ee ican Nah pp 6-82 4 CONTROLS ON HYDROTHERMAL ALTERATION AND MINERALIZATION INTRODUCTION ‘Alarge numberof variables influence the formation of alteration minerals in hydrothermal stems. These are {grouped into seven main categories (Browne, 1978) 1, Temperature Fluid chemistry Concentrations Host rock composition Kinetics of reactions Duration of activity or degree of equilibrium Permeability Airey these are all more or less interdependent, temperature and fluid. chemistry probably have the Strongest influence on the stjles of hydrothermal alter auion developed in Pacific Rim porphyryrelated copper gold systems Tnereasing temperature Favors the stability of progres- sively more dehydated mineral species. Ths is especially evident in clay/sheet silicate mineralogy in which progres- sively higher temperatures resule in the formation of the nieral sequencer smectite —> interlajered smectite (with gradually decreasing smectite content) ~> illite -> white mica, Similarly, zeolites become more dehydrated tinder hotter conditions, as illustrated by the sequence piilolite -> mordenite -> stilbite -> laumontite > ake Temperature also influences the degree of ordering oF cystallinity of minerals. Higher temperatures favor the formation of more crystalline minerals. Disordered kaolin ite and halloysite, for instance, form under ambient con- ditions, whereas more ordered kaolinite occurs under clevated hydrothermal temperatures, and well eystaline tickite develops under sill hott conditions, Tecan be seen from activity diagrams that uid com- position also has a strong influence on the alteration min- tralogy, whereas temperature has a marked influence om the actual position of phase boundaries. The ratios of com stituents ef, yg /ay ag4/4y+ are more important than absolute concentrations, For example, in active hydrother- inal sjstems, highly saline brines of the Salton Sea geo- thermal field (approximately 250,000 ppm toil dissolved folids) produce the same alteration assemblages at most temperature ranges asthe very dilute fluids (around 3,000 ppm total dissolved solids) of New Zealand, and some Tee- Linde geothermal fields (Weissberg et al., 1979). Absolute concentrations of components in hydro- thermal fluids have some effect on the nature of the aeration mineral produced, as this influences the degree Af aturation of the Tid wih respect to certain minerals, For example, sulfa, sulfides, and/or sulfates are aoc died with sotfstaras, and lepidoite is encountered inthe {lonstone geotherinal Felts where fs have high con- centrations of lithium (Browne, 1978). “The host rock composition to some extent control the alteration mineral assemblages. Skarn mineralogy forma in calearcous host rock, The secondary Kesar tnincral adularia is preferentally encountered where host ndor source rocks are potssiomich (eg, rhyolite or seine) Paragonite (Namica) under eertain cond done ouie asa ateraton product of lbite, wheres MUS coate forms from ered potstum feldapeta ‘Tue Kinetics or rates of alteraton/ mineral deposition more commonly afect the cretalinity of the minerals Mather than the species formed. Ainorphous site can form at moderately igh gmperatures where se Saturated fluids are qlienehéd (eg, geothermal surface Sipcwork). whereas cbse crystline quarts forms atthe rose temperanure but under static condons, hich per Bi dow ecmeigae, {The duration ofthe hydrothermal stem, oF the period during whieh permeabiliy has remained open, determines see, Cauttbnun has been established beaween the ct Tet ld amd hese rocks, Minerals hay form under SieGeclble condone ifequibsium has not been attained Permeability, commely 2s cilaional facture systems (chapter's) and locally as permeable lithologies, Brings Rees code into contact with hydromernmal Ruids, Phy we 205 agit alteration are. commonly encountered fuse the Bulge are at less than nevual ply whereas ropylie alteration s usually encountered in host rocks BonRltons of decreased permeabiliy further fom he sont fa lama ‘TEMPERATURE AND PH CONTROLS ON ALTERATION MINERALOGY ‘Temperature and fluid pH are the most important of the many factors which influence the mineralogy of hydrothermal systems. Under saturated, hot, hydrostatic conditions, pressure is directly related to temperature (Browne, 1978), whereas the gas pressure and the ratios of elemental concentrations are reflected in the fluid pH (Henley et al., 1984). The other variables (with the local exception of pethaps host rock composition and absolute fluid compositions) have only minor inffuence on alter- ation mineralogy0 __ Conner aN Leach The stability ranges for the common hydrothermal inerals encoutitered in Pacific Rim active geothermal and hydrothermal ore systems, are plotted in terms of tem- perature and fluid pH in Fig. 4.1. This figure is derived from a compilation of data from geothermal systems in the Philippines, Japan, US, Iceland, and New Zealand, in combination with thermodynamie and laboratory experi- ‘mental work on. various mineral phases. ‘The main refer- ences for this data are Steiner (1977), Browne (1978), Hemley et al, (1980), Elders et al. (1979), Leach et al (1985) and Reyes (19900). Fluid element concentrations and ratios, and pres- sures (partial pressure of gases, hydrostatic and lithologic pressures) are constant in Fig. 4.1. However, in many cases, these factors can substantially affect the temperature and pH stability ranges of the various mineral phases (Henley et al., 1984). Discussions of variations in these factors, which would add further axes to this diagram, is beyond the scope of this review. Absolute