Lithocaps – characteristics, origins and significance for

porphyry and epithermal exploration

David R. Cooke, Noel C. White, Lejun Zhang
Transforming the Mining Value Chain, Australian Research Council Industrial Transformation Research Hub, CODES,
University of Tasmania, Hobart, Australia

Zhaoshan Chang
James Cook University, Townsville, Australia

Huayong Chen
Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Wushan, Guangzhou, China

Abstract. Lithocaps are subsurface, broadly stratabound 2 Genesis

alteration domains that are laterally and vertically
extensive. They form when acidic magmatic-hydrothermal When magmatic-hydrothermal fluids exsolve from a
fluids react with wallrocks during ascent towards the
hydrous intrusive complex in the shallow crust, the fluids
paleosurface. Although lithocaps typically have steeply-
dipping structural roots, there is a significant component of may spontaneously split into large volumes of vapour and
lateral fluid flow involved in lithocap formation, either comparatively small quantities of brine (Henley and
through permeable aquifers and/or a well-developed McNabb 1978; Burnham 1979; Bodnar et al. 1985). The
fracture mesh. Lithocaps can have lateral dimensions brines can produce potassic alteration and porphyry-style
greater than 10 km and thicknesses of more than 1 km. In mineralisation in and around the apex of the intrusive
ancient settings, partially eroded lithocaps are typically complex. The vapour, which is the dominant fluid phase
exposed as silicified ridges and cliffs. These features do not volumetrically (e.g., Heinrich et al. 2004), ascends
mark the original paleosurface – instead they are erosional towards the surface, carrying acidic species such as HCl(g)
remnants of what was once an extensive subsurface
and SO2 (g).
alteration domain that may have been capped by low
temperature argillic- and/or propylitic-altered rocks. High
During the vapour’s ascent, it may condense into
sulfidation state mineralisation typically occurs in silicic- groundwater (e.g., Hedenquist and Taran, 2013). It could
altered rocks within lithocaps, either as stratabound also partially contract back to liquid, provided that
replacements, veins and/or breccia cement. The quartz-rich confining pressures increase through closure of the
mineralized domains can produce a resistivity high. Pyrite fracture mesh. In either scenario, the acidic fluid will be
is ubiquitous in lithocaps prior to weathering, and can yield cooling gradually, causing acidic species that remain
complicated chargeability responses, some of which may associated at high temperatures, such as HCl(aq), to
be associated with mineralization. The alteration dissociate, thereby increasing the acidity markedly due to
assemblages are invariably magnetite-destructive, and can the liberation of H+. Another important acid-forming
obscure the magnetic signature of an underlying porphyry
process involves the spontaneous disproportionation of
deposit. Combining SWIR and whole rock geochemistry
can provide effective vectoring tools within lithocaps. SO2 (g) around 400 to 350°C. This chemical reaction
liberates three moles of sulfuric acid and one mole of
hydrogen sulfide for every four moles of SO2 (Rye et al.
1992; Rye 1993). Acid-forming processes during vapour
1 Introduction ascent transform the fluids into some of the most
chemically aggressive hydrothermal solutions that nature
Lithocaps are volumetrically significant domains of can create. They have the capacity to alter most rock types
hypogene silicic, advanced argillic and argillic-altered into massive domains of quartz and/or quartz-alunite
rocks that can form above and to the side of shallow- through extensive water-rock interaction.
crustal hydrous intrusive complexes. A spectrum of
mineralisation styles associated with the intrusive
complexes can be obscured and/or at least partially hosted 3 Alteration zonation
by a lithocap (e.g., Sillitoe 1995, 2010; Chang et al. 2011;
Fig. 1). Lithocaps may host high-sulfidation state Two main components of hydrothermal fluid flow are
mineralisation. Some overlie and partially overprint required to form a lithocap – structurally controlled
porphyry deposits. Lithocaps can also overlie intermediate upflow from the deeper-seated magmatic fluid source, and
sulfidation veins, can be more than 1 km thick, and may lateral outflow, which can occur when the ascending
exceed 10 km in lateral dimensions (e.g., Yanacocha, Peru, magmatic-hydrothermal fluids reach their neutral
Shuteen, Mongolia). They can be particularly challenging buoyancy level and encounter a permeable stratigraphic or
for exploration due to their lack of easily mappable structural aquifer. Broad vertical and narrow lateral
alteration zonation patterns. alteration zonation patterns characterise the upflow

