyry copper
deposits resulting in strong acidic alterations and the formation of
kaolinite and/or pyrophyllite-alunite in the host rock. Such acidic
alterations are generally not seen in IOCG systems, which are
characterised by a low sulphide/oxide ratio (Hitzman et al. 1992).
Nevertheless, relatively speaking IOCG deposits are more sulphide-rich
than typical Kiruna type iron ores that almost entirely lack sulphides.
Hence, the hydrothermal fluids involved in the formation of IOCG
deposits contain more sulphur and H+ could consequently be generated
through the reaction above leading to a lower pH. Assuming that the
partitioning of Cl into apatite increases with decreased pH (as for annite;
Zhu and Sverjensky 1991), a lower pH of the fluids related to IOCG
deposits than for Kiruna type iron ores could be an explanation to the
higher values of Cl in the apatites. The enrichment of SO3 in Rektorn is
probably due to more oxidised conditions, which is also seen in the ore
mineralogy with hematite as the major component as well as the lack of
sulphides and minor occurrence of barite (Martinsson 2004). Peng et al.
(1997) showed that there is a correlation between increasing oxygen
9
fugacity, decreasing temperature and an increased uptake of SO3 in
fluor-apatite.
The distribution of REEs in hydrothermal minerals is often used
when discussing ore genesis. It is influenced by chemicalcrystallographical constraints, crystallisation kinetics, P-T conditions, and
the composition of the hydrothermal fluids (Lottermoser 1992). In
addition, it is necessary to take into account the effect of subsequent
metamorphism and hydrothermal alteration when using REE data in ore
genetic discussions. The REE patterns, as the halogen content, show a
clear difference between the apatite-iron ores and the IOCG deposits
(Fig. 3). The apatite-iron ores show an enrichment of the LREEs
(except for Ekströmsberg) while the IOCG deposits (including
Tjårrojåkka-Fe) show depletion. However, all of them show a clear
negative Eu anomaly.
The data from Kiirunavaara is in good agreement with data from
Harlov et al. (2002) where the depleted LREE pattern is interpreted as
high-temperature leaching of LREEs. Later, lower temperature (300 to
400°C) metamorphism resulted in further leaching of LREEs along
apatite grain boundaries and cracks. The depleted LREE pattern at
Ekstömsberg could also be due to secondary leaching seeing that the
sample show evidence of deformation and the apatite grains are rich in
inclusions and cracks filled with secondary minerals (mostly carbonates).
Frietsch (1974) also observed evidences of a later hydrothermal process at
Ekströmsberg, which had affected both the ore and the iron oxide
bearing host rock.
The LREE depletion at Tjårrojåkka cannot be explained in the
same manner. Firstly, no dark and bright areas were observed in the
apatite grains corresponding to leached and primary compositions of the
apatite, respectively, as in Kiirunavaara (Harlov et al. 2002). If the
pattern was a result of secondary depletion of LREEs, areas enriched in
LREEs with a steep pattern would be expected. Secondly, the deposits
have not been affected by any post-emplacement metamorphism, which
could have altered the apatite chemistry. The comparable pattern at
Nautanen also gives an indication that it could be the primary
composition of the apatites. However, the IOCG deposits sampled in
this study represent only the younger 1.77 Ga episode of IOCG
mineralisation in Norrbotten and the majority of apatite-iron ores in the
area formed around 1.9 Ga (Romer et al. 1994). The negative Eu
anomaly seen in all the samples probably reflects a relatively low oxygen
fugacity system during crystallisation (Puchelt and Emmermann 1976).
For oxygen fugacities below the hematite-magnetite buffer Eu is
predominantly present as Eu2+ (Sverjensky, 1984). The Eu anomaly
would therefore either result from inhibited incorporation into the Ca
10
site in the mineral lattice, or retention in the REE source. This could
either be a plagioclase bearing melt, or plagioclase bearing alteration
assemblages. Such are assemblages are potentially represented by the
regional albite-scapolite alteration (Frietsch et al. 1997).
According to Haas et al. (1995) Cl form more stable complexes
with LREEs than with HREE, which could be one of the reasons for
the LREE depletion pattern seen in the apatites in Kiirunavaara (Harlov
et al. 2002). REE chloride complexes are also more dominant under acid
pH conditions than under neutral and basic, when REE fluorides and
REE hydroxides dominate, respectively. This could indicate that during
IOCG mineralisation the fluids had a lower pH and the LREE formed
more stable complexes and did therefore not incorporate into the crystal
lattice of apatite.
Frietsch and Perdahl (1995) compared REE patterns from several
Kiruna type deposits with most of them showing a LREE enrichment
(Fig. 2j). A depleted pattern in Singhbhum deposit, which is spatially
related to U and Cu-Ni mineralisation, was observed and was
interpreted as a result of metasomatic alteration. The fact that the
unmetamorphosed El Laco deposit shows a steep REE pattern is another
indication that this is indeed the primary pattern for Kiruna type
deposits. Apatites from the Bafq district in Iran also show the same
enriched REE pattern as other “typical” Kiruna type iron ores, but are
more Cl-rich with average compositions between 0.54 and 0.76 wt.
(Daliran 2002). Data on apatite chemistry from IOCG deposits
(excluding Kiruna type iron ores) are few. At Bayan Obo, which is not a
typical IOCG deposit, La-enriched minerals have been interpreted to be
related to high temperatures and X(CO2) contents in fluid inclusions,
whilst lower La/Nd ratios formed from lower temperature dominantly
aqueous solutions (Smith et al. 2000).
The main difference between the Tjårrojåkka apatite-iron ore and
”typical” Kiruna type apatite-iron ores is the high concentrations of
sulphides in the surrounding ore breccia (Edfelt et al. 2005). The
Tjårrojåkka-Fe deposit has also been shown to be genetically related to
the Tjårrojåkka-Cu (Edfelt et al. 2007) and could hence represent an
iron-rich end-member of the IOCG group of deposits and therefore
have a different apatite chemistry compared to “typical” Kiruna type
apatite iron ores. Possibly the pH of the fluid was an important factor
influencing the apatite chemistry causing the distinct pattern between
Kiruna type iron ores and IOCG deposits. Fluids with a lower pH could
possible enhance the incorporation of Cl into the mineral but also allow
the LREEs to form more stable complexes with Cl resulting in the
depleted LREE pattern seen in IOCG deposits.
11
Conclusions
However preliminary, the results of this study suggest that there is
a fundamental difference in the apatite chemistry between Kiruna type
apatite-iron ores and IOCG deposits. Apatites from Kiruna type apatiteiron ores are F-dominated, with enrichment of LREEs and to some
extent S. Apatites from IOCG deposits show enrichment in Cl,
compared to the apatite-iron ores, and depletion of LREE. The variation
in apatite chemistry might be the result of IOCG deposits forming from
fluids with a lower pH. A lower pH would enhance incorporation of Cl
into apatite and LREE complexion with Cl, causing a depleted LREE
pattern. Within the IOCG group of deposits including the Tjårrojåkka
apatite-iron ore, a decrease in temperature could well be the cause of the
trend of decreased Cl. However, it cannot be ruled out that other factors
such as fluid composition and pressure also had an effect on the chemical
variation.
The available data indicate that some apatite-rich iron ores form
associated with fluids similar to those creating copper-rich IOCG
