Advancing Sctence and Discovery > a: “SS ae) Footprints: Hydrothermal Alteration and P Geochemical Dispersion Around Porphyry Copper Deposits Scott Hallley, Mineral Mapping Ply li, 24 Webb Sreet, Rossmoyne, WA 6148, Australia, John H. Dilles, Oregon State University, College of Earth, Oceanic and Aimospheric Sciences, 104 CEOAS Administrative Building, Corvallis, OR 97331, United States, and Richard M. Tosdal,’ PicachoEx LIC, 21 Quince Mill Court, North Potomac, MD 20878, United States ABSTRACT 1) Hydrothermal uteraion assemblages ‘Whole-rock lithogeochemical analyses combined with short-wave infrared (SWIR) spectroscopy provide a rapid and cost-effective method for pros pecting for porphyry-type hydrothermal systems. Lithogeochemistry detects trace metals to average crustal abundance levels and allows vectoring via gradients of chalcophile and lithophile elements transported by magmatic-hydrothermal ore and external circulating fluids that are dispersed and. ‘trapped in altered rocks. Of particular use are alka- lis in sericite and metals such as Mo, W, Se, Te, Bi, AAs, and Sb, which form stable oxides that remain. ‘in weathered rocks and soils. SWIR mapping of shifts in the 2,200-nm Al-OH absorption feature in sericite define paleofluid pH gradients useful f vectoring toward the center of the buoyant metal: bearing magmatic-hydrothermal plume INTRODUCTION Porphyry and related epithermal Au-Ag ores are the world’s most important ore deposits outside of iron and aluminum mines, produce most of the ‘Cu and Mo, and are the largest producers of AU and Ag globally. It has been known for over a cen- tury that metals in porphyry Cu deposits are zoned, with acental 'Comesponding author: email, tosdal@gmail com SEG 2015 miceswt 203) panel icos ARGILLIC ‘ vec etch Seiten cuca oan) FRGURE 1. 0) Yorical cross secon of atypical porphyry Cu dopost showing saibuion t hydrothermal ateraton and sufide minerals Alto shown are genealzed contours of the 2,200-nm peak measured in SWIRinsrumen's MT ee ee eo RC alae aed Hobart, TAS, Australia2 SEG NEWSLETTER No 100 « JANUARY 2015 HEREIN pins rhe Araon an GeochaclDipvion Aud Phy Capper Ceo ote) zone with Cu + Mo/Au that is enclosed in zones entiched in Zn, Pb, and Ag ang, in some cases, Min (Meyer etal, 1968). Gold-Ag may be present laterally away from (eg, Lang and Eastoe, 1988) or above (Hedenguist et al, 1998) the porphyry Cu core Exploration programs for porphyry Cu deposits rely on many techniques, but from a geologist’s perspective, ‘whole rock lithogeachemistry and short-wave infrared (SWIR) spectrome- try have become standard tools in ad tion to the hammer and hand lens. To assist this elfort, we established the ver- tical and lateral footprint of a porphyry Cu deposit using SWIR and lithogeo- chemistry (Fig. 1). We tracked alter- ation paths ~1 to 5 km vertically (¢., Yerington, Red Chris, Galore Creek) or up to 7 km laterally (Butte, Christmas, Highland Valley) from the porphyry ore center, To understand the metal disper- sion outside the ore zone, we focused on the D-type veins with alteration selvages containing sericite, pyrite, and chlorite, the latter being common in hydrolytic assemblages where rocks are dominantly of intermediate to mafic compositions, These veins extend vary- ing distances vertically and laterally from the ore zone. ‘The distribution of SWIR recognized minerals and changes in sock composl- tons of just two of the many elements (1, Bi) that were mapped vertically and laterally in the Ann Mason porphyry Cu-Mo deposit in Yerington and are shown in Figure 2 as examples, Petrog- raphy, electron microprobe analysis, and laser ablation-inductively coupled pplasma-mass spectrometry (LAICP-MS) of the hydrolytic mineral alteration assemblages analyzed in the lithogeo- chemical and SWIR data sets further constrain the interpretation of the resulting patterns (Alva:Jimenez, 2011; Cohen, 2011). METHODOLOGY Rocks were chosen as the sample medium in order to ascertain the primary elemental and mineralogic dispersion halos. However, in many environments during initial explora- tion, soil may be nearly as effective as rocks, as soils capture a geographic aver- age that may include both weakly and strongly altered rocks. 