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    REVIEW ARTICLE The role of magmas in the formation of hydrothermal ore deposits Jeftrey W. Hedenquist & Jacob B. Lowenstern Magmatic fluids, both vapour and hypersaline liquid, are a primary source of many components in hydrothermal ore deposits formed in volcanic arcs. These components, including metals and their ligands, become concentrated in magmas in various ways from various sources, including ‘subducted oceanic crust. Leaching of rocks also contributes components to the hydrothermal fiuld—a process enhanced where acid magmatic vapours are absorbed by deeply circulating meteoric waters. Advances in understanding the hydrothermal systems that formed these ore deposits have come from the study of their active equivalents, represented at the surface by hot springs and volcanic fumarol Wirar are the sources of metals concentrated in ore deposits? This question was fist addressed sn the sixtenth century by Agncola, who concluded that heated rainwater eaches metals from rocks and then transports the metals to the sites of ore deposition, A century later, Descartes proposed that vapours released during cooling and crystallization of the Farth’s interior fre responsible for filing fractures with ore. Thus, the stage was set for controversy between the Neptunists and the Plutoniss, 8 debate that continues today ‘iydrothermal systems posered by magmatic intrusions dom: nate fuid movement inthe upper crust, and are responsible for onvecting a large proportion of Farth’s heat to the surface. At the same time, the Nuids transport metals, forming the single most important class of ore deposi, those ofthe hydrothermal Category. For example, large, low-grade deposits of copper (pls molybdenum or god) within shallow igneueinteusions. known 4s porphiyries, provide more than hall of the world supply of copper and molybdenum. Other types of hydrothermal ore depo- ‘SU(Table 1), some of which form a a greater distance from the magmatic hearth, are also significant repositories of gold, silver. lead, aine, tin, tungsten and other elements. Nos-magmatic hydrothermal systems are also important in metallogenesis, such 4s the sedimentary-hosted deposit rich in copper ead and vine that form by compactve expulsion of fuis from large continen tal basins, and lode gold deposits associated with metamorph ism. Nevertheless, the fux of hydrothermal fluids responsible for these deposits is minor compared to that caused by circulation due o intrusion of magma There ie agrocment that many hydrothermal ore systems 10" (re. 4), the calculated Cu fux Is HOt yr (with >350 kg yr"! Au). High concentrations of Cu and other metals such as Av are also observed inthe aerosols that accompany other erupting volcanoes, such as Augustine it Alaska, MU Eta in lay (Table 2) and ehewhete Other evidence bearing on the relationship between magmas and ofe deposits comes from some correlations between the type ‘of metal deposit and the composition ofthe associated magma, For example, peralkalineintrsions with high K.0 of Na:O can host ores of lthophile elements suchas Zr. Nb and lanthanides, whereas more luminous F-ich systems are typically assoeiated TABLE Magnetic fas sesharged tom volsanoes nite Satu Ieiod, oi, op MLB, NZ" Japan —Augastne, Alska"®”” tay = Yer 198519901976 1987 1975, 4987 Sie ot Eruplon Fumarole Eruption _Fumarole Eruption sicnoree Tempe) 850 877 90070800 Fux oy) Ko 19 52ND 003 50 co: 05 Ge ND 2003 13 @ 00a 005 306 2003 Os-05 5 B06 009 S02 D003 02075 Guay), 10 088 31200 OTT 480-580 auugye”) >38 002 ND No 804.200 Abundance atios* Ny3(-10) 55 008 50-800 0s 40 Gy 10% 2400 19 23004700 23 1000 NO, not determined "ror comparison wih the erpted seosol the Na/S and Cu/S of ‘uarles White sland are 740 >and 28% 40 ® respecte, 520 with Sn, Mo and B ore bodies. Tin, and eommonly W. tends 10 be found associated with reduced magmas (as indicated by the absence of magnetite) whereas Cu ancl Mo ore deposits tend 10 ‘ecu with more oxidized magmas (containing magnetite)". ven within voleanie ares, correlations exist between the fectonic ecvironment and the metallogeny of an ore district”. If ore Formation were controlled solely by circulating meteoric water, ‘there various correlations would be unexpected Sources of metals in magmas Notwithstanding the evidence citod above for an association ‘between magmas and ore deposits, we sill want to know where ‘magmas aequie their metals and how these metals are concen- trated to form ore. Metals can enter magmas through a variety ‘of pathways, including mantle melting, mass transfer from the Subducting