deposits and that apatite chemistry could be a potential tool for
distinguishing copper mineralising apatite-iron systems from barren. This
allows the discussion whether some of the apatite-iron ores should be
considered as IOCG deposits and not apatite-iron ores of Kiruna type,
and if “typical” Kiruna type apatite-iron ores should be included in the
IOCG group of deposits at all. However, further research is clearly
required and additional data on apatite chemistry from both apatite-iron
and IOCG deposits is needed to confirm these results.
Acknowledgements
This study is part of the GEORANGE funded research project P7
on IOCG deposits in Norrbotten, Sweden. The electron microprobe
and LA-ICPMS work was carried out at the Marie Curie ACCORD
(Analytical and Computational Centre for Ore Deposits) PhD training
site at the Natural History Museum, London.
12
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15
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16
APPENDIX 1
Electron-microprobe analyses of apatites.
#1
#2
#3
#4
CaO
55.00
55.53
55.81
55.29
0.00
0.01
0.00
0.00
MgO
SrO
0.03
0.07
0.07
0.06
MnO
0.09
0.03
0.03
0.05
a
0.01
0.01
0.00
0.06
FeO
0.04
0.07
0.02
0.06
La2O3
0.08
0.07
0.05
0.06
Ce2O3
0.15
0.13
0.10
0.10
Nd2O3
41.50
41.74
41.06
40.83
P2O5
0.04
0.03
0.04
0.05
SO3
Cl
0.02
0.03
0.05
0.02
F
3.30
3.36
3.29
3.31
b
0.35
0.32
0.34
0.32
H2O
Total
100.60 101.41 100.87 100.21
F=O
1.39
1.41
1.39
1.40
Cl=O
0.00
0.01
0.01
0.00
Total
99.20 99.99 99.47 98.81
Calculated on the basis of 26(O,OH,F,Cl)
Ca
9.55
9.56
9.70
9.67
0.00
0.00
0.00
0.00
Mg
0.00
0.01
0.01
0.01
Sr
Mn
0.01
0.00
0.00
0.01
a
0.00
0.00
0.00
0.01
Fe
La
0.00
0.00
0.00
0.00
Ce
0.00
0.00
0.00
0.00
0.01
0.01
0.01
0.01
Nd
P
5.70
5.68
5.64
5.64
S
0.00
0.00
0.00
0.01
F
1.69
1.71
1.69
1.71
Cl
0.00
0.01
0.01
0.01
b
0.30
0.28
0.30
0.28
OH
#5
55.26
0.00
0.05
0.07
0.00
0.03
0.09
0.11
41.41
0.01
0.03
3.28
0.35
100.68
1.38
0.01
99.29
9.60
0.00
0.00
0.01
0.00
0.00
0.01
0.01
5.69
0.00
1.68
0.01
0.31
66814 EKSTR
#6
#7
#8
55.07
55.72
54.98
0.00
0.00
0.00
0.08
0.07
0.07
0.06
0.07
0.00
0.00
0.04
0.01
0.07
0.05
0.02
0.07
0.09
0.05
0.13
0.10
0.08
41.47
41.11
41.45
0.05
0.09
0.04
0.07
0.04
0.02
3.40
3.27
3.19
0.28
0.36
0.40
100.74 100.99 100.31
1.43
1.38
1.34
0.01
0.01
0.00
99.29 99.61 98.96
9.53
0.00
0.01
0.01
0.00
0.00
0.00
0.01
5.67
0.01
1.74
0.02
0.25
9.68
0.00
0.01
0.01
0.01
0.00
0.01
0.01
5.64
0.01
1.68
0.01
0.31
9.59
0.00
0.01
0.00
0.00
0.00
0.00
0.00
5.71
0.00
1.64
0.00
0.35
#9
55.01
0.00
0.08
0.00
0.00
0.08
0.07
0.13
41.52
0.01
0.04
3.20
0.39
100.54
1.35
0.01
99.18
#10
53.10
0.00
0.05
0.06
0.11
0.02
0.07
0.06
39.55
0.05
0.05
2.99
0.43
96.53
1.26
0.01
95.26
#11
55.08
0.00
0.05
0.08
0.00
0.02
0.08
0.08
41.61
0.04
0.05
3.16
0.42
100.66
1.33
0.01
99.32
#12
55.11
0.00
0.07
0.04
0.00
0.04
0.00
0.09
41.50
0.03
0.05
3.21
0.39
100.53
1.35
0.01
99.17
#13
54.32
0.00
0.07
0.06
0.00
0.07
0.02
0.05
41.64
0.04
0.04
3.15
0.42
99.87
1.32
0.01
98.54
9.58
0.00
0.01
0.00
0.00
0.00
0.00
0.01
5.71
0.00
1.65
0.01
0.34
9.68
0.00
0.01
0.01
0.01
0.00
0.00
0.00
5.70
0.01
1.61
0.01
0.38
9.58
0.00
0.00
0.01
0.00
0.00
0.00
0.00
5.72
0.00
1.62
0.01
0.36
9.59
0.00
0.01
0.01
0.00
0.00
0.00
0.01
5.71
0.00
1.65
0.01
0.34
9.50
0.00
0.01
0.01
0.00
0.00
0.00
0.00
5.76
0.00
1.62
0.01
0.36
66814 EKSTR
#14
#15
#16
#17
#18
#19
#20
#21
#22
#23
#24
#25
#26
CaO
55.13
53.02
55.23
55.19
55.12
55.43
55.17
55.39
55.62
55.53
55.20
55.16
55.13
0.00
0.65
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
MgO
SrO
0.06
0.03
0.08
0.08
0.05
0.08
0.07
0.08
0.06
0.06
0.06
0.06
0.09
MnO
0.07
0.08
0.02
0.06
0.04
0.00
0.07
0.04
0.02
0.01
0.00
0.01
0.05
a
0.03
0.78
0.05
0.00
0.02
0.01
0.00
0.02
0.00
0.02
0.08
0.02
0.03
FeO
0.02
0.00
0.00
0.03
0.02
0.00
0.00
0.01
0.02
0.02
0.01
0.00
0.03
La2O3
0.05
0.04
0.00
0.08
0.03
0.02
0.02
0.04
0.02
0.06
0.06
0.04
0.05
Ce2O3
0.04
0.03
0.05
0.01
0.04
0.06
0.07
0.06
0.04
0.03
0.11
0.07
0.13
Nd2O3
41.33
39.73
41.37
41.82
42.30
41.55
42.04
41.98
41.29
41.93
42.15
41.27
42.03
P2O5
0.02
0.01
0.03
0.02
0.06
0.00
0.02
0.00
0.01
0.00
0.02
0.02
0.03
SO3
Cl
0.03
0.01
0.03
0.04
0.03
0.00
0.02
0.03
0.01
0.03
0.05
0.03
0.01
F
3.46
3.19
3.30
3.07
3.18
3.42
3.39
3.37
3.38
3.41
3.26
3.43
3.37
b
0.25
0.35
0.34
0.47
0.43
0.29
0.32
0.32
0.31
0.30
0.38
0.27
0.33
H2O
Total
100.49 97.91 100.49 100.87 101.30 100.87 101.17 101.35 100.80 101.41 101.38 100.40 101.26
F=O
1.46
1.34
1.39
1.29
1.34
1.44
1.43
1.42
1.42
1.44
1.37
1.45
1.42
Cl=O
0.01
0.00
0.01
0.01
0.01
0.00
0.00
0.01
0.00
0.01
0.01
0.01
0.00
Total
99.02 96.57 99.09 99.56 99.96 99.43 99.74 99.93 99.37 99.96 100.00 98.95 99.83
Ca
9.56
9.51
9.60
9.59
9.49
9.58
9.49
9.52
9.64
9.54
9.50
9.57
9.48
0.00
0.16
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.00
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.01
0.01
0.00
0.01
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.01
a
0.00
0.11
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
Fe
La
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Ce
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.01
Nd
P
5.66
5.63
5.68
5.74
5.76
5.67
5.71
5.70
5.65
5.69
5.73
5.66
5.71
S
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
F
1.77
1.69
1.69
1.58
1.62
1.74
1.72
1.71
1.73
1.73
1.66
1.76
1.71
Cl
0.01
0.00
0.01
0.01
0.01
0.00
0.01
0.01
0.00
0.01
0.01
0.01
0.00
b
0.22
0.31
0.30
0.41
0.37
0.26
0.27
0.28
0.27
0.26
0.33
0.23
0.28
OH
Ekströmsberg 2
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
#13
CaO
56.49
56.70
56.55
56.72
56.08
57.08
56.73
56.86
56.42
56.73
55.33
55.78
56.35
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
MgO
SrO
0.06
0.09
0.05
0.07
0.01
0.07
0.07
0.08
0.06
0.05
0.07
0.07
0.06
MnO
0.03
0.01
0.00
0.01
0.03
0.03
0.03
0.02
0.03
0.01
0.01
0.00
0.04
a
0.00
0.39
0.03
0.10
0.04
0.02
0.08
0.45
0.00
0.32
0.02
0.05
0.03
FeO
0.06
0.03
0.00
0.04
0.02
0.00
0.01
0.06
0.01
0.01
0.01
0.04
0.06
La2O3
0.04
0.05
0.08
0.00
0.01
0.05
0.00
0.10
0.00
0.04
0.05
0.04
0.01
Ce2O3
0.07
0.04
0.09
0.05
0.09
0.08
0.01
0.03
0.01
0.01
0.03
0.02
0.09
Nd2O3
42.46
42.23
41.46
42.08
41.37
42.68
41.54
41.73
41.87
42.47
41.75
43.00
41.72
P2O5
0.11
0.01
0.05
0.00
0.08
0.03
0.03
0.01
0.04
0.03
0.12
0.03
0.00
SO3
Cl
0.08
0.08
0.08
0.05
0.04
0.03
0.07
0.04
0.06
0.04
0.09
0.04
0.07
F
3.31
3.36
3.31
3.45
3.24
3.30
3.32
3.37
3.28
3.16
3.19
3.36
3.32
b
0.37
0.34
0.34
0.30
0.38
0.40
0.34
0.34
0.37
0.46
0.40
0.36
0.34
H2O
Total
103.08 103.30 102.03 102.87 101.37 103.77 102.24 103.09 102.15 103.32 101.06 102.78 102.10
F=O
1.39
1.41
1.40
1.45
1.36
1.39
1.40
1.42
1.38
1.33
1.34
1.42
1.40
Cl=O
0.02
0.02
0.02
0.01
0.01
0.01
0.02
0.01
0.01
0.01
0.02
0.01
0.02
Total
101.66 101.87 100.62 101.40 100.00 102.37 100.82 101.66 100.76 101.98 99.70 101.35 100.68
Ca
9.57
9.61
9.72
9.63
9.70
9.62
9.73
9.68
9.67
9.64
9.57
9.43
9.67
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.00
0.01
0.00
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
Sr
Mn
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
a
0.00
0.05
0.00
0.01
0.00
0.00
0.01
0.06
0.00
0.04
0.00
0.01
0.00
Fe
La
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Ce
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
Nd
P
5.68
5.65
5.63
5.64
5.65
5.69
5.63
5.62
5.67
5.70
5.71
5.75
5.65
S
0.01
0.00
0.01
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
F
1.66
1.68
1.68
1.73
1.65
1.64
1.68
1.69
1.66
1.58
1.63
1.68
1.68
Cl
0.02
0.02
0.02
0.01
0.01
0.01
0.02
0.01
0.02
0.01
0.03
0.01
0.02
b
0.32
0.30
0.30
0.26
0.34
0.35
0.30
0.30
0.33
0.41
0.35
0.31
0.30
OH
29JREK9
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
#13
CaO
55.69
55.58
55.47
55.89
56.29
56.82
56.08
56.62
56.56
56.58
56.54
56.35
56.51
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
MgO
SrO
0.08
0.05
0.07
0.09
0.08
0.07
0.09
0.03
0.07
0.08
0.06
0.07
0.08
MnO
0.04
0.06
0.03
0.00
0.03
0.00
0.01
0.04