1 Vertical distribution of elements tours esr sta esha Syl en 5, sea Front imomcanvein | OA fn po | magmatic Pus FIGURE 1. (Cont) bb) Voricel variations in roce Charges in hydrothermal cloraion osvomblagos. ek, 2n tn CNA, 8 —— Tnckwepiaru © ARGILLIC eROPYLITIC sone: caicie ES clement in a porphyry Cu system, ¢| Schematic ond Wace laments rough a porphyry Cu system Viewed 28.6 safes of map views hough a vette system ©) Lateral distribution of elements Elevation of Highest Grade Cu| “a!No 100 « JANUARY 2015 SEG NEWSLETTER 3 pesssw b. usw open nt ena Faeuk Taitaat sip Frotnerma Aeration Zone Dominant Aydrox bearing Mineral HB vercArg Oz-Pyop-AlurTopan| [ET] Abie SersCnLPy loymbois eet dominant real posons of ste mines) TB serctestour->y Nes o pepe senate Fresh os [ERY Se-charedetiem weak son Sete gi ser) ohare el ovtnisraaeien rine gore 3 taumaine ooo esate: ite ek 50838 100% ME] Stem (GeCrx) ani (lol) Rosh rook “2EBEM = eens) Advanced agile ogee ONO! MeBN OB Zens 2210 84 © pxephyite S sm m 22% e [rots a [ss TTeoncenwaion TD Bionsenaon ~08 pom ipa 1-28 om feign (h a Bi ‘iteration Assemblages ‘9 Pyrophylitealuiterooaz Serie ate © soaie-aice © Kcslicate -ore zone © Albte-senite Albite (9 Frosh rk, FRGURE 2, Map of hyetemal aeration cssblages in he ein al the Arn Mason pry CMe depost tom Dies and Ena (1992 end " from J.H. Dilles (unpub. mopping, 2014) superposed on the geology from Proffett and Dilles (1984). Pale purple units are posimineral Tertiary volcanic rocks. ppb ls carlsw 20 mmo coun ef (eae pare peed eae es Pa ee ce eigenen eens Perper terete cle eel a rer epee eget dress eat eee nn eee ee ==>“4 SEG NEWS No 100 « JANUARY 2015 FERED opin tyre leratn ond Geochemical Dipesion Ain Paphyry Copper Depst ontned) Lithegeochemical analyses ‘Commercial laboratories provide rapid tumaround of chemical analyses including sample preparation, internal standardization, and replicates, In this study, we used ALS Global for 48 ele- ‘ments (ME-MS61 method) that include all major elements but silica, which is lost as iF, gas. The best sample dissols- tion combined with low detection limit is achieved winen rock is digested by a mixture of four acids (hydrofluoric-ni- tric-perchloric-hydrochloric), This dis- solution method liberates neatly 100% of all elements except for Zs, If, and a small percentage of heavy rare earth ele- ments (REE) and Y contained in refrac tory zitcon, Coupled with the ICP-MS + ICP-atomic emission spectroscopy (AES) instramental finish, the result ing assays report elements at detection limits similar to crustal abundance. At a minimum, assay values an order of magnitude or more greater than aver- age crustal abundances in rocks (Table 1) should be viewed as anomalous and attract further attention from an explo. ration program. Alternative sample digestion proce- utes are available but, compared to four-acid digestions, are more costly, lead to incomplete dissolutions, or have higher detection limits. Aqua regia dis solves sulfides and oxides effectively, but cannot dissolve silicate phases ‘where many useful pathfinder elements reside and, furthermore, that commonly survive weathering of rocks to form soil, Lithium metaborate flux results in complete dissolution of rocks so that total silica, Zr, and Hf concentrations are obtained, but this fusion technique 4s expensive, increases the sample blank, and produces higher detection limits for tuace elements, SWIR analyses Short-wave infrared spectra were col- lected from rock chips fom larger sam- ples analyzed for lithogeochemistry. As the SWIR spectrum is collected from small rock surface (-0.5-cm diameter), the sample volume is much smaller than the corresponding one for itho- geochemistry. Samples were broken in the field such that the effect of surface weathering is minimized. ‘The hydrous minerals that are the most widespread