S02 – Ore forming magmatic-hydrothermal processes along active margins 291

Figure 1. Schematic illustration of alteration zoning and overprinting relationships in a porphyry system (modified after Holliday and
Cooke 2007; Cooke et al. 2014). Lithocaps can overlie and partially overprint porphyry-style mineralisation associated with shallow-
crustal hydrous intrusive complexes. They may host high sulfidation-state mineralisation and can cover intermediate sulfidation state
epithermal veins. The lithocaps will overprint and be surrounded by propylitic alteration assemblages that vary from high to low
temperature alteration subfacies (i.e., actinolite, epidote and chlorite subfacies) as a function of proximity to the intrusive source. The
roots of the lithocap lie within the pyrite halo of the porphyry system. The degree of superposition of the lithocap into the porphyry
system is contingent on uplift and erosion rates at the time of mineralization, and will vary from province to province, and from district to
district. Abbreviations: ab – albite; act – actinolite; anh – anhydrite; Au- gold; bi – biotite; bn – bornite; cb – carbonate; chl – chlorite; cp
– chalcopyrite; epi – epidote; gt – garnet; hm – hematite; Kf – K-feldspar; mt – magnetite; py – pyrite; qz – quartz.

beneath lithocaps, whereas very broad lateral and vertical or vuggy quartz, forming as veins and/or replacements.
zonation patterns typify the overlying lithocaps. Pyrite is ubiquitous throughout all of the hypogene
alteration assemblages in lithocaps.
3.1 Alteration in the feeder system The broad vertical alteration zonation contrasts
markedly with the narrow (metres or less) alteration halos
Faults typically provide the focus for fluids to migrate that develop laterally around feeder faults in response to
upwards from magmatic fluid sources towards the water-rock interaction. At any given depth, the central
lithocaps environment (Fig. 1). These structural roots are silicic domains within the fault system will pass outwards
the sites where acidity increases gradually during fluid with sharp contacts through tight alteration halos (on the
ascent, either due to HCl dissociation and/or SO2 scale of centimetres to meters) to advanced argillic and/or
disproportionation. The combination of acidification and argillic alteration assemblages. At deeper levels, massive
gradual cooling produces a broad vertical alteration quartz–pyrite veins may have narrow quartz–pyrophyllite–
zonation pattern along the faults, potentially over the scale dickite halos. Similar veins at shallower levels may have
of a kilometre or more. Assemblages are zoned vertically quartz–alunite halos. In both cases, these narrow advanced
from deep-level quartz–muscovite upwards through argillic alteration halos will typically pass outwards to
quartz–pyrophyllite–dickite, to quartz–alunite and (at background argillic and propylitic assemblages over the
shallow levels) quartz–kaolinite and quartz–halloysite. The scale of meters or less.
core of the upflow zone is generally composed of massive High-sulfidation state mineralisation may be hosted
in the structural roots to a lithocap. In deeper parts of the