slab and meting of the erst. Most of Earth's sider ‘phil (Fe-loving) elements such as Sa, Mo, Au and the PI- aroup clements may be locked away in the Fe-Ni core causing thee crustal abundanees to be much less than those ofthe global bulk, Nevertheless, many ofthese elements are also present in Fe Ni sulphides in the upper mantle", During partial meling ‘of the mantle, these sulphides are partially consumed, and contr= ‘bute metals to basaltic iquids that then ascend into the erust, both along mid-ocean ridges” and at subduction zones (Fig 1). In the former setting these erupted. basalts are commonly altered, and together with their associated oceanic sediments, fre eventually subducted below the continental crust, inducing reeling in the mantle wedge beneath the voleanic are. Many arc ‘magmas show clear evidence for the addition of components Such as oxidized sulphur, alkal-group elements, water and Cl from the subducted slab", transferred asa fluid ora silicate smelt, The lack of abundant Clbearing phases in the manic, coupled with the high Cl contents of arc magmas (700- 2.000 ppm.) further supports the idea that Cig reeyeled during subduction oF seawsteraltered oceanic crust”. Subduction ray also contribute additonal metals. such as Cu and Zn, 10 the resulting are magmas, derived from hydrothermal mine taation ofthe subducted sea floor” ‘Ore components may aso be acquired during magma transit through the crust. For example, the isotopic signature of por phyey Cu deposits im Arzons is strongly correlated with that NATURE - VOL 370 + 18 AUGUST 1904 REVIEW ARTICLE DIVERGENT MARGIN Mid-ocean ridge Asthenosphere EA " Stripers Cal Seen CONVERGENT MARGIN Continental volcanic are ‘SOURCES OF METALS AND VOLATILES IN ARC MAGMAS FG. 1 Schematic section showing he principal components of magma geress, fi Row and metllogeness in ivrgent- and convergent margin sotings of the loc basement, implying that the intrusions contain a significant amount of assimilated crust, whereas in the case of Sh and W deposits such as those of southwest England and southwest Japan, the ore-bearing magmas may be produced enti- rely by molting of the crust”. Crustal melts produced in the presence of ether elemental C or Fe sulphide may be reduced ‘im nature, and are thus ideal for accumulation of Sn Fusion ‘of previously melted crustal rocks an result in high magmatic concentrations of F, due to the breakdown of refractory, Fich Inydrous silicates. These minerals may also contain significant amounts of Sn and Mo, which are concentrated with Fin some ‘ore deposits, But exceptions to these relationships are common, land the source of the metals may be less important in terms of | ‘netal concentration, than the magmatic processes that operate uring final ascent and differentiation of the magma ‘The effects of erstal fractionation, Crystallization is one of | the main contrals on the concentration of ore comportnts in ‘magmas. The dominant minerals that crystallize im most igneous systems ae silicates and oxides: elements that partition into these minerals can have their concentrations lowered. whereas incompatible elements (those that remain in the melt) may become more concentrated. The degree of compatiblity is a function of erystal structure, melt composition, magma oxida tion state, and the temperature and pressure of crystallization For example, Mo and Zn concentrations are commonly high in ‘magmas tha contain low abundances of Fe-Ti oxides und bane ite, minecals that tend to be vich in these clement The enrich- ment of Sn and W in granites formed from melting of erustal rocks, noted above, may also be due to the composition and low abundance of oxide minerals" in these reduced rocks, The lack of Cu mineralization astocited with high-silica granites may be attributed to the early crystallization of pyrrhotite (Fe, -.S). which acts as sink for Ca (and Aw?) and lower its concentration in the melt, Conversely, because Mo stats at lower concentration and is more incompatible than Cu, crystal fraetionaton is necessary to produce the higher Mo/Cu of bigh- NATURE - VOL 370 - 28 AUGUST 1994 silica granites". But even after extensive erystallization, metal Concentrations inthe magma ar still at least two oF three orders fof magnitude fess than grades of economic ore in associated porphyry-style mineralization (Table 3). Other processes are therefore necessary to concontrate metas from the magi ino an ore deposit. Fluids In magma. Given she appropriate fuid composition ‘most ore metals ein be partitioned strongly into « magmatic- hydrothermal fluid. as chloride, hisulphide and hydroxyacid