0.00
0.04
0.02
0.07
0.00
a
0.12
0.04
0.00
0.01
0.06
0.41
0.03
0.00
0.04
0.04
0.04
0.06
0.00
FeO
0.18
0.15
0.13
0.13
0.10
0.00
0.07
0.16
0.00
0.09
0.08
0.13
0.09
La2O3
0.37
0.48
0.27
0.26
0.17
0.05
0.13
0.24
0.07
0.06
0.19
0.18
0.20
Ce2O3
0.15
0.18
0.18
0.09
0.02
0.08
0.10
0.09
0.01
0.10
0.03
0.13
0.10
Nd2O3
41.65
40.74
41.11
42.63
41.36
42.44
42.37
42.58
42.82
42.27
42.45
41.77
42.28
P2O5
0.40
0.52
0.62
0.29
0.28
0.06
0.23
0.28
0.02
0.13
0.21
0.22
0.21
SO3
Cl
0.05
0.03
0.04
0.00
0.04
0.03
0.07
0.06
0.02
0.02
0.01
0.02
0.01
F
3.43
3.43
3.47
3.50
3.47
3.02
2.97
3.04
3.02
3.00
3.05
3.01
3.08
b
0.29
0.28
0.26
0.30
0.27
0.54
0.55
0.53
0.55
0.55
0.53
0.53
0.51
H2O
Total
102.49 101.54 101.65 103.19 102.16 103.51 102.15 103.66 103.16 102.94 103.19 102.54 103.07
F=O
1.44
1.45
1.46
1.47
1.46
1.27
1.25
1.28
1.27
1.26
1.28
1.27
1.30
Cl=O
0.01
0.01
0.01
0.00
0.01
0.01
0.02
0.01
0.00
0.00
0.00
0.00
0.00
Total
101.03 100.08 100.18 101.71 100.69 102.23 100.89 102.36 101.89 101.68 101.90 101.27 101.77
Ca
9.50
9.59
9.52
9.42
9.63
9.67
9.60
9.61
9.63
9.68
9.63
9.70
9.64
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.00
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
a
0.02
0.00
0.00
0.00
0.01
0.05
0.00
0.00
0.00
0.01
0.00
0.01
0.00
Fe
La
0.01
0.01
0.01
0.01
0.01
0.00
0.00
0.01
0.00
0.01
0.00
0.01
0.01
Ce
0.02
0.03
0.02
0.02
0.01
0.00
0.01
0.01
0.00
0.00
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.00
0.00
0.01
0.01
0.00
0.01
0.00
0.01
0.01
Nd
P
5.61
5.56
5.58
5.68
5.59
5.71
5.73
5.71
5.76
5.72
5.71
5.68
5.70
S
0.05
0.06
0.07
0.03
0.03
0.01
0.03
0.03
0.00
0.01
0.02
0.03
0.02
F
1.73
1.75
1.76
1.74
1.75
1.52
1.50
1.52
1.52
1.52
1.53
1.53
1.55
Cl
0.01
0.01
0.01
0.00
0.01
0.01
0.02
0.02
0.00
0.00
0.00
0.00
0.00
b
0.26
0.24
0.23
0.26
0.24
0.47
0.48
0.46
0.48
0.48
0.46
0.47
0.45
OH
#13
55.81
0.00
0.06
0.00
0.27
0.05
0.02
0.05
41.62
0.02
0.05
3.47
0.26
101.68
1.46
0.01
100.21
9.58
0.00
0.01
0.00
0.04
0.00
0.00
0.00
5.64
0.00
1.76
0.01
0.23
29JREK9
#14
#15
#16
#17
#18
#19
#20
#21
#22
#23
#24
#25
#26
#27
CaO
56.04
56.10
55.14
56.42
55.48
56.30
55.51
55.89
55.97
56.52
55.93
56.13
55.73
55.69
0.02
0.00
0.00
0.00
0.01
0.00
0.01
0.00
0.00
0.01
0.01
0.00
0.01
0.03
MgO
SrO
0.08
0.06
0.07
0.09
0.06
0.09
0.04
0.06
0.08
0.10
0.06
0.09
0.06
0.04
MnO
0.00
0.04
0.01
0.07
0.00
0.06
0.05
0.03
0.05
0.00
0.05
0.03
0.00
0.02
a
0.07
0.03
0.46
0.09
0.04
0.04
0.01
0.03
0.00
0.04
0.00
0.00
0.01
0.19
FeO
0.18
0.13
0.20
0.03
0.15
0.12
0.19
0.10
0.13
0.07
0.29
0.14
0.23
0.15
La2O3
0.40
0.33
0.36
0.12
0.27
0.28
0.38
0.28
0.28
0.12
0.33
0.38
0.48
0.47
Ce2O3
0.16
0.19
0.20
0.11
0.17
0.17
0.21
0.17
0.16
0.08
0.10
0.18
0.29
0.21
Nd2O3
42.67
42.55
42.15
42.85
41.48
41.98
41.16
42.76
42.15
43.31
40.83
42.31
42.45
41.98
P2O5
0.28
0.33
0.25
0.10
0.60
0.40
0.39
0.40
0.46
0.14
0.78
0.25
0.27
0.20
SO3
Cl
0.02
0.03
0.05
0.02
0.03
0.03
0.04
0.02
0.03
0.03
0.03
0.01
0.04
0.10
F
2.98
2.95
3.47
3.61
3.53
3.61
3.40
3.41
3.41
3.43
3.08
3.13
3.06
3.07
b
0.57
0.58
0.28
0.24
0.25
0.22
0.30
0.35
0.33
0.35
0.48
0.48
0.51
0.48
H2O
Total
103.47 103.30 102.65 103.75 102.08 103.29 101.69 103.50 103.06 104.19 101.95 103.14 103.14 102.63
F=O
1.26
1.24
1.46
1.52
1.49
1.52
1.43
1.43
1.43
1.44
1.30
1.32
1.29
1.29
Cl=O
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.00
0.01
0.02
Total
102.21 102.05 101.18 102.22 100.58 101.76 100.25 102.07 101.61 102.74 100.65 101.82 101.85 101.31
Ca
9.54
9.57
9.37
9.44
9.46
9.49
9.56
9.40
9.48
9.44
9.67
9.57
9.51 9.56
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00 0.01
Mg
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.01
0.01 0.00
Sr
Mn
0.00
0.01
0.00
0.01
0.00
0.01
0.01
0.00
0.01
0.00
0.01
0.00
0.00 0.00
a
0.01
0.00
0.06
0.01
0.01
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00 0.03
Fe
La
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.01
0.00
0.02
0.01
0.01 0.01
Ce
0.02
0.02
0.02
0.01
0.02
0.02
0.02
0.02
0.02
0.01
0.02
0.02
0.03 0.03
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.02 0.01
Nd
P
5.74
5.73
5.66
5.67
5.59
5.59
5.60
5.68
5.64
5.71
5.58
5.70
5.72 5.70
S
0.03
0.04
0.03
0.01
0.07
0.05
0.05
0.05
0.05
0.02
0.09
0.03
0.03 0.02
F
1.50
1.48
1.74
1.78
1.78
1.80
1.73
1.69
1.70
1.69
1.57
1.57
1.54 1.55
Cl
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.00
0.01 0.03
b
0.50
0.51
0.24
0.21
0.22
0.19
0.26
0.30
0.29
0.30
0.42
0.42
0.45 0.42
OH
29JREK14
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
#13
CaO
56.55
56.41
55.48
55.78
55.74
56.36
56.50
56.40
56.00
56.69
55.49
56.68
55.83
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.01
0.00
0.01
0.01
0.00
MgO
SrO
0.07
0.08
0.06
0.06
0.05
0.06
0.08
0.06
0.06
0.04
0.05
0.06
0.06
MnO
0.00
0.04
0.00
0.02
0.03
0.01
0.08
0.05
0.01
0.00
0.01
0.01
0.00
a
0.00
0.01
0.05
0.15
0.06
0.00
0.06
0.12
0.01
0.12
0.03
0.10
0.27
FeO
0.09
0.11
0.21
0.18
0.16
0.15
0.14
0.03
0.10
0.00
0.17
0.07
0.12
La2O3
0.32
0.14
0.40
0.35
0.27
0.20
0.25
0.15
0.27
0.06
0.40
0.05
0.36
Ce2O3
0.15
0.12
0.28
0.22
0.19
0.12
0.11
0.06
0.08
0.01
0.18
0.06
0.18
Nd2O3
42.06
42.49
41.79
42.17
42.04
43.45
41.48
41.99
42.25
42.94
42.14
42.74
41.58
P2O5
0.28
0.40
0.32
0.45
0.57
0.11
0.15
0.10
0.37
0.03
0.56
0.03
0.75
SO3
Cl
0.03
0.00
0.03
0.04
0.04
0.00
0.02
0.03
0.02
0.00
0.03
0.01
0.04
F
3.05
3.10
3.39
3.46
3.43
3.49
3.46
3.58
3.75
3.31
3.66
3.48
3.55
b
0.51
0.51
0.32
0.30
0.31
0.32
0.29
0.23
0.16
0.41
0.20
0.31
0.25
H2O
Total
103.11 103.40 102.35 103.18 102.90 104.28 102.60 102.82 103.08 103.60 102.91 103.61 102.98
F=O
1.29
1.30
1.43
1.46
1.45
1.47
1.46
1.51
1.58
1.39
1.54
1.47
1.50
Cl=O
0.01
0.00
0.01
0.01
0.01
0.00
0.00
0.01
0.00
0.00
0.01
0.00
0.01
Total
101.81 102.10 100.92 101.72 101.45 102.80 101.14 101.31 101.49 102.21 101.37 102.14 101.47
Ca
9.67
9.58
9.48
9.43
9.44
9.39
9.65
9.56
9.41
9.55
9.35
9.53
9.45
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.00
0.00
0.01
0.01
Sr
Mn
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.00
a
0.00
0.00
0.01
0.02
0.01
0.00
0.01
0.02
0.00
0.02
0.00
0.01
0.04
Fe
La
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.00
0.01
0.00
0.01
Ce
0.02
0.01
0.02
0.02
0.02
0.01
0.01
0.01
0.02
0.00
0.02
0.00
0.02
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.00
0.00
0.00
0.01
0.00
0.01
Nd
P
5.68
5.70
5.65
5.63
5.63
5.72
5.60
5.62
5.61
5.72
5.61
5.68
5.56
S
0.03
0.05
0.04
0.05
0.07
0.01
0.02
0.01
0.04
0.00
0.07
0.00
0.09
F
1.54
1.55
1.71
1.73
1.72
1.72
1.74
1.79
1.86
1.65
1.82
1.73
1.77
Cl
0.01
0.00
0.01
0.01
0.01
0.00
0.00
0.01
0.00
0.00
0.01
0.00
0.01
b
0.45
0.45
0.28
0.26
0.27
0.28
0.25
0.20
0.14
0.35
0.17
0.27
0.22
OH
#14
55.57
0.01
0.07
0.00
0.08
0.15
0.43
0.19
41.32
0.25
0.03
3.53
0.23
101.86
1.49
0.01
100.37
9.53
0.00
0.01
0.00
0.01
0.01
0.03
0.01
5.60
0.03
1.79
0.01
0.21
29JREK14
#15
#16
#17
#18
#19
#20
#21
#22
#23
#24
#25
#26
#27
#28
CaO
55.91
55.68
55.84
55.35
55.67
55.85
56.60
55.85
54.76
56.13
55.93
56.62
56.29
55.98
0.00
0.00
0.02
0.00
0.05
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
MgO
SrO
0.07
0.06
0.04
0.05
0.05
0.07
0.06
0.05
0.06
0.06
0.04
0.04
0.08
0.06
MnO
0.01
0.00
0.00
0.03
0.02
0.04
0.06
0.00
0.00
0.00
0.06
0.03
0.01
0.02
a
0.00
0.00
0.13
0.06
0.46
0.13
0.14
0.05
0.22
0.43
0.26
0.34
0.02
0.04
FeO
0.20
0.16
0.18
0.20
0.14
0.16
0.01
0.16
0.17
0.18
0.12
0.02
0.13
0.09
La2O3
0.44
0.32
0.43
0.47
0.38
0.44
0.03
0.40
0.46
0.35
0.26
0.05
0.16
0.26
Ce2O3
0.22
0.25
0.25
0.22
0.23
0.21
0.05
0.23
0.26
0.27
0.16
0.09
0.13
0.11
Nd2O3
42.33
42.20
41.57
41.18
41.27
41.94
42.74
42.16
40.94
42.06
42.09
43.16
41.89
42.11
P2O5
0.61
0.48
0.43
0.71
0.28
0.58
0.01
0.52
1.02
0.16
0.31
0.07
0.27
0.21
SO3
Cl
0.03
0.01
0.03
0.03
0.04
0.05
0.01
0.02
0.03
0.03
0.02
0.01
0.00
0.01
F
3.60
3.61
3.49
3.62
3.09
3.13
3.06
3.03
3.46
3.45
3.65
3.88
3.77
3.78
b
0.24
0.23
0.27
0.19
0.46
0.47
0.53
0.53
0.27
0.30
0.20
0.12
0.14
0.14
H2O
Total
