Investigation of the rare elements from the

porphyry copper deposits in Romania

Project PN-II-RU-PD-2011-3-0172

Scientific report
(abstract)

Project Director,
Dr. Mihaela Cioac

2013

I. Introduction

Porphyry copper deposits are the world's most important source of Cu but other
elements such as Mo, Au, Ag, Re, Sn, W, PGE, In, Se, Te, Bi could be recovered from these
deposits as subproducts or co-products of Cu extraction (Berger et al., 2008; Sinclair, 2007).
In this project, the main focus is on the trace elements contents in porphyry copper
deposits from Romania. Other geological aspects studied concern: the host minerals, the
spatial distribution of the selected trace elements in the studied deposits, the preferential
association between these elements with the type of host rock and type of hydrothermal
alterations and the geochemical conditions of transport and precipitation.
Seven deposits were investigated in this study: six from the Metallogenetic
Subprovince of South Apuseni Mts. (Roia Poieni, Bucium-Tarnia, Valea Morii, Colnic,
Rovina, Bolcana) and one (Moldova Nou from the Laramian magmatism of the Banatite
province in the Southern Carpathians.
Several investigation methods were used in this project in order to perform the
targeted objectives: optical microscopy, electron micro probe analyses (EMPA), inductively
coupled plasma mass spectrometry (ICP-MS), atomic absorbtion spectrometry (AAS), Laser
Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS), microthermometry
on fluid inclusions.

II. Geological background

Metaliferi Mts are caracterized by the existence of numerous types of ore deposits and
occurences, including porphyry copper, hydrothermal veins and intrusive breccia types. All
these are associated with volcanic and subvolcanic complexes, developed during the Neogene
magmatism. Fifteen porphyry copper deposits are known in this area. Most of them are
classified by Botinescu (1984) as Cu-Au type (Valea Morii, Musariu, Bolcana, Rovina, Voia,
Tlagiu, Larga, Trmpoiele, Valea Tisei, Muncceasca, and Bucium-Tarnia) and Cu-Mo
(Au) (Deva, Roia Poieni). Halga et al. (2010) classified the Colnic and Cireata ore deposits
as Au-Cu type. Two main petrographic types of host rocks are known: amphibole-bearing
microdioritic/andesitic rocks, at Roia Poieni, Tarnita, Bolcana and Colnic, and amphibolepyroxene-bearing quartz-dioritic/microdioritic rocks, at Valea Morii and Rovina.
The alteration-mineralization zonality is in accordance with the diorite type model
(Borco et al., 1998). The ore mineral assemblage from all deposits include magnetite,
2

chalcopyrite, pyrite, gold and subordinate bornite, rarely molybdenite (Roia Poieni, Bolcana,
Rovina, Colnic, Bucium-Tarnia), pyrrothite (Bucium-Tarnia, Colnic, Bolcana), rutile (Valea
Mori) etc. (Borco et al., 1984; Milu et al., 2004, Vlad, 1983; Berbeleac, 1985, Halga et al.,
2010, Andr-Mayer et al., 2001) in the inner part of the deposit, characterized by potassic
alteration. Phyllic alteration, with pyrite as the main metallic mineral, overprints the margin of
the potassic zone of all deposits. Polymetallic Au-Ag veins cross most of the investigated
porphyry copper deposits (Roia Poieni, Bucium-Tarnia, Bolcana, Valea Mori), forming a
system of veins with pyrite, sphalerite, galena, tennantite-tetrahedrite, chalcopyrite, native
gold and others in the mineral assemblage.
The porphyry copper deposits from Metaliferi Mountains are associated with the Miocene magmatism. The geochemical signatures of magmatic-volcanic products reflects a
gradual evolution, from normal calc-alkaline for 14.8-11 Ma products and adakitic-like
calc-alkaline geochemistry for 12.6-7.4 Ma products. The latest magmatic products apears as
few small bodies with alkaline features. (Rou et al., 2004). The genesis of the magma is
related to decompresional melting of a heterogenous source, placed at the crust-lithospheric
mantle boundary, but mixing with asthenospheric melts is not excluded (Rou et al., 2004).
Some porphyry Cu mineralized bodies (Moldova Nou, Ciclova, opot, TeregovaLpunicel) are known in Banat Mts., part of the Banatitic Magmatic and Metallogenetic Belt
(Vlad, 1983; Ciobanu et al, 2002).
Moldova Nou deposit (72 Ma) is one of the largest Cu deposit from Romania with
500 Mt at 0,35% Cu (USGS report, 2013). This deposit is located in Sasca-Moldova Nou
metallogenic district (Vlad, 1983) and is related to the Suvorov calc-alkaline quartz-dioritic
subvolcanic body (2.5 km in length and 100-300m in width). Copper mineralization of
Moldova Nou consists of magnetite, chalcopyrite and pyrite in the potassic alteration zone
and pyrite, chalcopyrite, molibdenite, subordinate tetrahedrite, sphalerite and anhydrite, in the
phyllic alteration zone from the upermost part of deposit (Vlad, 1983). A supergene alteration
(with covellite, bornite, chalcocite malachite, azurite, melanterite and crysocole) was
described by Vlad (1983).