complexes" (Table 3). AL magmatic. temperatures and ARLE 3 Typical metal concentrations in granites and por oes eo wo Goce EO GE EE A 22 ba SB 8 RS eas Bile came oo BE ae Ea 9 het Frerocjr he crore pratt fr the meal noire ots tr fh Foy erate oi ronan Site Uo ipa ane commen shanacet Yat ao fem vores coon ‘Fought strewn abut fer OH rer To Malone omens “ar Mos Sor Wich pry. at pes of ayy ee Canaan no ee dazominton posse. neta vein eon, hu eonmany rarer tom 31 Opa. and aah enee YOO ppm os on everage m9 ow eben san REVIEW ARTICLE pressures, nsulicient data exis to define the ideal conditions for parttioning of any given metal from a magma into an exsolved Hydrothermal uid. Even so, the limited data available indicate that metals such as Cu” can be scavenged by exsoving mag- rmatie Mus, especialy at low magmatic pressures”. raising the question: when do these fuids separate from magmas and What controls the uid composition? ‘Many magmas contain exsolsed ids during their ascent through the midale to upper crust. There is evidence that basalts from a variety of tectone settings are saturated with a COsrich ‘uid phase at depths >30 km (refs 36-38). Because ofits high solu in sfcate melt, H-O will represent only a small faction ‘ofthis fd in the deep crust although H.0 increasingly exsolves Aa Tow pressures until it dominates the Buid, as observed in vol fanic emanations (Table 2). Unless felsic magmas originate as Fsolated systems, and receive no input of volatiles from matic forerunners and subjacent heat sources. they t00 are likely to be saturated with a uid phase dhyoughout their history”. The addition of SO» and other gases to magmatic systems decreases the solubility of H.O and CO. in the melt by decreasing their activity inthe fluid phase(s) resulting in fluid saturation with even lower concentrations of gases dissolved in the melt. Thus. if magmas inthe upper crust are normally Mid-saturated, the ‘ey questions related to metal transport are not if or when fuid saturation occurs in the associated magma, but what controls fui composition, which fluids are most ikely to seavenge metals act (wt) FG. 2 The composition af miscible fads in the system #,0-NaC, 2359 function oF pressure at 800 and 600 Chine: the approx ‘ete dep stra tnesati pressure paces 23 wis Nacleouton (ies eel) exsoves rom » magma at 800 ‘Cand 1.500 dt an then Isothermal decomprosses wil Unik to ge 2 low-density vapour anda higheraty, ryporsane. squid at ~1.300bar, cherie ompleuod moat il pation to the lu. whereas gaseous como. emt wl be largely contained by the vapour. Upon fur isothermal ‘decompression (cued arows} the laud and vapour wi rogezsvey become more ard les saline, respecte by condensation of NaC Fh tqua fom the vapour The vapour of hightemperature voleanic fumodoies eoraina “100 ppm. NaC ana Is metal poor, woereas RE pressure vapour accompanying voir eustion este Nach ana Inetarich for examine, White sland, Table 2) The stiopld fields Iraeate tne composiuons of Wud incusions at temperatures and pressures type! of porpyey Cu formation. The potayapns show ep. Fasentatve quart hosted hud inlsins[ttoom tersratre) fom 8 porphyy Cu depot a, ypersatne Incusioncontaning Nat satratod Faw vapour buble. caugrer minerals of Pie, x. posshy nya, b, and Reema, sb, vapeurichincusion caxtang low falinty condensate bub of compresses gas and Smal opaaue ‘minerals Inclusons are eae ~50 ym long 522 From the silicate melt, and how much Muid can be channelled to Site of metal deposition ‘AL shallow crustal depths, metal partitioning becomes more complicated because magma may contain more than one non- Sicate id phase. For example, at Tkbar and 800°C, the NaCT-H.O system will consist of two phases (a low-density vap- four and a hypersaline liquid: Fig 2) ifthe bulk composition of ‘the Muids(s)exsolved from the melts between ~ and ~70 0 NaCl Indeed, the Cl contents of many silicic magmas are con- ‘stent withthe concentrations necessary 19 fest in saturation ‘with both vapour and a hypersaline quid". Addition of CO- {ang most probably'50:) will increase the field of immiseibility so thatthe tWo aalucous phases may coexist over a wide range fof erustal conditions (up to pressures > bat ef) The large density contrast between the vapour and hypersaline Iiquid commonly results in these two phases separating within the magma chamber or its adjacent hydrothermal sytem. The aqueous vapour contains CO:, SOs, HS, HCL and so on, and tends to ascend on formation, either discharging tothe surface as volcanic fumaroles (Table 2), oF becoming absorbed at depth, forming an acidic water that can leach the host rock™. The