103.65 103.00 102.68 102.12 102.14 103.08 103.30 103.00 101.66 103.42 103.09 104.43 102.89 102.80
F=O
1.52
1.52
1.47
1.53
1.30
1.32
1.29
1.28
1.46
1.45
1.54
1.64
1.59
1.59
Cl=O
0.01
0.00
0.01
0.01
0.01
0.01
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.00
Total
102.13 101.48 101.20 100.59 100.83 101.75 102.01 101.72 100.19 101.96 101.55 102.80 101.30 101.20
Ca
9.38
9.39
9.51
9.44
9.63
9.53
9.63
9.54
9.40
9.51
9.43
9.36
9.49 9.44
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00 0.00
Mg
0.01
0.01
0.00
0.00
0.00
0.01
0.01
0.00
0.01
0.01
0.00
0.00
0.01 0.01
Sr
Mn
0.00
0.00
0.00
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.01
0.00
0.00 0.00
a
0.00
0.00
0.02
0.01
0.06
0.02
0.02
0.01
0.03
0.06
0.03
0.04
0.00 0.01
Fe
La
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.00
0.01 0.01
Ce
0.02
0.02
0.02
0.03
0.02
0.03
0.00
0.02
0.03
0.02
0.01
0.00
0.01 0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.00
0.01 0.01
Nd
P
5.61
5.62
5.59
5.55
5.64
5.65
5.74
5.69
5.55
5.63
5.61
5.64
5.58 5.61
S
0.07
0.06
0.05
0.09
0.03
0.07
0.00
0.06
0.12
0.02
0.04
0.01
0.03 0.02
F
1.78
1.80
1.75
1.82
1.58
1.58
1.54
1.53
1.75
1.73
1.82
1.89
1.88 1.88
Cl
0.01
0.00
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.00
0.00 0.00
b
0.21
0.20
0.24
0.17
0.41
0.41
0.46
0.47
0.24
0.27
0.18
0.10
0.12 0.12
OH
29JREK20
#1
#2
#3
#4
#5
#6
#7
#8
CaO
52.95
53.22
54.62
54.69
54.82
55.14
54.77
54.57
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.02
MgO
SrO
0.07
0.09
0.07
0.10
0.05
0.08
0.08
0.06
MnO
0.06
0.04
0.04
0.05
0.04
0.00
0.01
0.05
a
0.06
0.00
0.00
0.04
0.05
0.00
0.02
0.00
FeO
0.01
0.04
0.02
0.05
0.00
0.06
0.09
0.12
La2O3
0.08
0.08
0.03
0.12
0.10
0.07
0.22
0.22
Ce2O3
0.08
0.04
0.05
0.10
0.07
0.03
0.13
0.12
Nd2O3
40.77
41.49
41.47
41.50
42.91
42.03
42.87
40.96
P2O5
0.05
0.04
0.04
0.06
0.00
0.00
0.11
0.16
SO3
Cl
0.03
0.00
0.00
0.04
0.01
0.01
0.02
0.02
F
3.27
3.44
3.37
3.27
3.32
3.33
3.39
3.41
b
0.32
0.25
0.31
0.35
0.37
0.35
0.34
0.27
H2O
Total
97.75
98.73 100.01 100.35 101.74 101.09 102.05 99.97
F=O
1.38
1.45
1.42
1.38
1.40
1.40
1.43
1.44
Cl=O
0.01
0.00
0.00
0.01
0.00
0.00
0.01
0.00
Total
96.37 97.28 98.59 98.97 100.34 99.69 100.61 98.53
Ca
9.43
9.33
9.51
9.52
9.36
9.51
9.32
9.53
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
Sr
Mn
0.01
0.01
0.01
0.01
0.01
0.00
0.00
0.01
a
0.01
0.00
0.00
0.00
0.01
0.00
0.00
0.00
Fe
La
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.01
Ce
0.01
0.00
0.00
0.01
0.01
0.00
0.01
0.01
0.00
0.00
0.00
0.01
0.00
0.00
0.01
0.01
Nd
P
5.74
5.75
5.70
5.71
5.79
5.72
5.76
5.65
S
0.01
0.01
0.00
0.01
0.00
0.00
0.01
0.02
F
1.72
1.78
1.73
1.68
1.67
1.69
1.70
1.76
Cl
0.01
0.00
0.00
0.01
0.00
0.00
0.01
0.01
b
0.27
0.22
0.27
0.31
0.32
0.30
0.29
0.24
OH
#9
55.20
0.00
0.07
0.04
0.01
0.08
0.09
0.08
42.25
0.03
0.04
3.10
0.47
101.46
1.31
0.01
100.15
#10
54.59
0.00
0.08
0.01
0.03
0.10
0.10
0.09
40.95
0.17
0.01
3.05
0.47
99.65
1.29
0.00
98.36
#11
54.66
0.01
0.08
0.04
0.04
0.10
0.22
0.15
41.74
0.10
0.03
3.40
0.30
100.86
1.43
0.01
99.42
#12
54.75
0.00
0.08
0.03
0.01
0.11
0.25
0.15
41.78
0.15
0.02
3.29
0.36
100.97
1.39
0.00
99.58
#13
55.04
0.00
0.06
0.00
0.02
0.17
0.27
0.12
41.24
0.14
0.02
3.44
0.27
100.80
1.45
0.00
99.35
#14
55.78
0.02
0.06
0.04
0.06
0.04
0.09
0.08
41.77
0.04
0.05
3.30
0.36
101.68
1.39
0.01
100.28
9.53
0.00
0.01
0.01
0.00
0.00
0.01
0.00
5.76
0.00
1.58
0.01
0.41
9.63
0.00
0.01
0.00
0.00
0.01
0.01
0.01
5.71
0.02
1.59
0.00
0.41
9.44
0.00
0.01
0.01
0.00
0.01
0.01
0.01
5.70
0.01
1.73
0.01
0.26
9.47
0.00
0.01
0.00
0.00
0.01
0.01
0.01
5.71
0.02
1.68
0.00
0.32
9.54
0.00
0.01
0.00
0.00
0.01
0.02
0.01
5.65
0.02
1.76
0.00
0.24
9.60
0.01
0.01
0.01
0.01
0.00
0.01
0.00
5.68
0.00
1.68
0.01
0.31
#15
#16
CaO
54.95 55.32
0.00 0.00
MgO
SrO
0.06 0.08
MnO
0.00 0.06
a
0.00 0.05
FeO
0.09 0.01
La2O3
0.07 0.06
Ce2O3
0.00 0.03
Nd2O3
41.87 41.19
P2O5
0.07 0.03
SO3
Cl
0.01 0.00
F
3.57 3.44
b
0.22 0.27
H2O
Total
100.89 100.54
F=O
1.50 1.45
Cl=O
0.00 0.00
Total
99.39 99.09
Ca
9.44 9.60
0.00 0.00
Mg
0.01 0.01
Sr
Mn
0.00 0.01
a
0.00 0.01
Fe
La
0.01 0.00
Ce
0.00 0.00
0.00 0.00
Nd
P
5.68 5.65
S
0.01 0.00
F
1.81 1.76
Cl
0.00 0.00
b
0.19 0.24
OH
29JNUK1
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
#13
CaO
55.70
55.96
55.23
55.40
55.77
55.52
55.93
56.09
56.41
55.90
55.76
56.15
55.99
0.03
0.00
0.01
0.04
0.03
0.01
0.00
0.00
0.01
0.00
0.00
0.00
0.00
MgO
SrO
0.05
0.06
0.06
0.05
0.03
0.05
0.07
0.09
0.08
0.07
0.07
0.05
0.07
MnO
0.07
0.05
0.07
0.05
0.05
0.05
0.08
0.01
0.01
0.00
0.01
0.01
0.00
a
0.02
0.00
0.08
0.01
0.00
0.06
0.00
0.00
0.02
0.10
0.02
0.00
0.01
FeO
0.17
0.13
0.33
0.21
0.19
0.16
0.04
0.10
0.01
0.14
0.15
0.17
0.07
La2O3
0.35
0.27
0.86
0.49
0.42
0.44
0.06
0.19
0.11
0.21
0.41
0.51
0.20
Ce2O3
0.20
0.19
0.39
0.28
0.20
0.24
0.08
0.11
0.08
0.16
0.20
0.24
0.10
Nd2O3
42.46
42.05
41.14
41.87
42.26
41.59
42.07
42.64
42.60
42.33
42.02
41.51
42.60
P2O5
0.20
0.26
0.19
0.26
0.40
0.38
0.11
0.06
0.08
0.15
0.26
0.23
0.14
SO3
Cl
0.02
0.03
0.03
0.03
0.02
0.05
0.01
0.00
0.02
0.02
0.04
0.04
0.01
F
2.91
2.91
2.91
3.08
3.10
3.01
3.41
3.39
3.43
2.94
2.88
2.88
3.30
b
0.59
0.58
0.55
0.49
0.49
0.51
0.32
0.35
0.33
0.57
0.60
0.59
0.39
H2O
Total
102.78 102.50 101.84 102.24 102.96 102.09 102.17 103.02 103.17 102.59 102.42 102.37 102.89
F=O
1.23
1.23
1.23
1.30
1.31
1.27
1.44
1.43
1.44
1.24
1.21
1.21
1.39
Cl=O
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.00
0.00
0.00
0.01
0.01
0.00
Total
101.55 101.27 100.61 100.94 101.64 100.81 100.73 101.60 101.72 101.34 101.20 101.15 101.50
Ca
9.56
9.64
9.65
9.55
9.52
9.60
9.55
9.50
9.53
9.60
9.62
9.73
9.50
0.01
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.00
0.01
0.01
0.00
0.00
0.00
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.00
0.00
0.00
0.00
0.00
a
0.00
0.00
0.01
0.00
0.00
0.01
0.00
0.00
0.00
0.01
0.00
0.00
0.00
Fe
La
0.01
0.01
0.02
0.01
0.01
0.01
0.00
0.01
0.00
0.01
0.01
0.01
0.00
Ce
0.02
0.02
0.05
0.03
0.02
0.03
0.00
0.01
0.01
0.01
0.02
0.03
0.01
0.01
0.01
0.02
0.02
0.01
0.01
0.00
0.01
0.00
0.01
0.01
0.01
0.01
Nd
P
5.76
5.72
5.68
5.70
5.70
5.68
5.67
5.71
5.69
5.75
5.73
5.69
5.71
S
0.02
0.03
0.02
0.03
0.05
0.05
0.01
0.01
0.01
0.02
0.03
0.03
0.02
F
1.47
1.48
1.50
1.57
1.56
1.53
1.72
1.69
1.71
1.49
1.47
1.47
1.65
Cl
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.00
0.00
0.01
0.01
0.01
0.00
b
0.52
0.51
0.49
0.43
0.43
0.45
0.28
0.31
0.29
0.50
0.52
0.52
0.34
OH
#14
53.40
0.00
0.06
0.00
0.08
0.76
1.61
0.63
41.33
0.34
0.03
3.16
0.42
101.80
1.33
0.01
100.46
9.30
0.00
0.01
0.00
0.01
0.05
0.10
0.04
5.69
0.04
1.62
0.01
0.37
#15
#16
CaO
56.18
56.18
0.00
0.00
MgO
SrO
0.08
0.07
MnO
0.01
0.01
a
0.03
0.01
FeO
0.10
0.05
La2O3
0.16
0.10
Ce2O3
0.15
0.09
Nd2O3
41.53
42.20
P2O5
0.31
0.14
SO3
Cl
0.05
0.02
F
3.31
3.33
b
0.36
0.37
H2O
Total
102.26 102.57
F=O
1.39
1.40
Cl=O
0.01
0.00
Total
100.86 101.16
Ca
9.63
9.57
0.00
0.00
Mg
0.01
0.01
Sr
Mn
0.00
0.00
a
0.00
0.00
Fe
La
0.01
0.00
Ce
0.01
0.01
0.01
0.01
Nd
P
5.62
5.68
S
0.04
0.02
F
1.67
1.68
Cl
0.01
0.00
b
0.31
0.32
OH
KUJ5044 80.10
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
CaO
54.75
55.07
55.11
55.77
55.89
56.59
56.47
56.45
56.11
56.08
55.00
56.43
0.04
0.01
0.00
0.02
0.01
0.01
0.00
0.00
0.01
0.00
0.00
0.00
MgO
SrO
0.04
0.06
0.06
0.05
0.06
0.08
0.05
0.05
0.02
0.05
0.05
0.05
MnO
0.02
0.04
0.00
0.07
0.01
0.02
0.03
0.00
0.04
0.07
0.08
0.02
a
0.76
0.03
0.09
0.97
0.10
0.23
0.13
0.19
0.12
0.83
0.14
0.56
FeO
0.21
0.20
0.20
0.19
0.19
0.01
0.05
0.02
0.02
0.00
0.19
0.02
La2O3
0.50
0.52
0.59
0.48
0.40
0.06
0.08
0.04
0.12
0.04
0.49
0.06
Ce2O3
0.26
0.23
0.24
0.21
0.20
0.02
0.06
0.12
0.06
0.05
0.23
0.02
Nd2O3
41.24
42.18
41.95
41.84
42.09
43.49
43.25
42.80
41.88
42.61
41.45
43.48
P2O5
0.34
0.24
0.33
0.23
0.22
0.01
0.04
0.01
0.05
0.02
0.32
0.07
SO3
Cl
0.07
0.06
0.08
0.02
0.05
0.04
0.05
0.01
0.01
0.03
0.06
0.04
F
3.02
3.07
2.93
3.00
2.77
2.87
3.08
3.14
3.11
3.06
3.01
3.19
b
0.49
0.49