292
Mineral Resources to Discover - 14th SGA Biennial Meeting 2017, Volume 1
fault array, mineralisation may produce massive sulfide superimposed onto the top of early-formed alteration and
veins rich in bornite, chalcocite and/or chalcopyrite (e.g., mineralisation features in any underlying porphyry deposit
Collahuasi, Chile; Masterman et al. 2005). At shallower (e.g., Lepanto – Far Southeast, Philippines; Chang et al.
levels, the quartz–pyrite-rich structures may be 2011). The degree of juxtaposition of the lithocaps and
mineralised with tennantite–tetrahedrite and/or enargite, porphyry environments will vary from district to district,
with gold occurring as a refractory phase in pyrite and depending on local uplift and exhumation rates, the local
enargite. Shallow quartz – pyrite veins may only contain history of mass wasting and the duration of magmatic-
traces of enargite, but can still be endowed with significant hydrothermal activity.
gold—silver mineralisation. Reactivation of faults can
result in several stages of tectonic-hydrothermal 3.3 Surface features
brecciation which can disrupt mineralization.
What are the surface expressions of modern-day
3.2 Alteration in the lithocap lithocaps? Wherever mountainous terrain overlies a
magmatic-hydrothermal fluid source, there is likely to be a
Huge volumes of lateral fluid flow are required to generate significant spatial separation between the surface
the large, stratabound alteration domains that compose a discharge sites for gases and boiling waters, with only
lithocap. The local environment needs to have significant intermittent fumarolic discharges of magmatic gases likely
topographic relief combined with an appropriate to occur at high topographic levels directly above the
permeability architecture at the time of alteration, in order intrusive complex. Significant lateral flow of acidic waters
to facilitate lateral flow. This agrees well with the facilitates their discharge at lower topographic levels,
geomorphologic evolution of the El Indio belt and other away from the main upflow zone. This means that the
deposits in the Andes (Bissig et al 2002, 2015). Once surficial boiling acid springs could be located kilometres
neutral buoyancy has been achieved, lateral migration of away from the area of fluid upflow. The upflow zone is
acidic solutions may occur along a permeable aquifer, most likely to be overlain directly by the sites of fumarolic
such as unconformity surface or poorly consolidated discharges (e.g., Palinpinon, Philippines; Rae et al. 2003).
volcaniclastic breccias. In the case of rocks that typically Such surface manifestations may be trivial compared to
have low permeability such as granitoids, fluids can flow the huge volume of alteration forming beneath the surface,
laterally through a well-developed fracture mesh and their significance could be easily missed.
Lateral fluid flow facilitates fluid migration from the
structural roots of the lithocap towards the paleosurface.
The surface discharge sites may be more than 10 km away 4 Landform modification by erosion
from the main upflow zone, and will be at a low point in
the local topography. Although the main fluid flow Ancient lithocaps may be partially exposed at surface,
direction is lateral, there is also a vertical component as cropping out as silicified ridges, ledges or cliffs. These
the fluids continue to migrate upwards towards areas of silicic outcrops are typically the erosional remnants of far
low topography. The topographic controls on fluid flow more extensive subsurface alteration systems that formed
imply that the alteration domains that define lithocaps may at the time of mineralisation. Today, they create degraded
be distributed asymmetrically around the causative landforms that some explorers refer to as ‘silica caps’.
intrusion, with outflow dictated more by topography than Silica caps are erosional remnants of what were once more
by proximity to the fluid source. extensive lithocaps. They typically contain high-
In contrast to the structural conduits beneath lithocaps, temperature alteration mineral assemblages (e.g., quartz –
the lithocap itself is characterised by very broad lateral alunite – pyrophyllite) and are therefore unlikely to have
zonation of alteration assemblages, transitioning outwards formed at the paleosurface. As they are recently formed
from central silicic cores composed of residual quartz topographic anomalies, they typically do not directly
(massive and/or vuggy textures), through advanced argillic overlie porphyry-style mineralisation. Instead, the
alteration (typically quartz–alunite) to argillic (quartz– porphyry deposit may be located several kilometres away
kaolinite ± illite) and lower temperature intermediate from the silica cap, beneath areas of more subdued
argillic (illite–chlorite) and propylitic (chlorite–calcite ± topography. This is because alteration assemblages that
epidote) assemblages. High sulfidation state form directly above a porphyry deposit (e.g., phyllic,
mineralization, if present, is typically hosted as intermediate argillic and/or propylitic alteration
replacements or breccia infill in the residual quartz assemblages) are likely to be less resistant to erosion than
domains. The same zonation patterns can occur vertically the silicic and advanced argillic alteration assemblages
around lithocaps, although it is important to realise that that characterise lithocaps, which tend to form on the
propylitic assemblages can occur both below and above shoulders of porphyry deposits, rather than silica caps,
stratabound domains of silicic and advanced argillic when searching for porphyry mineralisation.
alteration, particularly where several of these alteration Misunderstanding the origin and significance of ‘silica
domains have formed in what we call a ‘stacked’ lithocap caps’ could prove costly during lithocap exploration.
(e.g., Quimsacocha, Ecuador; McDonald et al., 2011). These domains are better described as massive and/or
When uplift rates are extreme, lithocaps may be

S02 – Ore forming magmatic-hydrothermal processes along active margins 293

vuggy quartz alteration zones, and should not be treated as Seymon and Alan Goode, and to the reviewers of this
the top of the hydrothermal system, unless there is article.
supporting evidence that minimal landscape degradation
has occurred after lithocap formation.
References