dense hypersaline guid remaining at depth wil be sicher in Cu and cher ehlorophile elements than the low-salinity vapoue™ Ev- ‘ence for these immiscible uid is abundant in intrusive rocks and some voleanie products”. However, it is in porphyry ore Seposits thatthe remnants of these fluids, rapped as inclusions in minerals, have been studied most intensively. Mineralization associated with intrusions Porphyry Cu mineralization is dominated by magmatic Mud in the early stage although late meteorie water isnot only common ‘but i perhaps eritical im enhancing porphyry metal concent tions to ore grade'™. These deposits typically consist of tl Dhies that ate both disseminated and located in veinlets; these ‘ceurrences are found within and adjacent to porphyriti ici to intermediate-composition intrusions, and commonly form at depths of 2-5 km under lithostatie pressures. Detailed studies fof hydrethermal alteration, minecalization and uid inclusions. integrated with stablisotope daa, indicate that the hydeother- smal systems that form these deposits are initially hot (>S00 (00°C) and dominated by a magmatic, hypersaline liquid coex- isting with a low-density vapour. Because of the depth and high temperature, ative examples have yet tobe studied. Zoned alter ation assemblages form asthe reactive, metal-beating magmatic ‘uid moves away from the intrusion, coals and reacts wath the country rock", The intrusions themselves are altered, vith a entra zone of biotite K-feldspar (K-sicate zone). tha typ- feally ives way outward to an intermediate 2one of quart pls chlorite, commonly overprited by sriite and pyrite (sercite zone), The wall rocks Farther from the inteusion may be altered to epidote, chlorite and abit (propyliti zone). igh-empera- ture Cusbiphide mineralization, accompanied by. magnetite may be present as sll atthe boundary of the K-silicae and sericite zones. Where preserved these alteration zones ae always ‘capped by rock that has been kashed by an acidic water Formed by the absorption of magmatie vapour into meteoric water. The resultant advanced argc alteration usually extends (0 the palaeosurface™ “The stone spatial association between plutons and porphyry felated ore deposits emphasizes the genetic role of magmas in the mineralization process. Another ine of evidence comes from the fu trapped as inclusions in minerals; many of these inch sons formed at nearsmagmatic temperatures of 700-00 °C. At room temperature, the hypersaline fu inclusions contain a borne, a vapour bubble and daughter erystals of halt, sylvite and minor ore minerals such as chaleopyrite (Fig. 22). The hyp fersaline liguid at its Capping. temperature contains 40 t0 60 ws NaCl equivalent (eg) and 250-5,000 pzpm. Cu", the ier based on the amount of Cu-bearing daughter minerals and recently confirmed by direct analysis clusions that trapped NATURE - VOL 370 » 28 AUGUST 1904 REVIEW ARTICLE FG, 3 9, Vaation in the O- and Hisoope composition of crust ‘magmas and waters (640 and 80, respecte relate to Standard Mes Oozan WaterSMOW, Fase magias uncevan by eomtnental ‘rust have sight beaver isotope ratios than island are magras, presumably cue icorparaton of crustal teal” Those magmate Water ae both scopcay dine ory that sssoclated wah mare ‘erised mid-ocean ridge basalts (MORB)™. Te stop cmpoetion ot ‘Subdvcton relsted matmate vapours ouigassng fom are veicanoes has 2 natn range", ening from ter parent are magmas du to Mroedonation during degassing, withthe degasces mek (open avons Boning down) Becoming lighter in Histape composition, Tere are two tends for neuval pM goctnermal water, ove caused by moore Wotervook iteraction (O'anitfom the meteors water Une" for ‘ramp, that of Wate, Wi), and the ther fom mang betweon meteor watrofyanabie focal sotopte composition and low salty ‘magyate vapour (small sod arrows wit tence pong tna ‘oteare vapour; for example, that of Broadlane. Br. Comat waters ‘tapped In sediment end nats relates to matamorphisn nave wide ranges of topic compestion™ (nt shown here b, Te Ketone com poution of myrothermal ids assocted wy porphyry ore depots oauces from te competion of hightemperature Kestieste aeration rinerals stppled fea)" Lowertompetue siete ateraton nd fates various tures (Gplaly plotng i te two large ccles) botwoon late-stage magmatic water (dere fro a degassed met) and meteore water wih 9 rang of otepe compostion depending on the palgeotatse ane attude: this meteor mater Is sometimes 0 shited™Wighsuphidaton’ waters (se text) are sia in Isotope amposto te vlcaie vapour, th wands projecting towards meteoric ‘ter of vara soap eompoaton open avons) depending