0.55
0.54
0.65
0.64
0.52
0.49
0.47
0.51
0.50
0.47
H2O
Total
101.73 102.20 102.13 103.40 102.62 104.06 103.82 103.31 102.03 103.35 101.52 104.41
F=O
1.27
1.29
1.23
1.26
1.17
1.21
1.30
1.32
1.31
1.29
1.27
1.34
Cl=O
0.02
0.01
0.02
0.00
0.01
0.01
0.01
0.00
0.00
0.01
0.01
0.01
Total
100.45 100.89 100.88 102.13 101.44 102.84 102.51 101.99 100.72 102.05 100.24 103.06
Ca
9.52
9.47
9.52
9.57
9.65
9.57
9.53
9.58
9.67
9.55
9.56
9.45
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.00
0.01
0.01
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.01
0.00
Sr
Mn
0.00
0.01
0.00
0.01
0.00
0.00
0.00
0.00
0.01
0.01
0.01
0.00
a
0.10
0.00
0.01
0.13
0.01
0.03
0.02
0.03
0.02
0.11
0.02
0.07
Fe
La
0.01
0.01
0.01
0.01
0.01
0.00
0.00
0.00
0.00
0.00
0.01
0.00
Ce
0.03
0.03
0.03
0.03
0.02
0.00
0.00
0.00
0.01
0.00
0.03
0.00
0.02
0.01
0.01
0.01
0.01
0.00
0.00
0.01
0.00
0.00
0.01
0.00
Nd
P
5.67
5.73
5.73
5.67
5.74
5.81
5.77
5.74
5.70
5.73
5.69
5.76
S
0.04
0.03
0.04
0.03
0.03
0.00
0.00
0.00
0.01
0.00
0.04
0.01
F
1.55
1.56
1.50
1.52
1.41
1.43
1.54
1.57
1.58
1.54
1.54
1.58
Cl
0.02
0.02
0.02
0.01
0.01
0.01
0.01
0.00
0.00
0.01
0.02
0.01
b
0.43
0.43
0.48
0.48
0.57
0.56
0.45
0.42
0.42
0.45
0.44
0.41
OH
KUJ225 698.60
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
#13
CaO
55.67
56.68
55.70
55.36
55.79
56.37
55.55
55.53
55.84
56.95
55.90
56.60
56.52
0.01
0.00
0.03
0.06
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.00
0.00
MgO
SrO
0.07
0.08
0.06
0.06
0.08
0.09
0.05
0.07
0.05
0.06
0.04
0.05
0.05
MnO
0.00
0.08
0.04
0.04
0.02
0.01
0.01
0.08
0.00
0.04
0.01
0.00
0.04
a
0.02
0.08
0.13
0.09
0.06
0.06
0.02
0.09
0.06
0.01
0.03
0.09
0.01
FeO
0.11
0.06
0.19
0.23
0.12
0.07
0.07
0.12
0.10
0.09
0.10
0.01
0.09
La2O3
0.24
0.02
0.34
0.42
0.27
0.13
0.22
0.34
0.28
0.19
0.26
0.05
0.31
Ce2O3
0.09
0.08
0.17
0.24
0.17
0.05
0.15
0.17
0.13
0.18
0.10
0.07
0.21
Nd2O3
42.47
42.80
42.27
41.94
42.89
42.53
42.63
42.38
43.11
42.45
42.37
42.60
42.63
P2O5
0.16
0.00
0.15
0.21
0.23
0.09
0.11
0.08
0.22
0.07
0.18
0.06
0.13
SO3
Cl
0.08
0.04
0.10
0.08
0.07
0.06
0.07
0.06
0.11
0.06
0.08
0.05
0.08
F
3.12
3.19
3.06
3.02
3.03
3.08
3.14
2.97
2.88
2.89
2.90
3.07
2.82
b
0.46
0.46
0.49
0.50
0.53
0.50
0.46
0.54
0.60
0.60
0.58
0.51
0.63
H2O
Total
102.51 103.55 102.71 102.25 103.26 103.02 102.48 102.43 103.38 103.59 102.58 103.15 103.53
F=O
1.31
1.34
1.29
1.27
1.28
1.30
1.32
1.25
1.21
1.22
1.22
1.29
1.19
Cl=O
0.02
0.01
0.02
0.02
0.02
0.01
0.02
0.01
0.02
0.01
0.02
0.01
0.02
Total
101.17 102.20 101.40 100.96 101.97 101.71 101.14 101.17 102.14 102.36 101.34 101.85 102.32
Ca
9.51
9.59
9.54
9.54
9.48
9.61
9.49
9.55
9.50
9.72
9.60
9.64
9.66
0.00
0.00
0.01
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.00
0.01
0.00
0.00
0.00
Sr
Mn
0.00
0.01
0.01
0.01
0.00
0.00
0.00
0.01
0.00
0.01
0.00
0.00
0.01
a
0.00
0.01
0.02
0.01
0.01
0.01
0.00
0.01
0.01
0.00
0.00
0.01
0.00
Fe
La
0.01
0.00
0.01
0.01
0.01
0.00
0.00
0.01
0.01
0.01
0.01
0.00
0.01
Ce
0.01
0.00
0.02
0.02
0.02
0.01
0.01
0.02
0.02
0.01
0.02
0.00
0.02
0.00
0.00
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.01
0.00
0.01
Nd
P
5.74
5.72
5.72
5.71
5.76
5.73
5.75
5.76
5.79
5.73
5.75
5.73
5.75
S
0.02
0.00
0.02
0.02
0.03
0.01
0.01
0.01
0.03
0.01
0.02
0.01
0.02
F
1.57
1.59
1.54
1.54
1.52
1.55
1.58
1.51
1.45
1.45
1.47
1.54
1.42
Cl
0.02
0.01
0.03
0.02
0.02
0.02
0.02
0.02
0.03
0.02
0.02
0.01
0.02
b
0.40
0.40
0.43
0.44
0.46
0.43
0.40
0.48
0.53
0.53
0.51
0.45
0.56
OH
KUJ225 656.45
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
#13
CaO
56.47
56.24
56.13
56.37
56.90
56.92
56.13
56.93
56.61
56.93
56.64
56.77
56.82
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.02
0.01
0.00
0.00
MgO
SrO
0.07
0.06
0.08
0.06
0.05
0.08
0.05
0.07
0.08
0.07
0.06
0.05
0.07
MnO
0.06
0.04
0.02
0.01
0.08
0.08
0.04
0.05
0.06
0.08
0.06
0.04
0.04
a
0.07
0.36
0.28
0.61
0.14
0.44
0.21
0.58
0.06
0.30
0.23
0.83
0.03
FeO
0.05
0.08
0.13
0.03
0.08
0.03
0.09
0.00
0.03
0.01
0.07
0.04
0.02
La2O3
0.17
0.24
0.22
0.03
0.07
0.06
0.18
0.05
0.11
0.05
0.12
0.10
0.10
Ce2O3
0.12
0.14
0.12
0.06
0.04
0.07
0.17
0.05
0.09
0.06
0.07
0.06
0.08
Nd2O3
42.16
41.99
42.06
42.36
42.28
42.53
41.65
41.74
42.03
42.64
42.51
42.79
42.53
P2O5
0.11
0.14
0.14
0.02
0.07
0.01
0.02
0.03
0.06
0.00
0.04
0.00
0.02
SO3
Cl
0.07
0.08
0.06
0.05
0.05
0.06
0.05
0.06
0.05
0.03
0.06
0.02
0.02
F
3.26
3.18
3.03
3.09
3.10
3.13
3.18
3.21
2.99
3.00
3.01
2.94
3.20
b
0.40
0.43
0.51
0.49
0.49
0.48
0.42
0.42
0.53
0.56
0.54
0.59
0.45
H2O
Total
103.00 102.98 102.78 103.18 103.34 103.87 102.20 103.16 102.72 103.75 103.41 104.22 103.39
F=O
1.37
1.34
1.28
1.30
1.30
1.32
1.34
1.35
1.26
1.26
1.27
1.24
1.35
Cl=O
0.02
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.00
Total
101.61 101.62 101.49 101.87 102.03 102.54 100.85 101.80 101.44 102.48 102.13 102.98 102.04
Ca
9.61
9.61
9.63
9.61
9.69
9.64
9.67
9.72
9.72
9.67
9.65
9.63
9.64
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.00
0.01
0.00
0.01
0.01
0.01
0.01
0.00
0.01
Sr
Mn
0.01
0.01
0.00
0.00
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
a
0.01
0.05
0.04
0.08
0.02
0.06
0.03
0.08
0.01
0.04
0.03
0.11
0.00
Fe
La
0.00
0.00
0.01
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
Ce
0.01
0.01
0.01
0.00
0.00
0.00
0.01
0.00
0.01
0.00
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.00
0.00
0.01
0.00
0.01
0.00
0.00
0.00
0.00
Nd
P
5.67
5.67
5.70
5.71
5.69
5.70
5.67
5.63
5.70
5.73
5.72
5.74
5.70
S
0.01
0.02
0.02
0.00
0.01
0.00
0.00
0.00
0.01
0.00
0.01
0.00
0.00
F
1.64
1.60
1.54
1.56
1.56
1.56
1.62
1.62
1.52
1.50
1.51
1.47
1.60
Cl
0.02
0.02
0.02
0.01
0.01
0.02
0.01
0.02
0.01
0.01
0.01
0.01
0.01
b
0.35
0.38
0.45
0.43
0.43
0.42
0.37
0.37
0.47
0.49
0.47
0.52
0.39
OH
#14
56.69
0.01
0.06
0.03
0.07
0.07
0.07
0.05
42.09
0.03
0.05
2.82
0.63
102.66
1.19
0.01
101.47
9.77
0.00
0.01
0.00
0.01
0.00
0.00
0.00
5.73
0.00
1.43
0.01
0.55
#14
56.78
0.00
0.07
0.03
0.58
0.00
0.09
0.03
42.73
0.07
0.04
3.12
0.50
104.02
1.31
0.01
102.70
9.60
0.00
0.01
0.00
0.08
0.00
0.01
0.00
5.71
0.01
1.55
0.01
0.43
#15
#16
CaO
56.53
56.44
0.01
0.00
MgO
SrO
0.07
0.07
MnO
0.04
0.00
a
0.23
0.39
FeO
0.02
0.00
La2O3
0.00
0.07
Ce2O3
0.09
0.12
Nd2O3
42.23
41.65
P2O5
0.06
0.06
SO3
Cl
0.03
0.06
F
3.28
3.21
b
0.40
0.41
H2O
Total
102.98 102.48
F=O
1.38
1.35
Cl=O
0.01
0.01
Total
101.59 101.11
Ca
9.62 9.69
0.00 0.00
Mg
0.01 0.01
Sr
Mn
0.00 0.00
a
0.03 0.05
Fe
La
0.00 0.00
Ce
0.00 0.00
0.01 0.01
Nd
P
5.68 5.65
S
0.01 0.01
F
1.65 1.63
Cl
0.01 0.02
b
0.35 0.36
OH
68313:120.20-120.45
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
#13
CaO
55.74
55.35
55.43
55.83
55.73
55.89
55.92
55.85
55.28
55.54
56.05
56.10
55.20
0.02
0.00
0.00
0.01
0.02
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.00
MgO
SrO
0.07
0.10
0.09
0.10
0.08
0.10
0.11
0.10
0.07
0.11
0.06
0.05
0.07
MnO
0.09
0.07
0.00
0.08
0.08
0.02
0.04
0.03
0.01
0.07
0.08
0.05
0.04
a
0.02
0.13
0.00
0.13
0.09
0.10
0.15
0.24
0.05
0.09
0.08
0.05
0.13
FeO
0.05
0.05
0.09
0.05
0.06
0.08
0.07
0.03
0.12
0.04
0.06
0.07
0.17
La2O3
0.15
0.09
0.15
0.16
0.20
0.23
0.25
0.16
0.16
0.08
0.17
0.09
0.29
Ce2O3
0.16
0.16
0.16
0.20
0.17
0.22
0.20
0.21
0.18
0.13
0.21
0.09
0.28
Nd2O3
42.06
42.03
41.42
41.79
41.92
42.02
42.62
42.08
42.43
41.97
42.08
42.12
41.84
P2O5
0.14
0.16
0.11
0.07
0.14
0.13
0.20
0.22
0.08
0.06
0.12
0.06
0.14
SO3
Cl
1.34
1.61
1.57
1.44
1.46
0.37
0.32
0.90
1.37
1.11
0.17
0.29
1.29
F
1.96
2.06
1.54
1.63
1.67
2.48
2.43
2.05
1.65
1.80
2.58
2.73
1.62
b
0.71
0.57
0.85
0.85
0.82
0.71
0.77
0.79
0.87
0.86
0.72
0.60
0.90
H2O
Total
102.50 102.40 101.39 102.35 102.43 102.35 103.06 102.67 102.26 101.86 102.37 102.30 101.96
F=O
0.82
0.87
0.65
0.69
0.70
1.04
1.02
0.86
0.70
0.76
1.09
1.15
0.68
Cl=O
0.30
0.36
0.35
0.32
0.33
0.08
0.07
0.20
0.31
0.25
0.04
0.07
0.29
Total
101.37 101.17 100.38 101.34 101.40 101.23 101.97 101.60 101.26 100.85 101.24 101.09 100.98
Ca
9.70
9.59
9.83
9.81
9.76
9.71
9.64
9.72
9.68