temperature and pH val- ues are not shown in Fig, 4.1 because of the influence other factors (above) could have upon the positions of the boundaries between mineral phases. In addition, itis more important in mineral exploration to determine, from alter- ation mapping, the relative, rather than absolute changes, in fluid conditions. The following discussions include the approximate temperature and pH ranges for most of these mineral phases. The different mineral groups categorized by increasing pH of formation are shown in Fig. 4.1 and described in the following paragraphs. SILICA GROUP MINERALS Silica minerals are the only significant stable alteration minerals to occur at very low fuid pH (generally below pH 2, Stoffregen, 1987) where they are commonly associated with small quantities of titanium-ron phases, such as rutile. Under these extremely acid conditions, opaline sil- ica, cristobalite, and tridymite are encountered within sur- ficial environments above the upper level of the chloride hydrothermal system, typically at temperatures of <100°C (Leach et al., 1985). Quartz is the main silica mineral at high temperatures. In Fig. 4.1, quartz or silica (cristobalite, tridymite, or amorphous silica) has been included in all mineral assemblages because hydrothermal fluids (in active geothermal systems) are most commonly saturated with respect to SiO, (Henley et al, 1984) Under higher fluid pH conditions, amorphous silica is encountered at temperatures <100°C. Quartz is alfiist always present at higher temperatures, whereas chal ceddony locally occurs at intermediate temperatures (gen- erally inthe range of 100°-200°C), especially under conditions of rapid deposition. The type of silica phase is also affected by the kinetics of deposition, For example, amorphous silica may form at temperatures up to 200°C in, rapidly quenched environments (e.g., scales in geothermal, surface pipeworks; Brown, 1986). ALUNITE GROUP MINERALS At fluid. pH alighi higher chan 2, alunite forms idler with the silea minerals over a wide temperature range (Stoffregen; 1987). It occurs in association with andalusite at high temperatures (typically >350°-400°C; Sverjensky et al., 1991). “The following four environments of alunite formation have been identified by Rye et al, (1992), using sulfur and ‘oxygen isotope data. The conditions of formation of alu- nite in these environments can also be inferred from its crystal form, as well as from the geological setting and min- eral paragenesis, 1. Stean-heated alunite develops under surficial environ- ‘ments by the oxidation of acid sulfate fluids from H,S gas which evolved from a boiling hydrothermal system at depth. Alunite deposited from these low pH steamheated waters commonly occurs as very fine-grained pseudo-cubic crystals. This steam-heated alunite may be encountered down to I-1.5 kim depths, in settings where acid sulfite fluids descend into’ wahing’ hydrothermal systems (Reyes, 1990b) 2. Supergene alunite develops from the production of sul furic acid by weathering of massive sulfide deposits and exhibits a poorly crystalline, very fine pseudo-acicular habit, 3, Magmatic alunite is derived from_magmaticdomi nated liquids and forms, well crystallized, commonly coarse-grained tabular to laihlike crystals which fill frac- tures, cement breccias, and deposit in leached vugs pseudomorphing phenocrysts or lithic clasts. Ahinite formed at higher temperatures, where it is intergrown with well crystalline muscovite ‘and/or andalusite, can also occur as large irregular crystals poikilitically enclos- ing quartz and other minerals, or as euhedral pseudo- shombic crystals, 4, Magmatic vein/breccia alunite occurs in veins and bree cias and is inferred to have heen deposited directly from volatilerich fluids which are ascending from a crystallizing melt (Rye et al, 1992). In this environment, alunite can occur as radiating prismatic crystals, KAOLIN GROUP MINERALS The kaolin group of minerals (Fig, 4.1) is derived from moderately low pH fluids (approximately pH 4 Reyes, 1990b), and coexists with the alunite group of minerals under a transitional fluid pH range (pH 3~# Stoflregen, 1987), Halloysite occurs mainly as a supergene weathering product, although there is some evidence (Harvey and Browne, 1991) that halloysice forms under very low temperature hydrothermal conditions. Zonations of hydrothermal kaolin group minerals with increasing depth and temperature have been identified in Philippine geothermal systems by Reyes (1990b) and Leach et al. (1985). Kaolinite is formed at shallow depths under low temperature conditions (<150°-200°C), and pyrophyllite forms at greater crustal depths, under higher temperature conditions (<200°-250°C). Dickite forms in a transitional setting between these ovo crustal levels and temperature ranges.~ ee eee ee ee ee er ee reer ere crcsssrsssvssse CONTROLS ON HYDROTHERMAL ALTERATION AND MINERALIZATION Eien Fe, a — INCREASING pH ————____» ana A fat Shs Hat Sn ee fe ee op a Sica “AX Siler SP Slca ‘chsmend CRSA] g & 847m Bn 9 HSNO Sica 4 ON ORAS k She ken obese SS | Te |g ie ‘Silica Silica, Sica Cio i} ° LL. £8 i Sm Ss Sricb S| HOHSM ucngm |B] & ZAR CSER OY Su SB alcns So] smacnd | NCHS | EL “Za Ge] Oe gk a ae ele] |e Os8axpe Kin 34° ch,» fo HO o1h Bf o) E A age 3 ibn BHe n KOK > ath Jz si Kk AS SOK SES crac} 1s 2 a+b PS 2 Sd ato | al Lecce Zt Soe cht : & yr a8 ay | a Ye oe Be dit BS a SY Glee = oly Ae ate AS as se 0 a @ a ni” Ok ZN Ok wae A Be FN Be S's e G50 4 a+ bp AN sna NN St Pep 3 < 2 , Ch = ii eR o NR E 5 5s 5 g @ 3 . 