on ors ton of te depose. The waters at prostate barren quar in Tow ‘sulphidator"gepostscommonty stom an sn ffm cal meteoric Water valses™ whereas hghavede ore samples (Comstock ode 0 ‘San ave both an O- and isotopic shit om local fpetworic water {Gpen sar caused bya component of magmatic wate such 9 huge shit cannot be caused by botng of meteor wate the immiscible vapour (Fig, 26) are low in salinity (<1-2 w1% NaCl oq) and relatively high in COs (= 10 wit re. 37). Constraints from 0 and H isotopes. The isotopic composition fof water in a magma as intially approximated by analysing minerals in eroded intrusions and then using mineral water frac+ tionation factors to calculate the values of the cooxstng water. ‘These data were used to define the sotopie composition of "pr= ‘mary magmatic water"™ (Fig. 3a; dote-line box). But because there ‘sa strong fractionation of H isotapes ‘uring carly NATURE - VOL 270 - 48 AUGUST 1904 Segassing™, the late-formed hydroxyl-bearing igneous minerals represent the isotopic composition of a degassed melt rather han that of the inital magmatic wale (Fig. 3; open arrows) Te best current estimate ofthe initial isotopic composition of 1.0 inare and crustal felsic magmas" (Fig. 3 solid-ine boxes) fs intermediate Between that of the degassed magma (dotted- Tine box) and the isotopically heayy outgassed 1150. the later sampled 2s voleanie vapour” (dashed-line box) “The O- and H-sotope compositions of hydrothermal minerals jn ore deposits also help to trace the origin(s) ofthe hydrother- ral water In porphyry deposits, hydroxyl-bearing minerals include biotite, ‘which forms close to the intrusion at near magmatic temperatures (>500-600 °C), chlorite and sericte (which form at ~300 °C) and kaolinite (~200 °C). Ealy-formed, high-temperature biotite and K-feldspar'** provide evidence thatthe 00 ofthe Duds altering the mtrusions have a narrow range of +6 t0 +%e (Fig 3h; stippled box), consistent with the water being in equiibrim with the lagge O reservoir in the associated magmas. But the 3D value of this early magmatic fluid (based on biotite compositions) has a wide range. from 35 19-75% (Fig. 3h) and is shifted to lower values than the primary water of most felsic and are mags (~20 10 ~43%e) ‘This may” be explained ‘by open-sjsiem degassing of the magma”, a8 noted above, which ean thus account for the large SD" variations (240%) at constant O.sotope composition ‘observed for biotite from a single deposit Lower-emperature alteration commonly has an isotopic signature indicating a large component of meteoric water”, although in some deposits there is also evidence that sea water fr en evolved formation water as present, and this saline quid may have had role in mincralizaion™, The isotope variations Of lower-temperature.scricite alteration among several North ‘American deposits are systematic with latitude and hence palaco- meteoric water composition" (Fig. 3h; hydrothermal waters tp ically plotting in the cicled areas). This meteoric water has ‘commonly been shifted in Oisotope composition through water Fock interaction before its flow past she intrusion” (for example, lower cirled area). But in some South American deposits®. there is eear evidence thatthe Nuid related to latestage seriite ‘simples had @ magmatic vapour component, as their composi tions indicate a uid with +5 t0 +8%m 30 and ~20 10 Ae OD (Fig. 3; dashed-line bow), Other Isotopes. The Pb- and S-isotope compositions of por hyry Cu ores from South and Nowth American porphyry Seposts?™*" are equivocal regarding theit origin, In some cakes there are Pbssotope trends consistent with subducted pelagic sediments a5 the major source of Pb, indicating that Pb was Feeyeled curing subduction and then coated to the porphyry Pyotr system Crustal soures spear ony oa imp {ant to the Pb budget of most of these systems in contrast, Sr sometimes shows high isotopic ratios, consistent ith a large crustal component"! In Arizona, however, there i strong cor relation between mineraling intrusions and the Pb-sotope composition of the lower-eustal basement The range of 3S fof most porphyry Cu deposits lies between ~3 and + 9%, (cof. 13), suggesting the bulk of the S was derived from local intru- sions, though the wide range of S-isotope composition in some teases may be caused by contribution from the wall rock". The fresh-rock 4S value has 2 geographical variation, which in island aes probably eflets a contribution from subducted mat- ine sediments”. Thus isotopic evidence from porphyry deposits indicaten a varity of courees for components such as HO, PD and, although it seems that