9.77
9.73
9.69
9.74
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
Sr
Mn
0.01
0.01
0.00
0.01
0.01
0.00
0.01
0.00
0.00
0.01
0.01
0.01
0.01
a
0.00
0.02
0.00
0.02
0.01
0.01
0.02
0.03
0.01
0.01
0.01
0.01
0.02
Fe
La
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.01
Ce
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.02
Nd
P
5.78
5.76
5.81
5.80
5.80
5.77
5.81
5.79
5.87
5.83
5.77
5.75
5.84
S
0.02
0.02
0.01
0.01
0.02
0.02
0.02
0.03
0.01
0.01
0.01
0.01
0.02
F
1.01
1.05
0.81
0.85
0.86
1.27
1.24
1.05
0.85
0.93
1.32
1.39
0.84
Cl
0.37
0.44
0.44
0.40
0.40
0.10
0.09
0.25
0.38
0.31
0.05
0.08
0.36
b
0.62
0.51
0.75
0.75
0.73
0.63
0.68
0.70
0.77
0.76
0.63
0.53
0.80
OH
#14
55.46
0.01
0.07
0.06
0.11
0.09
0.19
0.27
41.50
0.09
1.51
1.68
0.79
101.81
0.71
0.34
100.76
9.79
0.00
0.01
0.01
0.01
0.01
0.01
0.02
5.79
0.01
0.88
0.42
0.70
67306:250.61-250.86b
#1
#2
#3
#4
#5
#6
#7
#8
#9
CaO
55.42
54.96
54.98
55.17
55.31
55.54
55.46
55.25
54.77
0.02
0.00
0.00
0.00
0.00
0.00
0.02
0.01
0.00
MgO
SrO
0.09
0.10
0.08
0.10
0.07
0.11
0.10
0.08
0.12
MnO
0.07
0.05
0.02
0.06
0.07
0.11
0.03
0.03
0.06
a
0.09
0.06
0.05
0.10
0.03
0.06
0.06
0.05
0.02
FeO
0.02
0.00
0.02
0.05
0.03
0.03
0.03
0.02
0.03
La2O3
0.08
0.13
0.09
0.13
0.06
0.04
0.11
0.08
0.05
Ce2O3
0.09
0.12
0.09
0.11
0.04
0.08
0.10
0.07
0.10
Nd2O3
41.76
41.89
41.64
41.79
42.44
41.70
42.37
41.90
41.23
P2O5
0.03
0.13
0.10
0.05
0.05
0.03
0.09
0.07
0.08
SO3
Cl
0.94
1.01
0.99
1.01
0.93
0.97
0.97
0.99
0.93
F
2.03
1.99
1.96
1.95
1.89
1.99
1.79
1.88
1.81
b
0.77
0.77
0.79
0.79
0.87
0.78
0.91
0.84
0.88
H2O
Total
101.40 101.20 100.79 101.29 101.78 101.44 102.03 101.26 100.07
F=O
0.86
0.84
0.82
0.82
0.80
0.84
0.75
0.79
0.76
Cl=O
0.21
0.23
0.22
0.23
0.21
0.22
0.22
0.22
0.21
Total
100.33 100.13 99.75 100.24 100.78 100.38 101.06 100.25 99.10
Ca
9.75
9.68
9.73
9.73
9.70
9.78
9.73
9.75
9.81
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.01
0.01
0.00
0.01
0.01
0.02
0.00
0.00
0.01
a
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.00
Fe
La
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Ce
0.00
0.01
0.01
0.01
0.00
0.00
0.01
0.00
0.00
0.01
0.01
0.01
0.01
0.00
0.00
0.01
0.00
0.01
Nd
P
5.81
5.83
5.82
5.82
5.88
5.80
5.87
5.84
5.84
S
0.00
0.02
0.01
0.01
0.01
0.00
0.01
0.01
0.01
F
1.06
1.04
1.02
1.02
0.98
1.04
0.93
0.98
0.96
Cl
0.26
0.28
0.28
0.28
0.26
0.27
0.27
0.28
0.26
b
0.68
0.68
0.70
0.70
0.77
0.69
0.80
0.74
0.78
OH
#10
54.85
0.01
0.07
0.01
0.05
0.01
0.08
0.08
40.76
0.08
0.97
1.83
0.84
99.64
0.77
0.22
98.65
#11
54.77
0.00
0.09
0.05
0.07
0.04
0.08
0.11
41.89
0.07
0.88
1.87
0.88
100.79
0.79
0.20
99.80
#12
54.42
0.00
0.09
0.03
0.35
0.06
0.08
0.07
42.05
0.06
0.78
2.08
0.79
100.84
0.88
0.18
99.79
#13
54.30
0.00
0.07
0.05
0.02
0.02
0.08
0.12
41.88
0.11
0.86
2.01
0.80
100.32
0.85
0.19
99.28
#14
54.70
0.01
0.08
0.05
0.09
0.01
0.03
0.03
42.28
0.06
0.79
2.13
0.77
101.02
0.90
0.18
99.95
9.88
0.00
0.01
0.00
0.01
0.00
0.00
0.01
5.80
0.01
0.97
0.28
0.75
9.71
0.00
0.01
0.01
0.01
0.00
0.00
0.01
5.87
0.01
0.98
0.25
0.77
9.60
0.00
0.01
0.00
0.05
0.00
0.00
0.00
5.86
0.01
1.08
0.22
0.70
9.63
0.00
0.01
0.01
0.00
0.00
0.00
0.01
5.87
0.01
1.05
0.24
0.71
9.60
0.00
0.01
0.01
0.01
0.00
0.00
0.00
5.87
0.01
1.11
0.22
0.67
75316:328.50
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
#13
CaO
56.78
57.02
56.22
56.44
56.63
56.41
56.28
56.15
57.09
56.36
55.81
56.71
56.18
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
MgO
SrO
0.08
0.07
0.10
0.09
0.10
0.09
0.09
0.09
0.09
0.09
0.09
0.08
0.09
MnO
0.04
0.08
0.09
0.10
0.09
0.09
0.06
0.10
0.05
0.15
0.09
0.08
0.09
a
0.05
0.10
0.03
0.04
0.08
0.03
0.04
0.00
0.12
0.05
0.03
0.00
0.04
FeO
0.02
0.03
0.00
0.02
0.04
0.04
0.00
0.04
0.04
0.03
0.01
0.03
0.00
La2O3
0.05
0.02
0.00
0.01
0.01
0.05
0.05
0.02
0.00
0.01
0.04
0.00
0.02
Ce2O3
0.09
0.12
0.08
0.03
0.04
0.05
0.11
0.05
0.09
0.10
0.05
0.05
0.06
Nd2O3
42.19
43.38
42.72
41.96
42.89
43.20
42.71
43.13
42.21
42.83
42.23
42.09
42.73
P2O5
0.09
0.13
0.06
0.03
0.06
0.06
0.13
0.08
0.05
0.08
0.08
0.07
0.10
SO3
Cl
0.38
0.32
0.26
0.26
0.36
0.34
0.36
0.38
0.40
0.36
0.37
0.41
0.36
F
2.18
2.28
2.69
2.72
2.56
2.61
2.11
2.13
2.17
2.47
2.41
2.45
2.44
b
0.88
0.87
0.65
0.61
0.70
0.68
0.93
0.92
0.88
0.74
0.75
0.72
0.76
H2O
Total
102.81 104.42 102.90 102.32 103.55 103.65 102.87 103.08 103.18 103.26 101.95 102.69 102.87
F=O
0.92
0.96
1.13
1.15
1.08
1.10
0.89
0.90
0.91
1.04
1.01
1.03
1.03
Cl=O
0.09
0.07
0.06
0.06
0.08
0.08
0.08
0.09
0.09
0.08
0.08
0.09
0.08
Total
101.81 103.39 101.71 101.12 102.39 102.47 101.90 102.10 102.18 102.14 100.86 101.57 101.76
Ca
9.88
9.72
9.64
9.76
9.68
9.61
9.77
9.70
9.91
9.68
9.72
9.82
9.68
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.01
0.01
0.01
a
0.01
0.01
0.00
0.00
0.01
0.00
0.01
0.00
0.02
0.01
0.00
0.00
0.01
Fe
La
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Ce
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.01
0.00
0.00
0.00
Nd
P
5.80
5.84
5.79
5.73
5.79
5.81
5.86
5.89
5.79
5.81
5.81
5.76
5.82
S
0.01
0.02
0.01
0.00
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
F
1.12
1.15
1.36
1.39
1.29
1.31
1.08
1.09
1.11
1.25
1.24
1.25
1.24
Cl
0.10
0.09
0.07
0.07
0.10
0.09
0.10
0.10
0.11
0.10
0.10
0.11
0.10
b
0.78
0.77
0.57
0.54
0.61
0.60
0.82
0.81
0.78
0.65
0.66
0.64
0.66
OH
#14
56.69
0.00
0.06
0.09
0.05
0.01
0.05
0.04
42.99
0.02
0.31
2.50
0.75
103.55
1.05
0.07
102.42
9.70
0.00
0.01
0.01
0.01
0.00
0.00
0.00
5.81
0.00
1.26
0.08
0.65
75316:328.50
#15
#16
#17
#18
#19
#20
#21
#22
#23
#24
#25
#26
CaO
56.57
55.98
56.69
56.76
56.53
56.96
56.02
56.31
57.17
56.77
56.15
56.58
0.00
0.00
0.01
0.00
0.01
0.02
0.02
0.00
0.00
0.00
0.00
0.01
MgO
SrO
0.09
0.07
0.08
0.08
0.09
0.05
0.09
0.09
0.09
0.09
0.09
0.09
MnO
0.07
0.05
0.09
0.06
0.06
0.12
0.08
0.05
0.12
0.10
0.06
0.05
a
0.01
0.12
0.01
0.10
0.01
0.00
0.00
0.03
0.00
0.02
0.05
0.06
FeO
0.03
0.10
0.03
0.04
0.04
0.04
0.03
0.02
0.00
0.02
0.04
0.06
La2O3
0.08
0.10
0.06
0.03
0.06
0.10
0.19
0.09
0.01
0.01
0.02
0.03
Ce2O3
0.00
0.11
0.09
0.03
0.09
0.14
0.15
0.06
0.03
0.04
0.08
0.08
Nd2O3
41.66
41.86
42.83
43.02
42.36
42.81
42.17
41.81
42.70
42.96
42.30
42.11
P2O5
0.07
0.11
0.10
0.10
0.13
0.11
0.12
0.08
0.05
0.05
0.05
0.06
SO3
Cl
0.45
0.45
0.42
0.39
0.39
0.42
0.44
0.40
0.33
0.36
0.41
0.40
F
2.32
2.39
2.36
2.34
2.27
2.22
2.25
2.25
2.07
2.21
2.34
2.36
b
0.77
0.73
0.79
0.81
0.83
0.86
0.82
0.82
0.96
0.89
0.78
0.77
H2O
Total
102.10 102.08 103.55 103.74 102.86 103.85 102.37 102.02 103.54 103.51 102.36 102.66
F=O
0.98
1.01
0.99
0.98
0.96
0.94
0.95
0.95
0.87
0.93
0.99
0.99
Cl=O
0.10
0.10
0.10
0.09
0.09
0.09
0.10
0.09
0.07
0.08
0.09
0.09
Total
101.02 100.97 102.46 102.67 101.81 102.82 101.33 100.98 102.60 102.49 101.28 101.57
Ca
9.89
9.76
9.73
9.72
9.80
9.79
9.76
9.86
9.89
9.78
9.76
9.82
0.00
0.00
0.00
0.00
0.00
0.01
0.01
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.01
0.01
0.01
0.01
0.01
0.02
0.01
0.01
0.02
0.01
0.01
0.01
a
0.00
0.02
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.01
Fe
La
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Ce
0.00
0.01
0.00
0.00
0.00
0.01
0.01
0.01
0.00
0.00
0.00
0.00
0.00
0.01
0.01
0.00
0.01
0.01
0.01
0.00
0.00
0.00
0.00
0.00
Nd
P
5.75
5.77
5.81
5.82
5.80
5.81
5.81
5.78
5.84
5.85
5.81
5.78
S
0.01
0.01
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
F
1.20
1.23
1.19
1.18
1.16
1.13
1.16
1.16
1.06
1.12
1.20
1.21
Cl
0.12
0.12
0.11
0.10
0.11
0.11
0.12
0.11
0.09
0.10
0.11
0.11
b
0.68
0.64
0.69
0.71
0.73
0.76
0.72
0.72
0.85
0.78
0.69
0.68
OH
75311:255.96
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
#11
#12
#13
CaO
55.70
56.67
56.13
55.91
56.23
56.29
55.93
56.16
56.29
56.30
55.62
56.09
56.36
0.00
0.00
0.02
0.01
0.00
0.03
0.00
0.01
0.00
0.01
0.00
0.00
0.00
MgO
SrO
0.09
0.11
0.11
0.12
0.10
0.11
0.11
0.10
0.13
0.12
0.10
0.10
0.09
MnO
0.11
0.22
0.19
0.13
0.15
0.19
0.18
0.13
0.18
0.10
0.14
0.15
0.15
a
0.00
0.00
0.00
0.10
0.12
0.11
0.00
0.11
0.03
0.06