III. Trace elements geochemistry

One hundred bulk mineralized samples were analyzed in order to obtain information
about the mineralogy, petrography and geochemistry of the investigated porpphyry type
deposits. The samples show different degrees of hydrothermal alteration, from potassic to
3

phyllic and argillic. The mineralization in the potassic zone of all investigated deposits is
dominated by the assemblage chalcopyrite-pyrite-magnetite (hematite) bornite (covellite).
Other identified minerals are: gold (at Colnic, Rovina, Bolcana, Moldova Nou), molybdenite
(Colnic, Rovina, Moldova Nou), unidentified REE minerals (Moldova Nou).
The trace elements concentrations in whole rock samples were determined using AAS,
for gold, and ICP-MS, for the other elements (Mo, Re, Ag, Te, Se, In, Ge, PGE). The AAS
measurements were performed at SC Prospeciuni SA, Bucharest with pre-concentration by
fire assay method. The detection limit for gold is 0,01 ppm. The ICP-MS measurements were
performed at Guizhou Tuopu Resource and Environmental Analysis Center, using a Bruker
Aurora M90 spectrometer and the method from Qi et al. (2000) for sample preparation.

Rare elements in bulk rock

The mean bulk rock values of the main trace elements that are generally recovered
from porphyry copper type deposits (Au, Ag, Mo, Re) are: 0.28-0.88 ppm Au, ca. 2 ppm Ag,
<50 ppm Mo,. 0.02-0.3 ppm Re, 1.5-18 ppm Te, 3-5 ppm Se, 1.4-3.3 ppm Ge and <1 ppm In.
The pyrite concentrates from Moldova Nou have 206 ppm Te. PGE are < 2,1 ppm in bulk
rock samples and 6.5 ppb in pyrite concentrates from Moldova Nou.
There is a good to very good positive correlation between Cu, Au and Ag in the
potassic alteration zones of all deposits excepting Colnic. In, Se and Te show positive
correlations with Cu at Bolcana. A positive correlation of Cu with Se and In is indicated at
Bucium-Tarnia and Roia Poieni.
Au exhibits a good positive correlation with Te at Colnic (in the potassic alteration
zone) and Roia Poieni (in the sericitized samples) and a good positive correlation with Se, at
Valea Morii and Bucium-Tarnia.

Trace elements in minerals

The investigated metals and semimetals could be present in porphyry copper type
mineralization as own minerals (such as gold, molybdenite), but also as trace elements in the
network of some sulfides and sulfosalts such as pyrite, chalcopyrite, bornite, tetrahedritetennantite etc. The trace elements signatures of main minerals were determined using EMPA
and LA-ICPMS. EMPA analyses were performed at Rhodes University,

Grahamstown

(South Africa). LA-ICP-MS study of minerals (chalcopyrite, pyrite, bornite) and fluid
inclusions was performed at Institute of Geochemistry and Petrology, ETH Zurich.