8 Aeok i A fi mao ise ie 2 PEO KAS NEES ISN AA re cf tia 0 2] BI AAY NaN NNN g Conditions of See fp 5 Paaes faa na? co 5 non-dissociation BEERS Pe fnien] 8 Silica | Alunite | Al-K | Kaolin I-K illite | Chlorite} Calc - Silicate Group | Group | Group | Group | Group | Group | Group Group Mineral Abbreviations : Ab -albite; Act - actinolite; Ad - adularia; Al - alunite; And - andalusite; Bio - biotite; Cb - carbonate (Ca, Mg, Mn, Fe); Ch - chlorite; Chab - chabazite; Chd - chalcedony; Ch-Sm - chlorite-smectite; Cor - corundum; Cpx- clinopyroxene; Cr - cristobalite; Ct - calcite; Do - dolomite; Dik - dickite; Dp - diaspore; Ep - epidote: Fp - feldspar; Ga - gamet; Hal - halloysite; Heu - heulandite; | - ite; l-Sm -ilite-smectite; K - kaolinite; Lau -laumontite; Mt- magnetite; Mor - mordenite; Nat -natroite; Op - opaline silica; Pyr - pyrophyilte; Q- quartz; Ser - sericite; Sid - siderite; Sm - smectite; Stb - stilbite; Tr- tremolite; Ti -tridymite: \Ves - vesuvianite; Wai - wairakite; Wo - wollastonite; Zeo - zeolite | Propyiitic © 9 | Outer/ Sub Propyitic FES] stam EER pote vanced Bei EXQY Prato FEES] potassic es 4. ‘Common alteration mineralog2 Conner aN Ls Diaspore is locally encountered with alunite and/or aolinite group phases, commonly in zones of intense si ification, where it forms atthe expense of prophalite by the reaction: quattz + diaspore <-> pyrophyiite (emley etal, 1980). : Ee ILLITE GROUP MINERALS Where the fluids are ata fluid pH in the range of 5-6, the illitic group of minerals dominate (Fig. 4.1), and ¢o- exist with the kaolin group minerals at fluid pH 45, @epending on the temperature and fluid salinity (Hemley fet al, 1980; Reyes 1900). Depth/temperature relation- Ships of the illite group minerals are well documented from both sedimentary basins and active geothermal sy tems (Steiner, 197; Browne, 1991; Harvey and Browne, 1991). Smectite occurs at low temperatures (<100"~150°C), intetlayered illite-smectite at around 100°-200°C, illite at approximately 200°-250°C, and muscovite at >250°C. Sehiciee is a fine-grained muscovite which may contain ome illite, and is encountered at levels which are tran- Sitional between illite and coarser well crystalline mus: Conite (eg, Frieda River porphyry copper deposit, Papua Now Guines; Britten, 1981). Corundum forms at eemper tures in excess of 400°450°C (Hemley et al, 1980) with mnuscovite and/or andalusite (Lowder and Dow, 1978) “The smectite content within the interlayered illce- smectite cays progressively decreases with increasing tem- perature over the 100*-200°C range (Harvey and Browne, Tool), The crystallinity of illite and sericite increases with increasing temperature, and can be monitored by XRD analyses of the peak width, at half the peak height, of the {O01} reflection, (ie., the Kubler Index; Dunoyer de Segonzac, 1968}. The changes in muscovite crystallinity can also be monitored by XRD analyses. With increasing temperature there is a progressive change from a disor dered IM_mica to a well crystallized "2M. muscovite ‘Although muscovite is the common mica mineral present in coppergold hydrothermal systems, the sodic mineral phase paragonite is encountered in some systems where Fhe hott rock has a high Na:K ratio (eg. albite asthe pl goclage mineral). The vanadium mica roscoelite, and the Somiuim mica fuchsite, ate also locally common and are Geposited from fluids sourced by migration through mafic yoleanie rocks/intrusions CHLORITE GROUP MINERALS ‘Under generally near neutral pH conditions, chlorite: carbonate (Fig. 4.1) minerals become dominant, coexist: ing with illite group minerals in environments where fluid pH is 5-6 (Leach and Muchemi, 1987). Interlayered chlorkte-smectite occurs at low temperatures, grading to chlorite at higher temperatures (Kristmannsdotter 1984), Jn active geothermal systems, this transition occurs at significantly lower temperatures in rift environ pnents (e.g, Iceland, Kristmannsdotter, 1984) than in vol canie island terrains (e.g. Philippines, Reyes, 1990a), tnd possibly reflects a response to either fluid or host rock chemistry. CALCSILICATE GROUP MINERALS The calesilicate group of minerals (Fig. 4.1) form under neutral 0 alkaline pH conditions. Zeoliteschiorite ‘cathonate are formed under cool conditions, and epidote, followed by secondary amphiboles (mainly actinolite), progressively develop at higher temperatures. Zeolite min- Erals are particularly temperature sensitive. Hydrous 2e0- Tites (natrolite, chabazite, mesolite, mordenite, stibite, heulandite) predominate under cool conditions (<150°- 200°C), while less hydrated zeolites such as laumontite (150°-300°C), and wairakite (200°-300°C) occur at pro: gressively deeper and hotter levels in the hydrothermal ss fem (Steiner, 1977; Leach et al., 1983). In some systems prebnite and/or pumpellyite are encountered at tempera- {ures of around 250°-800°C (Elders ec al., 1979) in associ ation with, or in some instances in place of, epidote Epidote occurs as poorly crystalline incipient grains at temperatures of around 180°-220°C, and as well crystalline pases at higher temperatures (6220°-250°C; Reyes, Yo00b). Secondary amphiboles (mainly actinolite) appeat to be stable in active hydrothermal systems at temperatures S$a0°-300°C (Browne, 1978). Biotite predominates within, tr immediately adjacent to, porphyry intrusions, In active systems. secondary biotite develops at temperatures of 3800°-325°C (Elders et al., 1979). Active porphyry envi- Tonments are characterized by clinopyroxene (>300°C) fand_ garnet. (2325°-350°C) assemblages (Elders et al, 1979), However, hydrated garnets are locally encountered at significantly