in sericitic alteration are white micas/clays (muscovite/ilite commonly called “sericite”) and chlo- rite, Each has distinctive spectra that also yield compositional information (Thompson et al,, 1999). SWIR instru- ments efficiently analyze 500 to 1,000 samples per day in the laboratory, or in the field from samples archived in chip trays. ‘TABLE 1. Typical Pathfinder Elemental Ranges (pom) Metal Avera Poraiie Shallow sevice co 75 >200-0re 100 50 No 7 O5-ore 2-20 05-5 Sn 25 os10 2-30 biga w i Bed 2.20 oss Mo 1.400 S0 ppm for 4s), hence the need for analytical methods with low detection limits Sericitic zones also record anomalies of Cs and Rb in addition to Li and TL. AAs the sequence of metals above and beyond the Cu zone closely mimics the general decrease in solubility of metal chlorides in ore fluids during cooling (Reed and Spycher, 1984), the zonal arrangement of metals or metal ratios fs therefore a tool for targeting further exploration, ‘Comparisons of the six hydrothermal systems suggest that all contain similar ‘magmatic-hydrothermal trace metal anomalies; however, their concentra tions and ratios vary, as do the ore metal ratios, For example, if we consider the Yerington, Highland Valley, and Christmas calc-alkaline magmas (Cu- ‘Mo) as a baseline, the more silica rich ‘magmas at Butte (Cu-Mo) have sericitic zones relatively enriched in As, W, Sn, Cs, Sb, and Zn whereas the alkaline to hhigh-K magmas at Red Chris and Galore Creek (Cu-Au) have alteration zones relatively enriched in Te, Se, and Bi (Micko, 2010) Several elements are depleted from. ppotassic = seriitic alteration in the central Cu-Mo ore zone, Hypogene leaching results from hydrothermal destruction of the host igneous miner- als amphibole + pyroxene and feldspar, Several other elements (TI, Cs, Rb + Li) are likely dominantly supplied by the parent magmatic hydrothermal fluid and, because they are highly soluble in high-temperature chloride solutions, they are present in low abundance in the ore zone. Hypogene leaching in the Cu-Mo ore zone ean potentially contrib- ‘ute metals to distal polymetallic @Zn-Pb- Manta ores espchlly ppm, near the outer limits of16 SEG NEWS No 100 « JANUARY 2015 Fens: HydahernlAteaon ard GeachalDiprion Round Prphry Cope Depots one late sericitic alteration. Nonetheless, because leaching of different host racks will provide different ratios of these ‘metals, the amount and ratios will vary in the peripheral zones. There is no indication that mag. ‘matic-hydrothermal fluids contribute significant sulfides, ore metals, or trace metals to most of the propylitic zone that extends laterally away from the fore zone. In contrast, sodic-caleic alter alion leaches a suite of metals (Fe, K, (Cu, Zn, Ni, Li, Pb, As, Sb, and Co) that are moved upward and locally fixed in propylitic or shallower levels of sod: fc-caleic-altered zones. Magmatic fuids add trace metals to propylitic or sod: ic-calcic alteration at the interface with, potassic alteration or where lateral D veins cut propylitic zones. For example, the prominent Zn enrichment zone that is common on the margins of most porphyry Cu deposits is present where minor amounts of sericte and chlorite are in the rocks. MAPPING CHANGES IN SERICITE COMPOSITION "Sericite" isa field term that includes fine-grained white micas of indetermi- nate mineralogy (Meyer and Hemley, 1967). In most porphyry Cu environ. ments where rocks contain some potas. sium, sericite forms above about 300°C to as much as 550°C and is muscovite (EAL (AISi,)0,,(OF),) with a white to gray color. At low temperatures below about 300°C, sericite is fine grained, ‘may range from white to pale green in color, and is usually the potassium-defi- cient clay mineral illite (K,,,AL,(Al, suSi,..)0,_(OH),). The boundary between muscovite and illite is consid ered to be about 300°C (Reyes, 1990); however, both minerals are chiefly 2M. sheet silicates with an identical crystal structure, so the different names merely represent an arbitrary boundary in a sin- gle continuous solid