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GEOCHEMISTRY AND GEOCHRONOLOGY OF APATITE AND ZIRCON FROM

Rebecca N. Babiak1, Stephen Delgaudio Jr.1, John M. Hanchar1, Fernando Tornos2, Martin J Whitehouse3

1. Department of Earth Sciences, Memorial University of Newfoundland, St. John’s NL A1B 3X5, Canada,
2. Instituto de Geociencias (CSIC-UCM), 28040 Madrid, Spain
3Department of Geosciences, Swedish Museum of Natural History, SE-104 05 Stockholm, Sweden

Abstract: The Chilean Iron Belt in the Atacama Desert offers a unique opportunity to investigate both
Iron Oxide Copper Gold (IOCG) and Magnetite Apatite (MtAp) deposits in a geographically concentrated
setting. This unique setting allows for the comparison of apatite and zircon between MtAp and IOCG
deposits to better constrain differences and similarities between age, magma source, and fluid composition
associated with the different deposits types. Zircon from the Cenozoic El Laco and apatite from El Laco
and Incahuasi MtAp deposit in the Central Volcanic Zone are also included for comparison. Major and
minor elements in both minerals were analyzed in situ by EPMA, while trace element compositions and U-
Pb ratios were measured in situ by LA-ICPMS. Sm-Nd and Lu-Hf isotopes were measured in situ by LA-
MC-ICPMS in the same regions as the trace elements and U-Pb. U-Pb geochronology of the El Laco zircon
samples were done by SIMS due to their young age and their high U/Pb ratios. Ore apatites from the MtAp
deposits contain 0.3-3 REE wt%, multiple phases of Cl-fluid alteration coupled with S and REE enrichment,
and a general enrichment in LREE and HREE compared to their respective host. εNd values are negative
with respect to the Cenozoic MtAp deposits and positive with respect to the Cretaceous MtAp deposits,
indicating that crustal contamination may not be a necessary process in the formation of MtAp deposits.
Future zircon analysis will better constrain age, magma source, and oxidation state of host and ore samples
in both deposit types.

Keywords: MtAp, IOCG, apatite, zircon, Sm-Nd, U-Pb, Lu-Hf, trace elements

1. Introduction Iron oxide-bearing deposits under the “IOCG clan” classification can contain
economically significant amounts of iron +/- copper +/- gold +/- uranium +/- rare earth elements, making
these systems a priority research topic. However, differing mineralogy and deposit types have rendered an
all-encompassing genetic model implausible. The Atacama Desert in northern Chile boasts varying types
of IOCG clan deposit types including Paleocene to Miocene Cu- +/- Au +/- Mo porphyry systems (e.g.,
Chuquicamata, La Escondida (Charrier et al., 2007 and references therein) many of which are associated
with the Domeyko fault system, Cretaceous IOCG sensu stricto deposits (Punta del Cobre district)
associated with the Atacama fault system (AFS), and MtAp deposits of Cenozoic age and ~50 MtAp
deposits containing >100 Mt Fe in the Cretaceous Iron Belt (CIB), occurring on the peripheries of the AFS,
making Chile an ideal location for studies involving iron- +/- apatite +/- copper- +/- gold-bearing systems.
IOCG deposits sensu stricto occur globally in varying crustal settings, with fluid type/metal source
generating the most discussion. Three main fluid type/metal source models exist: 1) magmatic fluids/metals
are released from a magma body; 2) basinal fluids/metals are leached from wallrock; or 3) metamorphic
fluids (expelled during pluton emplacement)/metals sourced from wall rock (Williams et al., 2005; Porter,
2010; Barton, 2014). Magnetite-apatite (MtAp) deposits, the copper-poor end member of the IOCG clan,
are also highly debated with three different formation hypotheses: 1) complete metasomatic replacement of
host rocks by hydrothermal fluids of magmatic or connate derivation (e.g., Sillitoe and Burrows (2002); 2)
coalescence of buoyant microphenocrysts of magnetite and later cementation by hydrothermal magnetite
(e.g., Knipping et al., 2015); or, 3) crystallization of Fe-P-rich immiscible melts in a magmatic-
hydrothermal environment (e.g., Tornos et al., 2017).