lower temperatures (250°-300°C) in. the Tongonan geothermal field (Leach et al. 1983). The zonz- tions in ska mineralogy with respect to temperature are in many ways comparable to those in porphyry copper ens ronments, and are discussed jn more detail in Chapter 3. OTHER HYDROTHERMAL MINERALS Carbonate minerals are encountered over a wide range of pH and temperatures, and are associated with kaolin, illite, chlorite, and calcsilicate phases. A zonation in car bonate species with inereasing fluid pH is encountered in many hydrothermal systems (Leach and Corbett, 199 1994, 1995). FeMn carbonates (siderite-thodochrosite) coexist with kaolin and illitic clays, while mixed Ca-Mn- MgFe carbonates. (thodochrosite-ankerite-kutnahorite- dolomite) occur with illitic and chloritic clays, and Ca Mg, carbonates (dolomite-calcite) coexist with chlorite-calc-sil- jeate mineralogy. This zonation is interpreted to reflect the decreasing mobility of Fe, Mn, and Mg at progressively increasing fluid pH (Leach et al., 1985). Carbonate min; rals typically extend throughout all levels in bydro~ thermal systems, from surficial (o porphyry-elated skara environments. Feldspar minerals are associated with both chlorite and calcsilicate mineral phases. Secondary feldspars are {generally stable under near neutral to alkaline pH condi- tions. Albite occurs where fluids have a high ay,'/aj" a0 ‘and potassium feldspar a low ay,*/a4¢ ratio (Browne, 1978) ‘Adularia occurs as a low temperature secondary potassium feldspar species, whereas orthoclase is encountered at na 2222332383982 eeeeaeeaeae(CONTROLS ON HYDROTHERMAL ALTERATION AND MINERALIZATION 73 SE ann No Bp. high temperatures within the porphyry environment. Browne (1978) demonstrated that adularia preferentially occurs within high fluid flow permeable conditions, and. albite under low permeability conditions. Sulfate minerals are encountered over most tempera ture and pH ranges in hydrothermal systems. Whereas alu- nite forms under low pH (<3-4) conditions, anhydrite forms at a higher pH (Reyes, 1985) and temperatures sgreater than 100°-150°G, and gypsum develops in cooler environments (Harvey et al., 1983). Although jarosite commonly forms as a weathering product of sullides, it so occurs at shallow levels in acid environments in some Philippine active geothermal systems (Leach et al, 1985) Various hydrothermal mineral phases contain halogen elements (e-g., boron in tourmaline; and fluorine, chlo- rine, and phosphorous in apatite), which is inferred to indicate that the fluids contain a significant component of ‘magmatic volatiles. These phases are commonly associated. with sericite/mica formed at high temperature under moderately low pH conditions. ALTERATION ZONES ASSOCIATED : WITH ORE SYSTEMS AliiGtigh itis considered preferable to use the alter= ation mineral assemblages themselves to define the style of alteration, a classification of broad alteration types can be beneficial in describing overall characteristics of zoned alteration systems. Alteration stjles in most alumino silicate teks have been classified by Meyer and Hemley (1967) as propylitic, intermediate argillic, advanced argilic, sericitic, and potassic types. Rose and Bart (1979) indicate that the serictic type is identical to the phyllic alteration of Lowell and Guilbert (1970). The term argillic, which is now in ‘common wse, is synonymous with intermediate argilic. ‘The mineral assemblages within these five alteration vones are shown in Fig. 4.1 and may be summarized as: Advanced argillic alteration comprises mineral phases ‘which are formed under low pH (<4) conditions (ie, sil ica and alunite group minerals) in addition to assemblages hich contain both alunite and kaolinite group minerals Meyer and Hemley (1967) include high temperature Jaolin group phases (i., dickite and pyrophyllite without alunite group minerals) in advanced argillic alteration, and this convention has been followed in Fig. 4.1. Argillic (intermediate argilc) alteration assemblages con- sist of those formed at relatively low temperatures (>200°~ 250°C) and moderately low fluid pH (approx. 4-5), Rose and Bart (1979) defined this type of alteration as encom- passing those assemblages dominated by kaolinite and sunectite. However in Fig. 4.1, other low temperature Kaolin (halloysite) and illite (interlayered llite-smectite, ile) group minerals, which are not included in phyllic/ seticitic zones, are placed within the argilic type of alter~ ation, The argillic alteration assemblage may also contain chlorite group minerals subordinate to the illite group minerals Pyle alteration forms at similar pH ranges o the argillic aeration neal but higher temperatures (©200"-250°0), and is characterized by the presence of sericite (or mus: covite). The phyllic zone can also include higher tempera: ture members of the kaolin (pyrophyllite-andalusite) and chlorite group minerals where they are subordinate to sericite/muscovite lite aeration forms under near neutral to alkaline conditions characterized by the presence of epidote and/or chlorite (Meyer and Hemley, 1967). At relatively low temperatures (<200°-250°C), where alteration assem blages are dominated by zeolites in place of epidote, the term sub-propylitic may be applied. The occurrence of secondary amphiboles (generally actinolite) at high tem- Peratures (2280°-300°C) may be used to characterize an inner-propylitic alteration zone. Secondary albite and/or Kfeldspars are commonly encountered in propylitic alter ation assemblages, Potassic alteration forms at high temperatures, under neutral to alkaline conditions and