a magmatie source dominates the ‘rly history of the systems. As the distance from the magma to fre increase, such evidence weakens. Mineralization distant from magmatic intrusions ‘The term “spithermal refers to a class of hydrothermal ore Leposts formed at relatively low temperatures (<300°C) and shallow depths (surfice to 1-2 km; Table 1). Despite the shallow 523 REVIEW ARTICLE depth, there is stil evidence for a magmatic component fo the ude Epithermal ore deposits can be divided into two main types (Table 1), according to ther alteration mineralogy. One type is formed by acidic and oxidized Nui (high suiphidaion).typieal of acidic springs near volcanoes: the other type is formed by a pear-neutral pH, reduced lid (low sulphidation), as found in geothermal systems" High-sulphidation epitnermat ore deposits. Although formed a shallow depths, high-sulphidation ore deposis have charactr- iste that indicate involvement of magmatic components in their formation". The early stage of these deposits is characterized by extensive leaching of tho host rocks by Mids with a pH <2 (ref. $5) and an O- and H-isotope composition (Fig. 3: triangu- Jar area)"*similas to that of magmatic vapour” mixed with mete- orie water (Fig. 30; open arrows). The leaching creates 1 porous Silica residue (9S ws Si03) that may subsequently host ore such as Aucbearing Cu- and Fe-sulphides. The high- fulphidation style of mineralization shares many mineralogial and stable-isotope characteristics with the advanced agile zone fof alteration that caps porphyry Cu deposits, and indeed there is commonly a close spalial relationship between these ‘oposite The geothermal uid is oxidized, based on S Jsotope compositions ofthe sulphide and sulphate mineral a ‘majority of the sulphur species originate fom the disproportion- ation of magmatic SO, to form H,S0., Fluid inclusions in ore-related minerals, including Cu-sulpho- salts (transparent only to infrared wavelengths) and quar, ni- cate that the mineralizing Ruid may have a salinity of 2-3 wt NaCloq, though there can be marked increase in salinity with ‘epi, 10 20-30 w% NaCl eq below the ore zone”. This spatial Separation of low-salinity liquid associated with high-sulphida- tion ore above highersalinity guid at depth is distinct from that noted for deeper porphyry Cu deposits, where hypersaline brine coexists with low-salinity vapour; this separation may be caused by the high density ofthe brine, which cannot ascend easily to shallow depths. The close association of Cu and Au in the relatively oxidized high-sulphidation and porphyry environ- ‘ments suggcsts that both metals may be transported under simi- Tar conditions, though in the high-sulphidation pithermal environment mineralization is related to a lower temperature fan les sane igh Low-sulphidation epithormal ore deposits. In contrast to por- phyry and high-sulphidation deposits, magmatic signatures in Tow-sulphidation epithermal Au deposte are more elusive, Ore concentrations of Cu do not occur, presumably because the Tow Salinity, near-neutral pH and reducing (sulphide-dominant) fluids preclude effciom transport of Cu. tn general, low-sulph- idation deposits form distant from the inferred magmatic heat source’ at temperatures of 200, 300°C (ref. 57). Pressures are controlled by hydrostatic conditions, meaning that the maxi- mum temperature at 4 given depth jy constrained by boing, 4 common process in these systems", Although variety of lassifcations of this deposit type exist™, a divsion based on metal assemblage appears to reflect intrinsie geochemical difer ences. One style is Aurich (with Ag/Au of 1/10-to 10/1 and ‘only trae base metals), whereas the other is AB-rich (with Ag [Av of >100/1) with economic quantitis of Za and Pb present ‘The Aurich deposits are associated with low-sainty But gas- rich uids (<1-2 wis NaCl but up to-4 wt gases, mainly CO; with H:S)". By contrast, deposits rich in Ag and base metals re associated with more sine fluids (10-15 94% NaC. This dilference in salinity is important for the metal-transporting ‘capacity of the ids, as Au s transported as a bisulphide com- plex whereas Ag, Zn and perhaps Pb are dependent om transport by Cleomplexcs in this reduced envionment", The low-salinity Fuds of Aurich epithermal deposits are largely similar tothe ‘Muids of most active geothermal systems”, whereas there are no saline geothermal systems in a tctonic environment siilar to that hosting Ag- and base metal-rich epithermal deposits 528 This lack may be due to transient, tetonically-indveed pulses of saline. mineralizing Quid imo an otherwise low salinity, metal