2. Objectives and Samples The objectives of this study are twofold; firstly, to broadly interpret the
formation of MtAp deposits using apatite trace element geochemistry and Sm-Nd isotopes and to draw
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comparisons within the MtAp deposit class, and secondly, to use zircon U-Pb geochronology to constrain
ore emplacement, and to use zircon trace element geochemistry and Lu-Hf isotopes to distinguish MtAp
deposits from IOCG deposits. Four MtAp deposits, and one apatite-only deposit (for comparison) were
sampled for the apatite study, including El Laco and Incahuasi in the Cenozoic Central Volcanic Zone, the
most modern analogues of these systems. These MtAp deposits are generally hosted in andesite and contain
massive magnetite + apatite +/- actinolite and are pervasively altered by alkali-calcic +/- sodic +/- steam
alteration. The main objective of the present study are: 1) to use the geochemical data of the apatites from
the unaltered host rock (where possible), altered host rock, and ore, from Cenozoic and Cretaceous MtAp,
paired with Sm-Nd isotopes to understand: a) crustal contamination; b) fluid composition; and c)
mobilization of cations and REEs in the transporting fluids, leading to a broad interpretation of MtAp
deposit formation and comparison of these deposits through time; 2) U-Pb geochronology on the El Laco
host rock zircon crystals will constrain the age of the MtAp deposit, while Lu-Hf isotopes and trace
elements will provide insight into source and oxidation state of host (Ballard et al., 2002; Banik et al., 2017).
Additionally, one IOCG deposit (Tropezon) was sampled for the zircon study. Within the Cerro del Pingo
plutonic complex, Tropezon is hosted in andesitic rock showing, fault controlled, chlorite-sericite-epidote-
calcic alteration. Cu-Mo-Au mineralization is associated with pervasive Ca-Fe-K alteration of a host quartz
diorite (Tornos et al., 2010). U-Pb geochronology of zircon from both the host quartz diorite and the Cu-
Mo-Au mineralized ore will better constrain ore mineralization, while Hf isotopes and trace elements
analysis will be used to see a difference between the ore and host within the deposit. Zircon analysis of El
Laco and Tropezon will allow for a direct comparison between MtAp and IOCG deposits.

3. Analytical Methods Epoxy mounts of apatite and zircon separates were examined with
cathodoluminescence to reveal internal structures and zoning before both EPMA, LA-ICPMS, and LA-
MC-ICPMS analysis at Memorial University. Heavy minerals were separated using standard techniques,
including heavy liquid separation and a Frantz magnetic separator. Major and minor element compositions
of apatite crystals were measured using a JEOL JXA-8230 SuperProbe electron probe microanalyzer
(EPMA), trace elements were measured using a Finnigan Element XR high-resolution, double-focusing
magnet sector-inductively coupled-plasma mass spectrometer (HR-ICP-MS), coupled to a GeoLas 193 nm
Excimer laser system, and Sm-Nd isotope compositions were obtained by a ThermoFinnigan Neptune MC-
ICPMS, coupled to the same laser. Zircon mounts were dated and analyzed for trace elements by LA-
ICPMS and Hf isotope ratios were measured using LA-MC-ICPMS at the same facility. Due to the young
age and high U-Pb ratios in the Cenozoic zircon samples, a Cameca ims1280 large-format, high mass
resolution ion microprobe at the Swedish Museum of Natural History (NordSIM Facility) was used for U-
Pb geochronology.

4. Results and Discussion Preliminary results indicate ore apatites containing up to 0.3-3 wt% REE, are
evidence of one to four growth/ fluid alteration events, which varies depending on the deposit, and an
enrichment in REE and S in Cl-rich zones leading to the interpretation that Cl-rich fluids can mobilize and
carry REE and S (Fig. 1). Ores are enriched in both LREE and HREE when compared to their host rock
and there are consistently geochemical differences between the Cenozoic- deposits and the Cretaceous-
aged deposits. εNd values for El Laco and Incahuasi are -4 to -5, and -2 to -3 respectively, while εNd values
for Los Colorados and Carmen di Fierro are +3 to +5 and +3 to +6 respectively, indicating a greater degree
of crustal contamination in the Cenozoic-aged MtAp deposits and a greater mantle contribution in the
Cretaceous deposits. Apatite discrimination plots from the literature, most notably those by Belousova et
al. (2002) do not constrain the ore apatites from this study to strictly the “iron ores” fields. In addition, the
Mn-V-Mg ternary discriminant plot from Mao et al. (2016) used to distinguish IOCG and Kiruna-type (aka
MtAp) deposits displays a lack of conformity to the Kiruna-type field. U-Pb zircon geochronology by SIMS
from the El Laco host rock gave an age of ~2 Ma, constraining the age of the deposit to 2 Ma or younger.
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Rock/Chondrites Anders+Greevasse 1989-REEs

10000

1000

100

10
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Figure 1. CL image of grain 33 from sample INC-15-01 (Incahuasi ore) and X-ray maps of the same grain
for elements Cl, F, Fe, Nd, La, and S. Blue areas indicate areas of relative low concentrations and warmer
colours (red, pink) indicate areas of relative high concentrations. Green and blue circles indicate where
analysed by LA-ICPMS. The darker grey zone is enriched in Cl, Nd, La, and S as displayed by the X-ray
maps and enriched in all LREE and MREE, concentrations of HREE are similar, as displayed by the REE
diagram normalized to chrondrite values of Anders and Grevesse (1989). The ∑REE concentration between
the two zones differs by ~1 wt% (2.81(dark zone) vs. 1.82 (light zone) ∑REE wt%.