5 Exploration tools Bissig, T, Clark AH, Lee JKW, Hodgson CJ (2002) Miocene
landscape evolution and geomorphologic controls on epithermal
Although lithocaps are sites of profound mineralogical, processes in the El Indio-Pascua Au-Ag-Cu belt, Chile and
Argentina: Econ Geol 97: 971–996.
textural and geochemical changes to the protoliths, Bissig T, Clark AH, Rainbow A, Montgomery A (2015)
exploration for mineralisation within and beneath them Physiographic and tectonic settings of high-sulfidation
can be challenging. Fine grained clay minerals are epithermal gold-silver deposits of the Andes and their
abundant, and textural destruction is common. Short-wave controls on mineralizing processes: Ore Geology Reviews 65:
infra-red (SWIR) spectroscopy is an essential tool to aid in 327–364.
Bodnar RJ, Burnham CW, Sterner SM (1985) Synthetic fluid
mineral identification in these environments. Without
inclusions in natural quartz. III. Determination of phase
technological augmentation through the use of portable equilibrium properties in the system H2O-NaCl to 1000°C and
field-based SWIR detectors, field geologists will struggle 1500 bars. Geochim et Cosmochim Acta 49: 1861-1873
to map alteration zonation in lithocaps effectively. Burnham CW (1979) Magmas and hydrothermal fluids. In: Barnes
If high-sulfidation state mineralisation is associated HL (ed) Geochemistry of hydrothermal ore deposits, 2nd edn. J.
with domains of silicic alteration, then resistivity surveys Wiley and Sons, New York, pp 71-136
Chang Z, Hedenquist JW, White NC, Cooke, DR, Roach M, Deyell
may help to identify prospective domains. As gold CL, Garcia J, Gemmell JB, McKnight S, Cuison AL (2011)
typically occurs as a refractory phase in pyrite, Exploration tools for linked porphyry and epithermal deposits:
chargeability anomalies may be associated with high- Example from the Mankayan intrusion-centered Cu-Au district,
sulfidation state mineralization. But pyrite is ubiquitous Luzon, Philippines. Econ Geol 106: 1365–1398
throughout lithocaps, and only some of the pyritic rocks Cooke DR, Hollings P, Wilkinson JJ, Tosdal RM (2014)
may be gold-mineralized, making the identification of Geochemistry of porphyry deposits: In: Holland HD, Turekian
KK (eds) Treatise on Geochemistry, 2nd edn. Elsevier, Oxford, v
pyritic mineralized zones challenging. Furthermore, 13, pp. 357-381
weathering can result in complicated chargeability Hedenquist, JW, Taran, YA (2013) Modeling the formation of
anomalies, where pyrite is partially to completely replaced advanced argillic lithocaps: volcanic vapor condensation above
by limonites. Lithocaps are characterised by broad and porphyry intrusions. Econ Geol 108: 1523–1540
thick domains of magnetite-destructive alteration, and so Heinrich CA, Driesner T, Stefánsson A, Seward TM (2004)
Magmatic vapor contraction and the transport of gold from the
any positive magnetic anomaly associated with underlying
porphyry environment to epithermal ore deposits. Geology 32:
magnetite-bearing porphyry copper-style mineralisation 761-764
can be completely obscured. Henley RW, McNabb A (1978) Magmatic vapor plumes and ground-
Chang et al. (2011) demonstrated that a combination of water interaction in porphyry copper emplacement. Econ Geol
SWIR analyses, focussing on spatial changes in the alunite 73: 1-20
1480 nm peak positions, coupled with whole rock Holliday JR, Cooke DR (2007) Advances in geological models and
exploration methods for copper ± gold porphyry deposits.
geochemistry (filtered based on the presence of alunite and Decennial International Conference on Mineral Exploration 5,
absence of Cu, Au or Ag mineralisation), and augmented Toronto, Canada, Conference Proceedings: 791–809
where required by LA-ICP-MS analyses of alunite, can MacDonald PJ, Bissig T, Hart CJR, Barreno J, Viera F (2011) The
provide effective tools for vectoring towards the heat and hydrothermal evolution of the Quimsacocha high sulfidation Au-
fluid source responsible for lithocap formation. The Ag-Cu deposit, Azuay Province, Ecuador. Proc. 11th Biennial
intrusive complex responsible for the lithocap is the most SGA Meeting, v. II: 733-735.
Masterman GJ, Cooke DR, Berry RF, Walshe JL, Lee AW, Clark AH
likely site to discover any associated porphyry-style (2005) Fluid chemistry, structural setting, and emplacement
mineralisation. But it is not guaranteed that an intrusive history of the Rosario Cu-Mo porphyry and Cu-Ag-Au
complex that produces a lithocap will always form high- epithermal veins, Collahuasi district, northern Chile. Econ Geol
grade mineralisation, either of porphyry and/or epithermal 100: 835-862
character. More characterisation of mineralised and barren Rae AJ, Cooke DR, Phillips D, Yeats C, Ryan C, Hermoso D (2003)
lithocaps is therefore required to resolve whether tools can Spatial and temporal relationships between hydrothermal
alteration assemblages at the Palinpinon geothermal field,
be developed to assess the potential fertility of lithocaps Philippines: implications for porphyry and epithermal ore
with respect to mineralization. deposits. Society of Economic Geologists Special Publication 10:
223-246
Acknowledgements Rye RO (1993) The evolution of magmatic fluids in the epithermal
environment: the stable isotope perspective. Econ Geol 88: 733–
752
Thanks to all of our colleagues and industry research Rye RO, Bethke PM, Wasserman MD (1992) The stable isotope
sponsors in AMIRA projects P765, 765A, 1060 and P1153, geochemistry of acid sulfate alteration. Econ Geol 87: 225-262
particularly Jeff Hedenquist, Cari Deyell and Bruce Sillitoe RH (1995) Exploration of porphyry copper lithocaps.
Gemmell. Thanks also to AMIRA coordinators Adele AUSIMM Publication Series 9: 527−532
Sillitoe RH (2010) Porphyry copper systems. Econ Geol 105: 3–41

294
Mineral Resources to Discover - 14th SGA Biennial Meeting 2017, Volume 1