is characterized by biotite and/or K-feldspar + magnetite + actinolite + clinopyroxene. Where the host rock is a calcareous sedi- ment, skare mineralogy forms under similar conditions, and consists of zoned calcsilicate minerals such as C: garnet, clinopyroxene, and tremolite. CONTROLS ON THE DEPOSITION OF GANGUE MINERAL PHASES. ‘The main non-ore or gangue components, which are deposited directly from solution in ore-forming systems, are silica minerals (predominantly quartz) and carbonate minerals, with local abundances of sulfate mineral species. ‘The following sections outline the main factors which con. ol the deposition (and dissolution) of these minerals in hydrothermal systems, SILICA MINERALS. clude the presence nts (Fournier, 1986). In dilute, epither mal environments (ie., +<300°-3507°C) quartz will deposit upon cooling, with mas. imum solubility occurring around 850°C (Fig. 4.2). There- fore, rapid quenching of high temperature fluids in the upper regions of a fluid upflow conduit will pr asil. Acshallow levels in an epithermal system (<]00"-150°C), the various silica minerals deposited include amorphous silica, cristobalite, widymite, chalcedony, and. quart Although quartz is the least soluble of all the mineral phases, the rates of temperature change control the min- eral species formed (Saunders, 1904). For example, amor. phous silica is deposited as silica sinters under rapidly cooling conditions, where boiling hydrothermal Huis at >200°C rapidly cool to <100°C in surficial environments.4. Conner apn Lesctt 20 300 400 00 Temperature" ‘A Dilutionicooting of upwelling mesothermal uids B, Cooling of upweling epithermal fluids I S00 bars co on ri 00 él gl z 2 / z Eos / § tw i a 3 B20 pete) cue o ©. Porphyry veins formed by through pressure release Temperature °C (Quartz solubily as a function of temperature and salinity (I) and pressure (I). Redravin from Fournier, 1985b Fig. 42 Quartz solubility Cristobalite and chalcedony form under progressively slower cooling environments, The other silica minerals, recrystallize t0 quartz with time and/or increasing tem- perature (and pressure) along the following path: opal-A => beta cristobalite —> gamma cristobalite -> chalcedony ~ > quartz (Fournier, 1985b). Fine-grained silica, especially thin colloform banding, forms under rapid quenching conditions; whereas well-formed crystalline (druzy, crys talline, cockscomb, dog tooth) quartz forms where tem- perature drops are less rapid, commonly within open spaces (Saunders, 1994) Alteration under acidic conditions commonly results| in the formation of an intensely silicified host rock. At fluid pH <2, almost all cations except silica (and minor Fe, Al, and Ti) are leached from the rock (Stoffregen, 1987), and this results in the formation of a vuggy, residual quartz (White, 1991). In addition, sulfate-iiea complexes in low pH fluids may cause silica supersaturation (Fournier, 1985a), and therefore deposition of sulfate minerals, such as alunite or barite, from these fluids can result ia the pre- Increases substantially with increasing pressure and temper- ature, Therefore, rapid presure drops, possibly associated, with a change from lithostatic to hydrostatic pressures in a porphyry environment (Chapters 5, 8), can result in silica oversaturation, and give rise to quartz stockwork vein development (Fig. 4.2). Quartz deposition may also result from the dilution of this saline fluid by mixing with circu lating dilute meteoric dominated waters. CARBONATE MINERALS The solubility of carbonate minerals in_an aqueots solution (at pH 4-8) may be represented by the equation: MCO, + CO, + H,O = M® + 2HCO™ (there M= Ca, Mn, Mg, Fe) ‘The dominant control on carbonate deposition is increasing temperature; whereas dilution and pressure drops are only secondary factors (Fig. 43; Fournier 19850). Therefore, carbonate deposition occurs at shallovs levels by the heating af descending CO,rich waters. On the other hand, ifa fhuid, which contains signifi cant concentrations of dissolved CO,, boils rapidly, then release of CO, promotes carbonate deposition (Fig. 4:3) ‘ypically as bladed crystals (Simmons and Christenson, 1994). This release of CO, is accompanied by an increase in fluid pH which will inhibit quartz deposition, Blaced carbonate is, however, commonly replaced by quart. ‘This is interpreted to result from dissolution of carbonate and Peaeeenn2enaeaeneaneeeeeeeeeeeeneeneneeneneneaaeeneenn2a2nae2eCONTROLS ON HYDROTHERMAL ALTERATION AND MINERALIZATION 75 EES FSi yp om ‘aim pesaue m I os q e 2 So ‘ 3 a °2 ec) 2m Nae ° 10 By = 0 ma Bs Temperature “C Calcto solubity as a function of temperature and salinity (I) and pressure (I). ‘A. Descending cool bicarbonate fluids B. Upwelling and boing epithermal thids Temperature "e Redrawn from Eis, 1959 and 1969 FIG, 43 Calcite solubility deposition of silica in response to the decrease in fluid temperatures upon boiling (Simmons and Christenson, 1994). Thus, many epithermal systems contain quartz which pseuciomorphs platy carbonate. At pH <4 carbonates are dissolved. At temperatures of <100°C and neutral conditions (pH>6-7), HCO™ domi nates over dissolved CO, (Ellis and Mahon, 1977), and therefore travertine deposits are encountered at the sur face in some geothermal systems (e.g., Amacan, Philip- pines; PNOC-EDG, 1985a). ‘The controls on carbonate solubility under high tem: perature, saline conditions are not well documented. How. exer, comparisons with sulfate solubility, and the observed. deposition of carbonate minerals from magmatic brines in porphyry environments (Chapter 5), suggest that