EMPA results
Some grains of pyrite, chalcopyrite, bornite, galena, gold, enargite and tetrahedritetennantite were analysed for trace elements concentration (Au, Ag, Se, Te, Cd, Ge and In).
In the porphyry-type mineralization from Metaliferi Mts, but also at Moldova Nou,
the pyrite has Au, Ag and Te concentrations in a wide range of values, from below detection
limit to 1000 ppm for Au and Te and between 250 ppm and 860 ppm for Ag. Se has values <
70 ppm at Moldova Nou, but in the range of 50-330 ppm in approx. 50% of samples from
the deposits of Metaliferi Mts.
The chalcopyrite presents detectable values for Ag, Au, Te, Se and In: up to 950 ppm
Au, 600-1300 ppm Te, 250-2000 ppm Ag, <50 - 400 ppm Se. In is detected in few gains and
Ge is constantly below detection limits.
The bornite from Roia Poieni and Bolcana porphyry Cu deposits shows values up to
920 ppm Au, 1400 ppm Te, 4,830 ppm Ag in some grains, although other grains have
contents of these elements below detection limits. Se presents a mean value of 216 ppm at
Roia Poieni and 560 ppm at Bolcana. In and Ge were not detected.
In addition, minerals from associated base-metal veins-type mineralization were
investigated at Moldova Nou (pyrite, tetrahedrite, enargite, galena, and sphalerite).

LA-ICP-MS results
The smooth LA-ICP-MS profiles outline the existence of some microinclusions
containing high concentrations in trace elements. For example, high Te, Au and Ag
microinclusions were identified in pyrite at Moldova Nou (hessite?), while microminerals
with Pb and Te (altaite?) are included in chalcopyrite from Bolcana. Gold microinclusions in
pyrite, chalcopyrite or bornite were founded in all deposits.
Excluding the measurements that indicate the presence of microinclusions, all results
show low concentrations in trace elements. Quantitative LA-ICP-MS data on chalcopyite
show large range of values (1.03-0.03 ppm Au, 0.0-43 ppm Te, 5-92 ppm Ag, 146-482 ppm
Se etc.). The higher values in trace elements such as Au, Ag, Te, were measured on the
samples from Colnic. Chalcopyrite from Moldova Nou presents lower Zn and Se, but higher
As relative to the chalcopyrite in the porphyry copper deposits from Metaliferi Mts.
The pyrite is more inhomogeneous showing broad compositional variations in the
same deposit. For example, at Colnic, some elements vary by one order of magnitude or more
from one sample to onother (Au: 0.27->10 ppm, Zn: 55.89->1000 ppm). In the case of pyrite

from Moldova Nou, Cu and Zn have smooth spectrums that indicate zonality in their
distribution.
LA-ICPMS investigations on bornite were done only for Moldova Nou and Roia
Poieni deposits. Bornite from Roia Poieni is enriched in Ag, Te, Bi and Se compared with
bornite from Moldova Nou, the latter having higher concentrations of As, Sb, Ge, In and Sn.
Gold is detected only in the bornite from Roia Poieni (0.35 ppm).
PGE (Pd and Pt) are below detection limits in all measured sulfide grains.
V. Fluid inclusions analysis. Case study: Moldova Nou
In this project, fluid inclusions study was focused on Moldova Nou porphyry type deposit.
Micropetrographic study shows the presence of numerous types of brine inclusions and vapor
inclusions, forming a boiling assemblage. Most of the inclusions present a negative crystal
shape, ca. 10m in size, rarely larger. Only halite is present as a transparent solid phase and
occupies 20-40% vol. in brine inclusions. Chalcopyrite has been found in most brine
inclusions, as daughter mineral. The salinity of brine inclusions ranged between 34% and 48%
NaCl eqv., and was estimated using the final dissolution temperature of halite (270-420C)
(method of Bodnar and Vityk, 1994).
Chemical composition of brine inclusions was analysed using LA-ICPMS method.
The equivalent salinity (NaCl+KCl+FeCl2), was considered as an internal standard.
Preliminary results showed high values of Cu, Fe, Zn and Pb (hundreds ppm). Bi, Mo, Ag and
Te are detected in some inclusions (85-585 ppm Bi, 30-1183 ppm Mo, 15 - 142 ppm Ag, 48585 ppm Te).

VI. Disscutions and conclusions

All investigated deposits have Au-rich porphyry copper geochemical signature (> 0.2
g/t Au , ~ 1-2 ppm Ag, < 0.005% Mo). Most trace elements concentrations (Au, Ag, Te, Bi,
In) show significant enrichment. Platinum group elements (PGE) record very low values in all
deposits, commonly < 1 ppb, occasionally higher (1.6 ppb Pd at Moldova Nou and 1.21 ppb
Pd at Bucium-Tarnia).