barren hydrothermal system, a prooess we have not yet seen. Stuble-isotope studies of low-sulphidation deposits commonly demonstrate the predominance of meteoric water’. with O- Jsotope compositions of hoth water (Fig 3h; ‘O-shft’} and rook ‘modified to varied degrees by their mutual interaction”. How- ver, most samples studied to date have been late-stage, barren ‘Quai veins, formed after the period of ore deposition”, Where Samples are associated directly with bonanza (high-grade) ore, such as from the famous Comstock lode, Nevada (Fig. 36, sold Star). large shift in both 3"O and SD values from the composi- tion of local meteor water (open stat) is taken as evidence for a significant magmatic-water component”. Paradoxically, the evidence for meteoric-wvater dominance in epithermal systems is ‘most obvious where magmatism was most voluminous, because the large magmatic heat source creates large and long ved cells of convecting metcori water, convection that will erase most of the evidence for any early component of magmatie water. For txample, in the Pacific Northwest of North Americ, region fof many eroded plutons, the rocks exposed over >37% of the "3 O-totope signature indicating alteration by mete- Furthermore, the S- and C-sotope evidence indi- cates that many epthermal deposits can have a magmatic source for both clement although there is commonly also a sedimen- tary component to the S, as well as occasionally an influx of organic C. The resulis of Pb-isotope studies on a variety of| epithermal deposits indicate several souress for the Pb, including Teaching of basement rocks and the overlying voleanc rocks oF thee intrusive equivalents, not surprising given that meteoric ‘water convection can extend to depths of $7 km (ref. 62). The muliple sources of components in Tow suphidation epi= ‘thermal fluids is caused largely by the extensive amount of inter action between thermal waters and crustal rocks that occuts in this environment. Any reactive magmatic components are neutralized and reduced, in turn deriving components from the thos rocks, This proces leads to an intcgrated isotopic signature that may mask & varity of discrete Muds present in the early sages of activity: that i. pulses of fd recorded by cycles of ‘mineral deposition. Despite the overprinting that may oecur ia epithermal deposits, advances in microanalytical techniques now lly the isotopic composition of preserved domains in minerals to be analysed, domtins that show evidence for a varity of lserete wate and gas sources including magmatic and erst ‘Geothermal systems, In some volcanic arc-hosted gothermal stems, the evidence for a magmatic component i common and unequivocal. These systems are characterized at depth By neural-pH fluids of low salinity (<1 we» NaCh but variable 4 content (up to 4 wes, including CO, and HS)". Coupled With their alteration mineralogy, these characteristics indicate they are analogous to the epthermal systems responsible for forming jow-sulphidation ore deposits; indeed, in two of the world’s largest and youngest epithermal Au deposits (Hishikar, Japan and Ladolan, Papua New Guinea) late-stage waters (70 1o1>130"C) sil flow through the eins The advantage in studying active systems i that disrete Mids can be simpled, allowing an examination of ime sices through the history of hydrothermal activity. For example, the isotopse compositions of the highest temperature waters in a variety of| those geothermal sysems have two different trends (Fig. 34) fone trend suggests a mixture of up to S0% magmatic water with local meteoric water, whereas the other indicates only meteoric \water-rock interaction” (horizontal arrows). In the ease of the Broadlands geothermal sytem, New Zealand, the deep thermal ‘water (Fig filled cick, Br) hasa H-shift that indicates about 220% component of low-slinity magmatic vapour mixed with local meteoric water (open circle). The deep liquid is also gas rich (~2 wt mainly CO,), and has a N,/At ratio characteristic fof are “magmatism (caused by. subduction of | Ne-ich NATURE - VOL 370 - 28 AUGUST 1994 REVIEW ARTICLE sediments)". By contrast, the deep liquid from the nearby Wai- kei geothermal system (filled crle, Wk) has an isotopic com position similar to meteoric water that slightly O-shifted. This fluid is low in total gas content (<0.1 wt), and has a Ns/ At ratio typical of airsaturated ground water, indicating no Significant magmatie contribution fo the system. Ths distinc: {ion in fuid composition may help explain the observed ciffer- fences in mineralization between these. (wo stems, The Broadlands system is mineralized locally