under hot, saline conditions, carbonate solubility may similarly decline with decreasing temperature, SULFATE MINERALS The solubilities of sulfate minerals are also strongly con tvolled by temperature, and like easbonate minerals exhibit an inverse relationship with inereasing temperature undet dite conditions (Fig. 4; Blount and Dickson, 1969). Gyp- sum deposits in preference to anhydrite at low temperatures (<100°=150°G; Leach eta, 1985). In highly saline porphyry cnvizonments, anhydrite solubility decreases proportionally with decreasing temperature (Blount and Dickson, 1969), and 2s.a consequence, anhyelite is commonly deposited in porphyry environments. At high activities of sulfur, and/or low fluid pH, alunite will deposit in preference to anhy: rite (Reyes, 1985) Barice is the least soluble of the sulfate minerals and will preferentially deposit, from a dilute solution, upon heating at temperatures ‘above about 100°C. (Fig. 4.45 Blount, 197 in Barnes, 1979). Under saline conditions, barite solubility decreases with temperature (Fig. 4.4), Therefore, the common occurrence of barte in the central zones of high sulfidation systems is inferred to result from the cooling of hot magmatic derived fluids (e.g., Nena, Frieda River Copper, Papua Nev Guinea; Chapter 6) CONTROLS ON METAL DEPOSITION, GOLD Gold is possibly transported as a chloride complex (AuCT) under deep mesothermal and porphyry environ- ments, and its deposition is controlled by decreases intem- perature, pressure, and salinities (Henley, 1973; Fig. 4.5) In low sulfidation mesothermal and epithermal systems (<300°-350°C), gold is preferentially transported in near neutral fluids asa bisullide complex (Au(HS)"; Seward, 1982). In this case the controls to gold deposition are more complex, and dependent upon a wide range of fac- tors, which are dominated by: changes in fugacity of oxy= gen, activity of sulfur, and pH, as well as temperature and salinity (Seward, 1982)76. Conner axp Lect 00 bas Se oe oa 6 m oe > a wo g El - = a B 2 z \ E | > 8 1 Neo a te 0 a fn eA a we Temperature" Temperature*C Bare solbity as a function Anycite soll a atten ol temperature and sal of temperature and sain ‘A Upwoling high ulation tuds A Upwling porphyry copper ful in possi alteration zones, 8, Descending acid sulfate ids 8, Descending acd sute tds Redravin from Blount, 1977, in Bares (1979) Redrawn from Blount and Dickson (1969) G4 Bart and anhydrite solubility piled, tm NaCl ay,5=10°, SO,/H26=10"" J-200°C ayje =10%, tm NaCl, SO,/H2S=10"" Epihermal wacSiecal i f NS yiiel 2 s e Beh a XN a z ey se & 5 ee ae ? See 8 a Zn 3 So cucr \ 48 Cutis)3 2 s er High Low i SBlceton Sedation | S ray ata 1 io ‘ i 3 ae 2 388 me 4 ¢ . Temperature" oH Solubility of Au, Cu and Zn Relative to Temperature and pH eck and mci te Large (1694 AuCirZn Solubility~-+- +r rrr rrr eer wre wrwrvreoseesessvsesssssaaa CONTROLS ON HYDROTHERMAL ALTERATION AND MINERALIZATION. 7” SEE Rbsene ne 6108p. oe ‘The influence of temperature and fuid pH (under di- ute, reducing conditions) on gold mineralization is illus trated in Figure 4.5. The solubility of the gold complex ‘Au(HS)®, increases with decreasing temperatures, but ‘decreases with decreasing fluid pH (Seward, 1978). The deposition of gold at epithermal/shallow meso- thermal levels can be summarized by the equation (Brown, 1986): Au + HS... +HS"= Au(HS);+ 1/2H,, In these environments, gold deposition from a chio- ride hydrothermal fluid can result from boiling, mixing with oxygenated metcoric waters, or mixing with an acid sulfate fluid (Brown, 1989; Spycher and Reed, 1989). Fig. ‘ure 4.6 illustrates the hypothetical changes in the fluid pHi and fo, which could be expected in each of these scenarios and are represented by paths A, B, and C respectively A. Boiling The exsolution of H,S upon boiling is an efficient mechanism for gold deposition at shallow, epithermal lev- els (Seward, 1982); however, boiling also causes an increase in pH and decrease in temperature, both of which increase gold solubility (path A in Fig, 4.6). Brown (1986) showed that flashing (ie., sudden pressure release and associated boiling) of deep hydrothermal fluids to atmospheric pressure at Broadlands geothermal field, New Zealand, deposited high concentrations of gold, silver, and copper in scales in surface pipework (Chapter 2). He cal- culated that the amount of gold deposited represents a decrease in solubility of approximately three orders of magnitude between the deep hydrothermal system at 260°C, and 100°C at atmospheric pressure Quartz, adularia, and quartz pseudomorphed by bladed carbonate commonly occur in mineralized epithermal veins, and their presence is taken as evidence for boiling as a mechanism for gold deposition in epithermal environ- ments (Hedenquist, 1991), However, as illustrated in Chapter 8, although gold-silver mineralization is hosted in the banded quartz, adularia, and locally bladed carbonate veins, most gold typically occurs in thin sulfide bands which commonly contain low temperature clays (eg. smectite, kaolinite, or chlorite). Therefore the presence of adularia’ and/or bladed carbonate in auriferous banded epithermal veins cannot, ia themselves, be used a8 evi dence for yold mineralization as a result of boiling. B. Mixing with oxidized waters ‘A change in the oxidation state of a mineralized fluid, caused by the mixing of a deep hydrothermal fluid with an Au (HS)3:28= 0510" — Es- 10109 — | auch 3s fog fos pH F (Gold solubiity as HS- and Clr complexes as a function of pH, fo, and ZS (moatted fom Seevard, 1982; Brown, 1996) A: Boiling B: Mixing with