Some of the detected trace elements were probably present in the crystal networks of their
host minerals, but some were also identified as mineral microinclusions in chalcopyrite, pyrite
and bornite. The gold concentration in sulfide network is low (< 1 ppm), excepting Colnic. In
the case of Colnic, the porous pyrite presents higher concentrations of Au, Te, Ag, Zn, As
etc., probably because of its rapid cristalization. Positive correlation of Cu with Au, Ag, In, Bi
in most ore deposits, especially in the potassic zone, suggests a common magmatic source of
these elements. Sericitization and argilization processes contributed to the redistribution of the
trace elements (enrichment of Mo, Re and Te and depletion of Cu respectively). The trace
element distribution in the main sulfide minerals shows no significant difference between the
deposits

in

the

Metaliferi

Mountains

(Miocene

province)

and

Moldova

Nou

(Banatite/Laramian province). At Moldova Nou, fluid inclusions study shows that the trace
elements were transported as chlorides in hypersaline fluids and the precipitation of metals
was controlled by the boiling processes at 300-450C.
EMPA results evidenced a preference of Au for pyrite, while Ag, Bi and Se show
values of hundreds ppm in bornite. Very high concentration of Te in bulk rock (hundreds ppm
in some samples from the sericitized samples from Moldova Nou and Roia Poieni) could
indicate the presence of tellurides in these samples.
Bulk rock results on the investigated samples from the porphyry Cu deposits in Romania,
suggest depletion in PGEs relative to mantle and some modest enrichments in Ir and Pd
relative to upper crust.
Chemical composition and microtermometry measurements of the fluid inclusions in
samples from Moldova Nou indicate a salinity of 34-48% NaCl eqv. and significant
concentrations of some metals (Cu, Mo, Ag, Pb, Zn, Mn, Pb, Cs, Ba) and, occasionally, Te
and Au.

References
Berbeleac I. 1985. Gold ore deposits (in Romanian). Editura Tehnic Bucureti. 315p
Berger B.R., Ayuso R.A., Wynn J.C., Seal R., 2008. Preliminary Model of Porphyry Copper
Deposits. USGS Open-File Report.
http://pubs.usgs.gov/of/2008/1321/pdf/OF081321_508.pdf)
Borco M., Vlad S., Udubaa G., Gbudeanu B. 1998. Qualitative and quantitative
metallogenetic analysis of the ore genetic units in Romania. Romanian Journal of Mineral
Deposits 78, Special Issue, Pages 1-160.

Borco M., Krautner H.G., Udubaa G., Sndulescu M., Nstseanu S., Bioianu C., 1984.
Map of the mineral resources, 2nd edition. Explanatory note. Institute of Geology and
Geophysics, Bucharest
Botinescu S., 1984. Porphyry copper systems in the South Apuseni Mountains Romania.
Anuarul Institutului de Geologie i Geofizic LXIV,163-75.
Ciobanu C., Cook N. J. Stein C. H. 2002. Regional setting and geochronology of the Late
Cretaceous Banatitic Magmatic and Metallogenetic Belt. Mineralium Deposita (2002) 37:
541567
Halga S., Ruff R., Stefanini B., Nicolici A., 2010. The Rovina Valley Project, Apuseni Mts.,
Romania. Gold copper porphyry discoveries in a historic mining district. Romanian Journal
of Mineral Deposits 84, 12-15.
Milu V., Milesi J.P., Leroy J.L., 2004. Roia Poieni copper deposit, Apuseni Mountains,
Romnia: advanced argillic overprint of a porphyry system. Mineralium Deposita 39, 173
188.
Rou E., Szakacs A., Downes H., Seghedi I., Peckskay Z., 2004. Timing of MioceneQuaternary magmatism and metallogeny in the South Apuseni Mountains, Romania.
Romanian Journal of Mineral Deposit 81, special issue, 33-38.
Sinclair W.D., 2007. Porphyry deposits, in Goodfellow, W.D., ed., Mineral Deposits of
Canada: A Synthesis of Major Deposit-Types, District Metallogeny, the Evolution of
Geological Provinces, and Exploration Methods. Geological Association of Canada, Mineral
Deposits Division, Special Publication, 223-243.
Vlad S.N., 1983. Geology of porphyry copper deposits (in Romanian). Editura Academiei,
Bucharest