solution (Cohen, 2011), Sericite forms chiefly via hydrolytic alteration of feldspar and, to a lesser extent, from mafic minerals, via reac tions such as the following: 1.SKAISi,O, (Kspar) +11" 0.SKALAISi,) ©,(OH), Ginuse) + K' + 3810,; 1.SNaAlsi,0, (abite) +H" + 0.5K" © 0.SKAL,(AISL}O, (ON, (aus) + 1.5Na! +3810, and] 1,SCaALSi,0, (anorthite) + 2H" + @ KAL(AISi,)O,,(OFD, (muse) + 1 These reactions consume acid, release Na and Ca, and are produced by acidic fuids. Sericite (muscovite and ilite) is stable over a relatively wide range of log(K /H’) at a given temperature that reflects pli changes from acidic low Iog(K/H") to more neutral high log(K"/ H}) conditions. Therefore, pH or adidity, can vary considerably in the sericite field, and can be mapped by the mica composition. Mapping pH gradients with swik Yor the purposes of quickly mapping the mineralogic changes in the seric- ste-chlosite-altered rocks, the abikty of the SWIR instruments to obtain rapid identification of minerals and their solid-solution compositional changes 4s of particular value (Thompson et al, 1999). In the porphyry environment, the wavelength of the 2,200-nm absorp. tion feature corresponding to the Al-OH bond energy of sericite-bearing samples is critical. In sercite, including both muscovite and ilite, the wavelength of the 2,200enm feature shifts from 2,195 ‘nm in muscovite (owaed 2,220 nim in phengite, as ALis replaced by (Fe, Mg) + Si. This coupled Tschermak-type substi- tution is controlled by the pitas well as the concentrations of Fe") and (K°) of the hydrothermal system via the follow- sng reaction’ 2KAL,(AISi,)O, (OND, (muse) + K+ 15Fe* + 4.58i0, + 31,0 # 3KFe, Al,, (Al, Si, J0,,(08D, (phen) + 4H ‘The acidity of the hydrothermal uid helps determine the proportions of muscovite and phengite in the mica Mauscovitic white mica (including illite) ‘means an acidic environment, whereas a phengitic composition means a moze neutral environment. Therefore, the position in the white mica wavelength ‘an be used as a hydrothermal pH indi- cator, and changes laterally and vert cally in the porphyry Cu environment (Big. 12). Furthermore, the position of the 2,200-nm absorption is not very sensitive to the K content and whether the mica is muscovite or illite. Above the core of a porphyry Cu deposit, the position of the 2,200-nm absorption shifts to lower values in the spectra of sericite-chlorite-altered rocks as the fluid pHT decreases, because acids in the rising uid continuously disso- ciate during cooling and destroy the ability of the rocks to buffer the fluid (ig. 1a). Upward fuid flow is rapid along the permeability fabric, whereas lateral pressure gradients are smaller as acid enters the rock via slow diffusion, Consequently, along the centers of fluid flow channels, the water/rock ratios are high and pH is low, whereas, laterally, the water/rock ratio quickly decreases and rock-buffering and neutral pI dominate. Local-scale evidence for the changes is readily evident in steeply dipping D veins with inner pervasive serictic alteration enclosed laterally by ‘weakly altered halos of feldspar-seric- ite-chlorite cutting rocks that may only have chlorite replacing mafic silicates, Laterally, the position of 2,200-nm absorption increases, reflecting a tran- sition toward low fluid flux and a more neutral pH] environment (Fig. Ta), In the shallow envizonment influenced by surface topography, the low-pH ‘magmatic or mixed magmatic-meteoric groundwater moves laterally to produce extensive distal sericitic and advanced argillic zones. A complication to the general pattern arises, such as at Red. Chris and Butte, where the lower-tem- perature acid-stable environments are telescoped upon the higher-temperature silicate alteration assemblages (Meyer et al, 1968; Norris et al, 2011). WEATHERING ‘Weathering of rocks that are initially pytite rich and contain little feldspar produces sulfuric acid and supergene Teaching that removes Cu, Ag, Pb, and Zn, Nonetheless, many elements useful as magmatic tracers are not