oxidizing fds 18: nengwin ons Fuld Pate 250°C; 1.0m NaCl, 0.01m S, pHS. Foo, =1 HematterChlotte 2 (1) Gold solubiity as a function of log to, (Romberger 1986} D: Hypothetical oxidation of Broadlands ‘geothermal fluid at 260°C with 1.5418 Au FIG. 46 Gold solubility78. CORBETT Ap Lescet oxidizing surficial water, has been shown experimentally to ‘COPPER promote gold deposition (Brown, 1989). The solubility of gold (asa bisulfide complex) in a near neutral pH fluid at 260°C relative to changing fo, conditions is illustrated in Fig. 46. Increases in fo, of aud in equilibrium with pyrite + pyrthotite wil initially be accompanied by an increase in gold solubility (path B, Fig. 4.6), however, im the region of ure’ salinky, pEl, and increases in TLS cone ee the pyrite/hematite or chlorite phase boundaries, small (Barnes, 1370) However, it has been Meerited (Barnes increaser in Oxidadion can decrease gold solubility by many 1979; Henley and Brown, 1985; Brown, 1986) that copper ‘orders of magniuude (Romberger, 1986; path D, Fig. 4.0). may be preferentially ansported asa binulfide comples ix In several southwest Pacific Rim low sulfidation gold Jow temperature (<200°-250°C) epithermal environmen Sepsis there isa close association of hypogene hematite and under dilute and near neutral conditions. This is sup. and gold mineralization (White etal, 1995; Chapters 7 ported by the common occurrence of low-grade, but sy and 8), and chlorite and/or chloritesmectite occur in sul- Rican, copper which accompanies geld inches fide bands which host most of the gold mineralization in jn many epithermal quartz vein deposits (Chapter 8) some banded epithermal deposits (e.g., Cracow, eastern q Australia; Chapter 7: Hishikari, Chapter 8). These are taken as evidence that the increase in the oxidation state LEAD AND ZING may be a significant mechanism for gold deposition and. These metals are transported as chloride complexes formation of bonanza gold deposits tunder most hydrothermal conditions (Barnes, 1979), and eit deposition results from decreases in temperatures C. Mixing with low pH fui (path A, Fig. 4.7), salinities (path B in Fig. 4.7), and pres: Experimental and computer modelling studies (Brown, sure (Henley, 1985a, 1985b) 1989; Spycher and Reed, 1989) illustrate that mixing of near neutral pH chloride hydrothermal fluids with acid sulfae waters an be an efficient mechanism for te dep SILVER sition of gold in epithermal systems (path C, Fig. 4.6); how- Silver is transported mainly as a bisulfide complex in ‘ever, the affects of dilution and cooling counterbalance dilute conditions, and as a chloride complex in hotter this decrease in solubility. Gold mineralization in some more saline conditions (Seward, 1976; Barnes 1979: Fig New Zealand and Philippine geothermal systems may be 4.7). Therefore, silver mineralization mimics base metal related to the mixing of deep hydrothermal fhuids with sus- phases at deeper levels of hydrothermal systems, and gold ¢ acid sulfate waters (Chapter 2). The recognition of _atshallower,epithermal levelsrAdany sthywest Pacific Rion sulfate minerals in some low sulfidation epithermal gold. high sulfidation systems are remarkablyJow in silver, unlike systems (White et al., 1995; Chapters 7 and 8) also suggests thostin, the eastern Pacific inferring that either dhe hot, that acid sulfate waters may locally have been involved jn very acidic fluids are Ag-depleted,,or that Ag-complexes {gold deposition, are much more soluble than gold under tow pkL condi- In high sulfidation systems, gold is interpreted to be Yions (Fig. 4.7). Arsenic and antiinony Are also probably Copper is probably transported as a chloride complex (cither as CuCl or CuCl*) over temperature and pH ranges which are encountered in most hydrothermal 5 tems (Crerar and Barnes, 1976; Barnes, 1979; Fig. 4.5). Copper deposition is controlled by decreases in tempera: transported either as HAu(SH), oF the chloride complex ansporied as bisulfide complexes and so display spatial AuCl,- (Giggenbach, 1992). It has been proposed (Heden- dist ions similar to, gold (Spycher_and-Reed, 1989). Guster ae 1904) that ANCk, is te Corton cotiper” Aelelfeason inthe mned Shecw woR keno He pol wacaper idee taton pe ane et gu Re ee tar for tooo SESLIOL percent Gt) covclicnd a igh sicete tas a pha ea een nee a slo tems. The common association of copper and gold miner. peratures (Spycher and Reed, 1989), (Hedenguist ot l,, 1994) to support the concept thet 7 AOSte adr uk Bt are tn oa eee et _ gold in these environments, because copper i prabsbly The ser content of gold is commonly given as fine 2iso transported as a chloride complex (CuCl!) Cooling, "ESS (+ Au/Au+Agx1,000). Previous waiters (Morrison et posite omuning wth groundace iste whee th; 2891) showed tat Archean, Ste Bey and Mtn ‘nin mechanism of gold deposition from these complexes ol systems have high and consistent fnenesses; howeveh pie pease Src Forty, slGnogen and piel ces Other complexes wich anspor gold in high sun: ibt we tnenene ranges wih each lac These spe" dation systems have also been proposed, AWHS® has been ®t Wide variations may be explained by: Sedna arte ie ead ate Pre ee ry eene and elsewhere (Seward, 1989) it has been postulated that Sarees a amin aes oes Beane EA nt cong ee RE Stine! chiowacbininds crple: Fae GOLD FINENESS + The attribution of deposits from widely differing geo logical environments in a single class, such as both high sulfidation gold (e.g., Mt. Kasi Fj) and adulariasericte epithermal goldsilser (eg, Hishikari, Japan) grouped within the epithermal class, and shallow level carbonate- P-AUCHS),]. base metal gold (eg., Wau, Papua New Guinea) andCONTROLS ON HYDROTHERMAL, ALTERATION AND MINERALIZATION 79 ego a SET Fasc ep. coe 5 10mg kg choride 8:10 mg/kg chloride re 24 Solubilties of zine (as sphalerie), lead (as galena), siver (as argontite) and gold as a function of Bo temperatute, salinity and complexing agent 2 {fechawn from Henley 1986a and 19856) 2 24 Copper (as chalcopyrite) data extrapolated and (inocfed trom Hervey and Hunt, 1992) g 44 Metal deposition as chore complex from cooling (A) and dition (8). 