5. Conclusions Preliminary apatite results suggest that a complex fluid alteration history plays a
significant role to the formation of REE-enriched MtAp deposits and that sulphur is present but is not able
to form sulphides. εNd values suggest that magma source environments have evolved through time from a
mantle source to a continental crust source. Future work will include zircon geochronology, trace element
analysis, and Hf isotopes. The zircon data along with additional apatite geochemistry and Sm-Nd isotope
concentrations will aid in the discussion and the implications for a genetic model for MtAp formation and
comparisons with other deposits within the IOCG clan.
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Acknowledgements The study was funded by a NSERC Discovery Grant (JMH) and supported by SEIDI
project 2014-55949-R (FT). We thank Compañía Minera del Pacífico (CMP) especially Rodrigo Munizaga for
permission to sample at at El Laco and Los Colorados.

References
Anders, E., and Grevesse, N., 1989, Abundances of the elements: Meteoritic and solar. Geochimica and Cosmochimica
Acta, v. 53, pp. 197-214.
Ballard, J.R., Palin, M.J., and Campbell, I.H., 2002, Relative oxidation states of magmas inferred from Ce (IV)/Ce
(III) in zircon: application to porphyry copper deposits of northern Chile: Contributions to Mineralogy and
Petrology, v. 144, p. 347-364
Banik, T.J., Coble, M.A., and Miller, C.F., 2017, Porphyry Cu formation in the middle Jurassic Yerington batholith,
Nevada, USA: Constraints from laser Raman, trace element, U-Pb age and oxygen isotope analyses of zircon:
Geosphere, p. GES01351.
Barton, M., 2014, Iron oxide (-Cu-Au-REE-P-Ag-U-Co) systems: Treatise on Geochemistry, v. 13, p. 515-541.
Belousova, E.A., Griffin, W. L., O’Reilly, S.Y., and Fisher, N.I., 2002. Apatite as an indicator mineral for mineral
exploration: trace element compositions and their relationship to host rock type. Journal of Geochemical
Exploration, v. 76, pp. 45-69.
Charrier, R., Pinto, L., and Rodrigues, M.P., 2007. Tectonostatigraphic evolution of the Andean Orogen in Chile in:
Moreno, T., and Gibbons, W., (eds) The Geology of Chile. The Geological Society, London, 21–114.
Knipping, J.L., Bilenker, L.D., Simon, A.C., Reich, M., Barra, F., Deditius, A.P., Lundstrom, C, Bindeman, I., and
Munizaga, R., 2015. Giant Kiruna-type deposits form by efficient flotation of magmatic magnetite suspensions.
Geology, v. 43, pp. 591-594.
Mao, M., Rukhlov, A.S., Rowins, S.M., Spence, J., and Coogan, L.A., 2016. Apatite trace element compositions: A
robust new tool for mineral exploration. Economic Geology, v. 111, pp. 1187-1222.
Porter, T., 2010, Current understanding of iron oxide associated-alkali altered mineralised systems. Part 1—An
overview: Hydrothermal Iron Oxide copper–gold and Related Deposits: A Global Perspective, v. 3, p. 5-32.
Sillitoe, R.H., and Burrows, D.R., 2002. New field evidence bearing on the origin of the El Laco magnetite deposit,
northern Chile. Economic Geology, v. 97, pp. 1101-1109.
Tornos, F., Velasco, F., and Hanchar, J.M., 2017. The magmatic to magmatic-hydrothermal evolution of the El Laco
deposit (Chile) and its implications for the genesis of magnetite-apatite deposits. Economic Geology, v 112, pp.
1-34.
Tornos, F., Velasco, F., Barra, F., and Morata, D., 2010, The Tropezón Cu–Mo–(Au) deposit, Northern Chile: the
missing link between IOCG and porphyry copper systems? Mineralium Deposita, v.45, p. 313-321.
Williams, P.J., Barton, M.D., Johnson, D.A., Fontboté, L., De Haller, A., Mark, G., Oliver, N.H., and Marschik, R.,
2005, Iron oxide copper-gold deposits: Geology, space-time distribution, and possible modes of origin:
Economic Geology, p. 371-405.