with Aurich proc ates in hot springs (to 80 ppm.) and wellhead pipes (10 6 wt fef, 66), and Pb-Zn sulphides are common at depth, whereas precious metals and Pb-Zn sulphides are absent at Wairaket ‘The difference in mineralization also correlates with Pb-sotope signatures. Broadlands sulphide minerals have a homogenous signature, identical 1 that of foal cale-alkaline intrusions, sug- sting these are the source rocks, ether through contribution from a magmatic fluid or by leaching, whereas the Pb-isotope compositions of altered rocks from Wairakei indicate that most ‘ofthe Ph was leached from sedimentary rocks. Similar geothermal systems with variable magmatic inputs (based on chemical and isotopic signatures) are common also in other ctcumm-Pactic voleanie ares", Dailig in some sSs- tems in Japan and the Philippines has encountered deep fractures containing ho, acide Nude within otherwise neutral-pH waters; the acidity is caused by an absorbed magmatic vapour that is not neuralzed by water rock interaction" Perhaps such a mage ‘matic dui, although neutralized at depth, direlly contributes ‘metals to the Broadlands system. Alternatively, the acidic vp. ‘our may conteibute only ligands such as CI” and HS, using the resulting Mud to leach metals Feom the wall rock. This var: ability in magmatic signatures between geothermal systems may bbe eased by intermittent contributions (or lack theoot) of mag rmatie uid. Thus, gas and isotopic analysis of uid inclusions in orecelated versus barren minerals will help to determine the role of magmatic contributions to hydrothermal ud compos fiom and ofe formation, ‘Magmatic fluids and hydrothermal environments ‘We have mentioned the relationship between magma type and syle of intrusion-related mineralization, stresing the ned for metal scavenging from the magma by an exsolving aqueous fui Here we examine how this magmatic fuid may be involved in mineralization away from the intrusion. ‘The acidic environmont. Studies of high-sulphiation epither- mal ore deposits have confirmed the involvement of fuids with isotopic, composition similar to hightemperature voleanic vapours?" (Fig. 36). When such vapours are absorbed by rmeteorie water, they form acide springs, which commonly have {pH of 05-15 (rel 68). The composition of these acidic springs feflecsisochemical dissolution ofthe rocks through which they flowed, a process that forms leached zones similar to those that host ofe in high-sulphidation deposits. However, studies of the metal concentrations of high-iemperature fumarole™” associ- ted with quiescent depassing of volcanoes indicate that these ‘vapours cannot form ore deposits". For reasonable ifespans of ‘magma degassing and hydrothermal activity related to 8 single intrusion (~10" yrs ref. 2), the metal luxe related to fumaroles (Cable 2) and their associated acide oprings™ are insuficiet to account forthe amount of Au (10,1001) and Cu (>10":) found in high-sulphidaton ore deposits! There are several possible explanations for this seming para dx. First, these deposits may form over much longer time spans, in association with multiple intrusions (as suggested for some porphyry deposits"). Second, the acidic water may leach metals Ss il eacts with the wall rock at depth”. Third, the greater ‘depths of these deposit (in contrast the surficial fumaroles) means that pressures are high, thus inereasig the concentration ‘of metal chlondes inthe vapour’ For example aerosols assoc ated with magmatic eruption are responsible for much higher ‘etal fluxes than quicscently degassing voleanoes, even though 18 Aucust 1994 NATURE - vot 370 the discharge femperatures and flux of species such ex H.O, and Clare similar (compare White Island and Satsuma Iwojin ‘Table 2). Ths observation can be explained ifa relatively NaC- and metal-rich vapour, equilibrated with a magma at a pressure ‘of several hundreds of bar (Fig. 2), accompanies eruption. this accounting for the high Na/S and Cu/ in aerosols, in marked ontrast 10 the low Na/'S and Cu/S in the metal-poor fumsaroic ‘Yapour associated with quiescent degassing. Absorption of Similar high-pressure and metal-rich vapour by a hydrothermal ‘System may therefore frm the low-salt ful (<5 Wt" NaCl) responsible for mineralization in high-suiphidation systems ‘The deeper, high-salinity (<30 t's NaCl) fluid beneath these deposits refered to earlier, may be related to the immiscible hnypersaline counterpart ofthe vapour. The neutral-pH environment. Te sources) of Au and other retals in low-silnity, neutral-pH @uids of low-sulphidation

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