0.00
0.16
0.00
FeO
0.04
0.00
0.07
0.07
0.05
0.02
0.09
0.05
0.03
0.04
0.00
0.07
0.06
La2O3
0.06
0.06
0.14
0.09
0.14
0.11
0.08
0.06
0.07
0.11
0.06
0.04
0.07
Ce2O3
0.12
0.08
0.20
0.11
0.08
0.10
0.14
0.13
0.07
0.12
0.12
0.08
0.10
Nd2O3
41.73
43.24
41.31
41.92
42.21
41.84
41.84
42.44
42.30
42.10
42.48
42.14
43.08
P2O5
0.10
0.05
0.12
0.13
0.09
0.11
0.10
0.07
0.06
0.12
0.08
0.08
0.09
SO3
Cl
0.76
0.55
0.84
0.77
0.75
0.70
0.79
0.66
0.77
0.57
0.69
0.62
0.74
F
2.03
2.16
2.09
2.25
2.14
2.23
2.07
2.19
2.06
2.23
2.45
2.59
2.02
b
0.83
0.86
0.77
0.72
0.79
0.75
0.81
0.79
0.83
0.79
0.64
0.58
0.88
H2O
Total
101.57 104.00 101.97 102.34 102.84 102.56 102.13 102.89 102.81 102.65 102.39 102.71 103.63
F=O
0.86
0.91
0.88
0.95
0.90
0.94
0.87
0.92
0.87
0.94
1.03
1.09
0.85
Cl=O
0.17
0.12
0.19
0.17
0.17
0.16
0.18
0.15
0.17
0.13
0.16
0.14
0.17
Total
100.54 102.97 100.90 101.22 101.77 101.47 101.08 101.82 101.77 101.58 101.20 101.47 102.61
Ca
9.81
9.71
9.87
9.73
9.76
9.80
9.80
9.73
9.78
9.79
9.60
9.67
9.70
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.01
0.03
0.03
0.02
0.02
0.03
0.03
0.02
0.02
0.01
0.02
0.02
0.02
a
0.00
0.00
0.00
0.01
0.02
0.02
0.00
0.01
0.00
0.01
0.00
0.02
0.00
Fe
La
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
Ce
0.00
0.00
0.01
0.01
0.01
0.01
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.01
0.00
0.01
0.01
0.00
0.01
0.01
0.01
0.00
0.01
0.01
0.00
0.01
Nd
P
5.81
5.85
5.74
5.77
5.79
5.76
5.79
5.81
5.81
5.78
5.80
5.74
5.86
S
0.01
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
F
1.06
1.09
1.09
1.16
1.10
1.14
1.07
1.12
1.06
1.15
1.25
1.32
1.03
Cl
0.21
0.15
0.23
0.21
0.20
0.19
0.22
0.18
0.21
0.16
0.19
0.17
0.20
b
0.73
0.76
0.68
0.63
0.70
0.66
0.71
0.70
0.73
0.70
0.56
0.51
0.77
OH
#14
55.78
0.06
0.13
0.19
0.35
0.03
0.06
0.09
42.59
0.11
0.62
2.09
0.86
102.95
0.88
0.14
101.93
9.68
0.02
0.01
0.03
0.05
0.00
0.00
0.00
5.84
0.01
1.07
0.17
0.76
#15
#16
#17
#18
#19
CaO
56.52
56.10
56.09
56.23
56.09
0.00
0.00
0.03
0.00
0.00
MgO
SrO
0.11
0.10
0.09
0.10
0.09
MnO
0.11
0.13
0.17
0.22
0.18
a
0.01
0.06
0.08
0.08
0.37
FeO
0.02
0.02
0.00
0.05
0.04
La2O3
0.06
0.05
0.04
0.08
0.13
Ce2O3
0.17
0.14
0.11
0.08
0.13
Nd2O3
43.07
42.20
42.63
42.82
41.43
P2O5
0.09
0.11
0.12
0.08
0.13
SO3
Cl
0.78
0.81
0.73
0.77
0.75
F
1.96
1.99
2.05
2.18
2.09
b
0.90
0.85
0.85
0.78
0.80
H2O
Total
103.80 102.56 103.00 103.45 102.23
F=O
0.83
0.84
0.86
0.92
0.88
Cl=O
0.18
0.18
0.16
0.17
0.17
Total
102.80 101.54 101.97 102.36 101.18
Ca
9.73
9.78
9.72
9.67
9.85
0.00
0.00
0.01
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.02
0.02
0.02
0.03
0.03
a
0.00
0.01
0.01
0.01
0.05
Fe
La
0.00
0.00
0.00
0.00
0.00
Ce
0.00
0.00
0.00
0.00
0.01
0.01
0.01
0.01
0.00
0.01
Nd
P
5.86
5.82
5.84
5.82
5.75
S
0.01
0.01
0.01
0.01
0.02
F
1.00
1.02
1.05
1.11
1.08
Cl
0.21
0.22
0.20
0.21
0.21
b
0.79
0.75
0.75
0.68
0.71
OH
28KOM 39B
#35
#36
#37
#38
#39
#40
#41
#42
#43
#44
#45
#46
#47
CaO
56.78
57.12
56.63
56.70
56.87
56.68
56.51
56.44
56.72
56.44
57.23
57.06
57.15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
MgO
SrO
0.07
0.11
0.10
0.12
0.09
0.11
0.10
0.10
0.12
0.11
0.10
0.12
0.10
MnO
0.08
0.22
0.10
0.15
0.13
0.16
0.11
0.16
0.13
0.13
0.13
0.14
0.16
a
0.45
0.05
0.15
0.10
0.18
0.05
0.32
0.06
0.23
0.08
0.25
0.02
0.07
FeO
0.05
0.01
0.03
0.03
0.02
0.07
0.00
0.00
0.02
0.05
0.05
0.01
0.07
La2O3
0.13
0.05
0.00
0.03
0.03
0.05
0.01
0.03
0.00
0.02
0.05
0.03
0.01
Ce2O3
0.14
0.04
0.05
0.01
0.06
0.05
0.04
0.00
0.01
0.06
0.06
0.02
0.09
Nd2O3
43.28
43.34
42.61
42.22
43.50
42.74
42.66
43.00
42.10
42.45
42.76
42.50
42.79
P2O5
0.07
0.06
0.05
0.06
0.03
0.05
0.05
0.09
0.03
0.03
0.07
0.03
0.11
SO3
Cl
0.04
0.20
0.21
0.21
0.21
0.23
0.19
0.18
0.22
0.26
0.20
0.22
0.21
F
3.08
2.97
2.96
2.86
2.97
3.04
3.07
2.69
2.61
2.82
2.80
2.84
2.82
b
0.53
0.54
0.52
0.57
0.54
0.48
0.47
0.68
0.69
0.57
0.62
0.58
0.61
H2O
Total
104.69 104.71 103.39 103.03 104.63 103.70 103.52 103.44 102.88 103.03 104.33 103.56 104.18
F=O
1.30
1.25
1.25
1.20
1.25
1.28
1.29
1.13
1.10
1.19
1.18
1.20
1.19
Cl=O
0.01
0.04
0.05
0.05
0.05
0.05
0.04
0.04
0.05
0.06
0.05
0.05
0.05
Total
103.39 103.41 102.10 101.78 103.33 102.37 102.19 102.27 101.73 101.79 103.11 102.32 102.95
Ca
9.54
9.59
9.64
9.72
9.54
9.60
9.58
9.63
9.79
9.67
9.71
9.73
9.69
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.01
0.03
0.01
0.02
0.02
0.02
0.01
0.02
0.02
0.02
0.02
0.02
0.02
a
0.06
0.01
0.02
0.01
0.02
0.01
0.04
0.01
0.03
0.01
0.03
0.00
0.01
Fe
La
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Ce
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
Nd
P
5.74
5.75
5.73
5.72
5.77
5.72
5.72
5.80
5.74
5.74
5.73
5.73
5.73
S
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.01
0.00
0.00
0.01
0.00
0.01
F
1.53
1.47
1.49
1.44
1.47
1.52
1.54
1.36
1.33
1.43
1.40
1.43
1.41
Cl
0.01
0.05
0.06
0.06
0.06
0.06
0.05
0.05
0.06
0.07
0.05
0.06
0.06
b
0.46
0.47
0.46
0.50
0.47
0.42
0.41
0.60
0.61
0.50
0.54
0.51
0.53
OH
#48
57.12
0.00
0.09
0.15
0.02
0.02
0.04
0.03
43.29
0.04
0.20
2.83
0.61
104.45
1.19
0.04
103.21
9.64
0.00
0.01
0.02
0.00
0.00
0.00
0.00
5.77
0.00
1.41
0.05
0.54
#49
#50
#51
CaO
56.79
56.87
57.13
0.00
0.00
0.00
MgO
SrO
0.08
0.11
0.10
MnO
0.12
0.13
0.16
a
0.03
0.04
0.00
FeO
0.00
0.02
0.01
La2O3
0.03
0.07
0.03
Ce2O3
0.00
0.05
0.00
Nd2O3
44.14
43.11
42.88
P2O5
0.10
0.08
0.05
SO3
Cl
0.25
0.23
0.19
F
2.85
2.83
2.87
b
0.61
0.60
0.59
H2O
Total
104.99 104.13 103.98
F=O
1.20
1.19
1.21
Cl=O
0.06
0.05
0.04
Total
103.74 102.89 102.73
Ca
9.48
9.63
9.68
0.00
0.00
0.00
Mg
0.01
0.01
0.01
Sr
Mn
0.02
0.02
0.02
a
0.00
0.00
0.00
Fe
La
0.00
0.00
0.00
Ce
0.00
0.00
0.00
0.00
0.00
0.00
Nd
P
5.82
5.77
5.74
S
0.01
0.01
0.01
F
1.41
1.41
1.44
Cl
0.07
0.06
0.05
b
0.53
0.53
0.51
OH
28KOM39A
#1
#2
#3
#4
#5
#6
#7
#8
#9
#10
CaO
56.28
56.29
56.19
56.75
55.90
56.28
56.47
56.27
56.60
56.38
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
MgO
SrO
0.08
0.09
0.09
0.06
0.11
0.09
0.08
0.09
0.10
0.06
MnO
0.14
0.11
0.03
0.03
0.09
0.13
0.09
0.07
0.09
0.09
a
0.00
0.04
0.01
0.04
0.00
0.05
0.00
0.00
0.06
0.08
FeO
0.00
0.07
0.06
0.00
0.00
0.04
0.02
0.01
0.00
0.00
La2O3
0.02
0.02
0.06
0.03
0.00
0.03
0.06
0.05
0.01
0.02
Ce2O3
0.06
0.03
0.04
0.00
0.02
0.05
0.01
0.00
0.00
0.01
Nd2O3
42.49
42.27
42.83
42.34
42.38
41.76
42.48
42.66
41.68
41.92
P2O5
0.06
0.04
0.07
0.08
0.13
0.06
0.09
0.04
0.08
0.02
SO3
Cl
0.15
0.18
0.15
0.15
0.26
0.20
0.18
0.09
0.18
0.17
F
2.52
2.60
2.83
2.88
2.55
2.55
2.81
2.95
2.52
2.54
b
0.76
0.71
0.61
0.58
0.72
0.72
0.61
0.56
0.74
0.74
H2O
Total
102.56 102.45 102.95 102.93 102.16 101.95 102.89 102.78 102.06 102.01
F=O
1.06
1.09
1.19
1.21
1.07
1.07
1.18
1.24
1.06
1.07
Cl=O
0.03
0.04
0.03
0.03
0.06
0.04
0.04
0.02
0.04
0.04
Total
101.46 101.32 101.72 101.69 101.03 100.83 101.67 101.52 100.96 100.90
Ca
9.73
9.74
9.61
9.72
9.68
9.81
9.68
9.62
9.87
9.82
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Mg
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Sr
Mn
0.02
0.02
0.00
0.00
0.01
0.02
0.01
0.01
0.01
0.01
a
0.00
0.01
0.00
0.00
0.00
0.01
0.00
0.00
0.01
0.01
Fe
La
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Ce
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Nd
P
5.81
5.78
5.79
5.73
5.80
5.75
5.75
5.76
5.74
5.77
S
0.01
0.01
0.01
0.01
0.02
0.01
0.01
0.00
0.01
0.00
F
1.29
1.33
1.43
1.46
1.30
1.31
1.42
1.49
1.30
1.30
Cl
0.04
0.05
0.04
0.04
0.07
0.05
0.05
0.02
0.05
0.05
b
0.67
0.62
0.53
0.50
0.63
0.63
0.53
0.49
0.65
0.65
OH
a
All Fe as Fe2+; bCalculated assuming the (F,Cl,OH) site is filled; For descriptions of samples see Table 1
#11
#12
55.98
56.19
0.00
0.00
0.11
0.10
0.06
0.10
0.01
0.05
0.00
0.01
0.01
0.04
0.03
0.04
42.39
42.49
0.08
0.06
0.21
0.21
2.38
2.42
0.82
0.80
102.09 102.50
1.00
1.02
0.05
0.05
101.04 101.43
9.74
0.00
0.01
0.01
0.00
0.00
0.00
0.00
5.83
0.01
1.22
0.06
0.72
9.74
0.00
0.01
0.01
0.01
0.00
0.00
0.00
5.82
0.01
1.24
0.06
0.71
APPENDIX 2
Rsults of LA-ICPMS analyses of apatites.