4 a 200 200 300 Temperature "C FIG. 4.7 Zine, lead, and copper solubility porphyry coppergold (eg., Guinaoang, Philippines) grouped within the porphyry class © The comparison of bullion data (e.g., Waihi, New Zea- land), which also incorporates silver from phases other than gold, with microprobe determinations from gold grains. Figure 4.8 presents histograms of the finenesses of hypogene gold from selected southwest Pacific gold and coppergold prospects and deposits, based on the classifi- cation used for these systems in this volume. The data is derived. from unpublished microprobe analyses by Ken Palmer (Victoria University, Wellington, New Zealand) for T. Leach, except where indicated, Figure 48 indicates that there is a systematic decrease in ‘gold fineness at progressively cooler and. shallower crustal levels (or distal to the intrusive source), from 920), through + quartz-sullide gold * copper (average = $50), and. © carbonate-base metal gold (average = 765), to * epithermal quart silvergold systems (average = 685) * porphyry coppergold /skarn (average White (1981) also noted that gold commonly occurs at a loyser fineness in deposits formed at shallow epithermal levels, and computer modelling (Spycher and Reed, 1989) suggests that this may be related to decreases in tempers ture in the absence of other silver minerals. These zona- tions therefore indicate that temperature is probably the ‘most important control on gold fineness in i related gold-copper systems. Wide ranges in gold fineness within a single deposit is interpreted to reflect wide tem perature ranges during mineralization. For example, at Kidston, eastern Australia, gold is associated with both quartz-sulfide and carbonate-base metal vein styles; and at Me. Kare, Papua New Guinea, gold in the roscoelite-bear ing epithermal quartz silvergold mineralization was deposited over a wide temperature range of approximately 250°C to <100°-150°C (Chapter 7). ‘The fineness of gold in intrusion-related epitherniat ‘quartz silvergold systems, and adulariasericite epithermts} old-silver systems is closer to the fineness of gold in eat Bonate-base metal gold systems, than would be expectert from only the generally cooler coniitions of mineral tion. This may be a function of # Many carbonate-base gold metal systems form at vey shallow epithermal levels (e.g Maniape, Papua Nev Guinea; Karangahake, New Zealand) and therefore the gold is silversrich.80. CORBETT ANY LACH rleite epithermal gold-siiver || y+ Ware HIANZ * ‘oven. Aue he, Haha sen a Epitharmal quartz gold-eilver Tame NZ Porgra Zoe PN Kare PN. {Sota vor 4 Carbonate-base metal gold oS Taare NZ) Pores coer P| Meret, € Aut. | ‘reds Five, PNG, ass eg, Saloon enego oth, PW Quartz-culfide gold + copper son, ex (onan) PIS, High eultidation gold-copper Yoreavens. ©) MaKe Porphyry sk Fil ae Number ot analyses @ Bement) 6.Tee rp es © mana cy @ eexgera. com a & rei © ances fees So et @ sanens en © Famseoa. 988) er apie averea Fic.48 Gold finenessCONTROLS ON HYDROTHERMAL + The preferential partitioning of silver into other miner als (Ag-sulfosalts, sulfides, and tellurides) in epithermal systems could result in less silver being available to be incorporated into the native gold/electrum (Afifi et al, 1988). Spycher and Reed (1989) showed that gold deposited under low pH conditions is ata very high fineness, This is supported by the data on high sulfidation systems in the southwest Pacific Rim (Fig. 4.8). Free gold in high sulfidation systems is only observed in very shallow, epithermal environments, however, even under these cool conditions the fineness of gold is very high (average of 935 for Mt. Kasi, Fiji; Peak Hill, eastern Australia; Zone A at Wafi River, Papua New Guinea). The low silver content of southwest Pacific Rim high sulfidation systems contrasts ALTERATION AND MINBRALIZATION 81 with the high silver systems in South America (e.g., La Coipa; Oviedo etal., 1991). METAL ZONATIONS ‘The vertical and horizontal zonations in metals, which are observed in many Southwest Pacific gold-copper sys- tems, are a result of the mechanisms of transportation and deposition of these metals and their relative solubilities under variable physio-chemical conditions. Based on the above discussions, Fig. 4.9 summarizes how metals may be complexed under decreasing temperatures away from a source intrusion in both high and low sulphidation sys- tems. The different environments that mineralized fluids encounter at progressively shallower crustal levels is inter~ preted to produce the observed zonations in precious, base and toxic metals. LOW SULPHIDATION HIGH SULPHIDATION Choe Complex Tanspon | __Bt-Sufle Conpox Tanapont ioe complex Tanspon | ave 1 depen i Sure aes Fala ae | A a [eee | I i “hein EI ag as | L wwe fi q | 5 se Sepostion Zn-Pb a ee : ty Set i | | eonson | | ce enton i 13) Lee-zn" = Ty] 4 { oe L. : hed ba oe ee fy anu | Sting sion : as sepeion i 1 4“ ioade Contos | eve cu, Pb, Zn, AU, Ag. SB. As, (?7Hg), 7Mo Leare Ft + Grystal ty 4 Met + E> F164 Mechanisms for meal onations in hydvothenmal stems