leached and remain in rocks and derivative soil. ‘There are three suites of nonleachable elements: (1) chalcophile elements (Mo, As, Sb, Te, Se, Bi) that were trace impu: nities in pyrite or minute sulfide grains associated with pyrite, (2) lithophile ore minerals (W, Sn) that form stable oxide complexes, and (3) lithophile alkali and alkali earth elements that follow potas- sium and remain fixed in sericite and chlonite Ba, B, Cs, Li, Rb, TD. Hence, during surface weathering where micas and chlorite are stable, many trace ele- ments largely remain in the rock and also soll. Even extreme acid weatheringNo 100 « JANUARY 2015 SEG NEWSL 7 accompanied by hydrolytic destruction of sheet silicates may lead to complete leaching of the alkalis, Zn, and TL However, elements that form oxides are not leached and remain detectable Understanding the behavior of elements in the weathering profile allows the explorer to use trace elements as vec tors, even in highly weathered terranes. CONCLUSIONS ‘SWIR and Uithogeochemistry are simple and relatively inexpensive but powerful tools for the exploration geologist, as well as for geometallurgy (Halley, 2013). Samples of rocks and soils collected on. 2 grid spacing as broad as 500 m can be used to identify anomalies and gradi- cents in mica mineral compositions and ‘race metal abundances during initial exploration for porphyry Cu deposits. Sampling of rocks must be selective, preferably in altered rock selvages to veins, as uid flow is rapidly channel- ized outside the mineralized core both, upward and outward. Nonetheless, a sulle of rock analyses must be used with caution for targeting, and always within the context of geology. For example, at Yerington, the mineral deposits were Lulted 90° west by Cenozoic normal faulting so that they are exposed in cross section. In this case, the min. cralogic and geochemical vectoring ‘cannot be used ad hoc. Any lithogeo- chemical and SWIR analyses must be done in concert with basic mapping of the geology, hydrothermal alteration mineralogy, and ore sulfides and oxides Mapping D veins with sericitic selvages that extend kilometers upward and ‘outward from the porphyry ore center remains one of the simplest geologic guides to targeting the center. Further- more, these sericite-chlorite-pyrite alter ation zones are ideal for geochemical vectoring because they will preserve a ‘magmatic fingerprint of lithophile ace ‘metals in the mica structure and of chal: cophile elements within and associated with pyrite Lastly, there is an enhanced focus con exploring under cover and at depth; however, in many parts of the world, ‘mineral deposits are still hidden by a leached weathering profil. In these places, new discoveries should still be possible through soil geochemistry Af the program considers what works and what does not work in those envi- ronments. Traditional assay packages include Cu, Zn, Pb, Au, and Ag that are leached at surface and therefore not useful vectors in many weathering envi- ronments, but the oxyanion elements (As, Mo, Sn, W, Te, Se) are robust and will be preserved. \ cost-effective and recommended methodology is a four: acid digest to achieve a reliable dissolu: tion of several refractory elements and ICP-MS analyses to provide sufficiently low detection limits near elemental crustal abundance. ‘ACKNOWLEDGMENTS, ‘This paper is a partial summary of a three-year industry project on footprints of porphyry copper deposits funded principally by Barrick, Teck, Freeport, Imperial Metals, BHPBilliton, and Vale, with additional grant support from Geo- science British Columbia, NSERC, and the USGS, ALSGlobal is further thanked. for its generous analytical support. We ‘thank Pacmag Metals Lid for providing access to two drill holes in the Ann Mason deposit, Numerous MDRU-UBC and OSU students made important con- tributions to the project. Comments by Marco Einaudi, John Muntean, Brock Reidell, and Peter Winterbum improved the clarity of the manuscript. 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