2#
71
356
82
539
203
21
257
39
240
45
118
15
86
11
3#
84
520
104
662
236
25
287
43
263
52
138
18
102
14
4#
77
377
77
513
198
20
246
37
223
42
107
14
77
10
5#
841
2665
263
1221
305
32
324
46
281
53
135
17
96
12
6#
106
250
38
208
72
8
115
19
135
30
84
11
66
10
66814 EKSTR
7#
8#
9#
27
50
74
105 188 308
22
39
66
159 261 430
68
97
149
8
10
15
117 153 204
20
25
32
138 169 210
30
37
44
85
104 121
11
14
16
65
80
93
9
12
13
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
1#
407
2107
222
1188
351
37
391
59
369
72
193
25
149
20
10# 11#
422
19
1402 82
119
18
547 128
141
60
13
7
183 106
28
17
183 122
39
27
106
76
14
10
80
57
11
9
12#
24
89
18
125
55
7
98
16
112
25
69
9
52
8
13#
23
106
25
179
75
8
123
20
134
29
82
11
59
9
14# 15# 16#
14
299
24
62 1139 107
14
99
24
104 473 166
45
128
71
6
12
8
84
159 115
14
24
18
96
155 124
21
33
27
58
88
74
8
11
10
44
67
55
6
9
8
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
29JREK9
1#
2#
3#
4#
5#
6#
7#
8#
9# 10# 11# 12# 13# 14#
1535 2697 2018 3340 2787 1829 2882 2193 347 2151 1332 2698 2663 2151
3215 5347 4514 6993 5636 4328 5835 4430 1009 4249 3296 5695 5749 4447
217 382 323 529 386 301 399 289
95
274 228 379 388 298
883 1418 1261 1918 1614 1207 1528 1138 421 1094 908 1506 1583 1162
165 237 230 321 283 211 252 193 101 184 165 245 260 198
20
26
27
34
25
24
28
22
14
21
19
24
26
22
170 231 232 304 290 213 238 188 135 180 167 215 235 193
22
30
30
39
38
27
30
24
20
23
22
26
29
26
119 179 173 236 248 161 174 134 129 130 133 147 171 155
23
36
34
48
52
32
36
26
27
25
26
29
34
31
57
96
86
130 142
84
93
66
72
65
69
75
89
82
7
13
11
17
19
11
12
8
10
8
9
10
12
11
40
74
63
97
110
63
69
46
56
47
52
55
65
64
5
10
8
14
15
9
9
7
8
7
7
7
9
9
15#
2310
5205
362
1381
225
25
198
26
152
30
81
11
62
9
16#
2249
5186
364
1411
235
26
219
29
168
33
89
12
68
9
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
29JNUK1
1#
2#
3#
4#
5#
6#
7#
8#
9# 10# 11# 12# 13#
2010 1948 2959 2815 2316 3498 3117 2247 2284 802 1993 2688 2960
4523 4457 6661 6147 5411 8010 7254 5498 5451 2216 5113 6369 6872
366 356 562 482 385 739 703 382 430 160 343 484 629
1449 1399 1869 1838 1564 2108 2012 1585 1569 648 1368 1779 1811
256 242 304 302 263 331 321 263 258 117 227 287 284
29
27
36
31
29
35
33
29
28
14
27
32
32
271 234 291 275 247 277 257 234 228 118 210 262 253
39
31
40
35
32
34
29
29
28
17
27
34
33
258 181 260 211 196 197 158 164 161 106 164 211 203
57
36
56
42
39
39
29
31
31
22
33
43
42
161
95
161 111 103 104
70
78
79
61
86
115 114
22
12
22
15
13
14
9
10
10
9
12
15
15
128
69
132
86
79
78
48
55
58
52
67
89
93
18
10
19
12
11
11
6
7
8
7
9
12
13
15#
2398
5629
393
1508
240
27
220
29
181
37
104
14
82
11
16#
3200
7446
513
1913
291
31
237
28
153
30
78
10
56
8
14#
2465
6091
487
1623
260
30
221
29
164
32
81
11
60
8
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
KUJ5044 80.10
1#
2#
3#
4#
5#
6#
7#
8#
9#
2986 2629 2711 3155 2826 1481 2753 2309 55
6072 5525 5689 6552 5878 3336 5783 5110 250
571 418 442 542 452 261 406 359
49
1792 1685 1722 1940 1762 1099 1629 1461 293
289 287 295 321 292 210 264 244 103
32
31
32
35
31
24
29
27
13
261 274 280 294 277 216 238 230 141
34
36
37
39
37
29
31
30
21
206 220 228 236 224 181 185 178 132
42
44
45
48
46
37
37
36
26
113 121 122 130 125
99
97
96
71
15
16
17
17
17
13
13
13
9
89
96
99
105 101
78
76
77
54
12
14
14
15
15
11
11
11
7
10#
74
286
56
323
111
14
149
22
141
29
78
10
60
9
11# 12# 13# 14# 15# 16#
86
264 377 1996 104 569
425 1333 1497 4537 501 1977
78
117 126 318
66
157
434 563 568 1294 363 712
136 144 137 226 115 166
17
17
16
24
14
19
166 163 153 207 143 178
24
23
22
28
21
26
154 149 136 169 133 163
31
30
28
34
27
33
84
84
77
94
73
89
12
11
10
13
10
12
67
68
63
78
57
73
9
10
8
11
8
11
1#
La
97
Ce 379
Pr
84
Nd 511
Sm 138
Eu
15
Gd 135
Tb
16
Dy 91
Ho 16
Er
37
Tm 4
Yb 21
Lu
3
2#
118
414
83
481
120
12
115
15
81
14
31
4
21
3
3#
30
113
22
132
40
5
60
9
60
11
22
2
12
1
68313 120.20
4#
5#
6#
7#
8#
9# 10# 11# 12# 13# 14# 15# 16# 17#
326 269 332 326 214 220 191 308 436 372 455 320 221 200
1374 982 1184 1210 1093 786 609 1039 2273 1064 2361 1280 1560 1384
243 212 225 219 150 149 120 193 261 198 234 176 191 165
1411 1231 1268 1236 834 850 662 1086 1463 1059 1166 903 1148 990
330 299 284 286 187 192 152 250 333 236 237 187 292 245
32
28
27
26
19
19
16
25
31
22
23
18
29
24
254 233 212 215 138 144 139 190 250 176 176 143 225 187
27
24
23
23
15
15
15
20
27
18
19
15
25
20
134 119 110 112
70
74
76
98
129
89
91
76
120
97
22
20
18
19
12
12
13
16
21
15
15
13
21
17
56
48
45
47
29
30
30
40
53
34
35
29
48
41
7
6
6
5
4
4
3
5
7
5
5
4
6
5
44
36
32
35
19
21
20
27
41
25
26
21
33
30
6
5
4
5
3
3
3
4
6
3
4
3
5
4
1#
La
112
Ce 388
Pr
77
Nd 447
Sm 114
Eu
12
Gd 105
Tb
12
Dy 70
Ho 13
Er
30
Tm 4
Yb 22
Lu
3
2#
63
288
61
340
92
10
89
11
59
11
29
4
21
3
3#
112
460
93
519
135
15
134
17
94
17
45
6
31
4
4#
57
277
71
496
167
22
179
22
122
23
57
7
42
6
5#
45
217
56
392
138
18
145
18
99
18
45
6
33
5
6#
128
499
109
637
177
22
165
21
115
21
51
7
40
6
67306 250.61b
7#
8#
9#
89
69
58
374 332 271
86
83
68
540 547 448
166 168 150
21
21
19
160 165 154
20
20
19
111 115 104
20
21
19
53
53
50
7
7
6
39
41
36
6
5
5
10#
61
281
70
469
156
20
166
21
115
22
54
7
43
6
11#
57
263
66
454
150
19
160
20
113
21
53
7
38
5
12#
133
435
86
482
134
17
132
16
91
15
41
5
29
4
13#
51
198
46
292
100
14
103
13
73
14
35
4
23
3
14#
144
465
95
535
152
20
154
19
104
19
48
6
34
5
15#
40
180
47
320
116
17
128
16
90
17
42
5
32
4
1#
La
15
Ce
84
Pr
21
Nd 149
Sm 40
Eu
6
Gd 39
Tb
4
Dy 20
Ho
4
Er
10
Tm 1
Yb
7
Lu
1
2#
8
45
12
91
27
5
29
3
16
3
7
1
8
1
3#
4
28
8
77
31
6
39
4
23
5
14
2
9
2
4#
5
35
11
92
36
8
45
5
27
5
15
2
12
2
5#
24
130
32
222
58
8
51
5
28
6
14
2
10
2
6#
23
131
32
226
59
8
53
5
27
5
13
2
10
2
75316 328.50
7#
8#
9#
22
32
14
125 166
84
31
40
22
220 258 164
59
64
48
7
9
7
56
57
55
6
6
6
26
30
32
5
6
6
14
14
16
2
2
2
10
11
10
2
2
2
10#
35
177
42
294
89
11
91
11
54
11
29
4
21
3
11#
93
411
88
567
140
17
134
15
81
15
40
4
28
4
12#
139
571
114
659
152
18
132
14
73
14
36
4
25
4
13#
5
36
11
105
56
6
72
9
55
11
29
3
19
3
15#
30
179
49
379
126
12
136
15
80
16
41
5
30
4
16#
35
178
46
322
102
10
107
12
64
13
31
4
23
4
1#
La
135
Ce 835
Pr
102
Nd 619
Sm 176
Eu
28
Gd 177
Tb
21
Dy 119
Ho 23
Er
60
Tm 8
Yb 43
Lu
7
2#
152
935
112
673
195
31
192
24
132
26
67
9
49
7
3#
217
1322
156
905
253
41
238
30
167
32
83
11
61
9
4#
162
971
120
727
207
32
207
25
141
28
70
9
50
7
5#
141
688
104
625
178
28
180
22
124
24
62
8
44
7
6#
117
574
114
741
224
33
215
27
153
30
75
10
55
8
75311 255.96
7#
8#
9#
169
28
43
1081 162 202
136
45
48
812 342 329
226 129 104
36
14
13
209 147 107
26
18
13
145 102
72
27
20
14
69
52
36
9
7
5
53
39
27
7
6
4
10#
84
412
87
566
177
25
178
22
122
23
59
8
45
6
11#
127
849
112
683
193
31
186
22
123
24
63
8
46
7
12#
147
937
123
752
210
34
202
25
136
26
67
9
49
7
13# 14# 15#
116 148
88
633 1052 359
100 126
62
625 755 247
177 214
72
28
35
10
172 202
57
21
24
7
116 138
38
22
27
6
57
69
18
7
9
3
43
53
13
6
8
2
16#
132
877
115
701
200
33
188
23
127
25
64
8
49
7
1#
8
34
8
55
25
4
38
6
36
8
22
3
19
3
2#
6
26
6
38
18
3
29
4
28
6
18
2
14
2
3#
4
17
4
34
18
3
34
5
33
8
21
3
17
3
4#
3
15
4
28
15
3
27
4
29
7
19
2
15
2
5#
8
36
8
58
26
4
39
6
38
8
22
3
19
3
6#
9
37
8
53
24
4
34
5
32
7
20
3
17
3
28KOM 39A
7#
8#
9#
8
8
6
32
35
25
7
8
6
50
58
43
23
27
21
4
4
3
35
41
33
5
6
5
33
39
33
7
8
7
20
24
19
3
3
3
16
19
16
3
3
2
10#
4
20
5
34
18
3
29
5
30
7
19
2
15
2
11#
5
24
6
39
18
3
32
5
31
7
19
3
15
2
12#
7
28
6
41
20
3
32
5
31
7
19
3
15
2
13#
6
24
5
40
19
3
31
5
32
7
20
3
17
3
16#
5
21
5
34
18
3
28
5
31
6
18
2
14
2
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
14#
5
36
11
106
51
6
71
9
50
11
28
4
19
3
14#
6
27
6
47
23
4
37
5
36
8
23
3
18
3
15#
7
31
7
47
22
3
35
5
33
7
21
3
16
3
APPENDIX 3
Detection limits for microprobe and LA-ICPMS analyses of apatites.
Detection limits for microprobe analyses
wt %
P
0.07
Ca
0.05
Mg
0.02
F
0.06
Cl
0.03
S
0.03
Mn
0.04
Fe
0.08
Sr
0.02
La
0.05
Ce
0.05
Nd
0.08
Detection limits for LA-ICPMS analyses
ppm
min
max
(average)
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
0.06
0.09
0.04
0.30
0.18
0.04
0.13
0.03
0.09
0.02
0.08
0.02
0.10
0.02
0.01
0.01
0.01
0.08
0.07
0.02
0.05
0.01
0.04
0.01
0.04
0.01
0.05
0.01
0.17
0.24
0.08
0.60
0.38
0.09
0.23
0.05
0.19
0.04
0.16
0.04
0.24
0.05

The Tjårrojåkka Apatite-Iron and Cu (

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