IX Congreso Peruano de Geologia. Resumenes Extendidos. Sociedad Geol6gica del Peru, Vol. Esp. 1(1997), Lima, p.

121-127

HYPOGENE OXIDATION AND LATE DEPOSITION OF PRECIOUS METALS IN THE PIERINA HIGH-SULFIDATION DEPOSIT AND OTHER VOLCANIC AND SEDIMENTARY ROCK-HOSTED GOLD SYSTEMS
DONALD NOBLE1, BRIANPARK-LJI, WILLIA.\f HENDERSON2 & CESAR VmAL3 C. B. E.
Mackay School of Mines. University of Nevada, Reno. Reno. Nevada 89557. U.S.A. U.S.Mineral Laboratories. 6723F 32nd Street. North Highlands. California 95660. U.S.A.

Companiade Minas Buenaventaura S.A.. Carlos Wllardn 790.Lima 13. Perno

INTRODUCTION
Hypogene oxidation was an important process during the formation of high-sulfidation gold deposits at Pierina, Yanacocha, Tantahuatay and other districts, and may be important in certain sedimentary rock-hosted deposits, including some of the sandstone-hosted gold deposits of northern Perf. Mineralization at Pierina involved a complex sequence of events that included a stage of pervasive hypogene oxidation. Gold and, to a greater extent silver, was mostly introduced by late hydrothermal solutions that destroyed pyrite, enargite and native sulfur and deposited barite. Various minor elements were introduced at one or more times as hydrothermal activity proceeded, and a number of elements, including Fe, Ti, Te, Se, TI, Zn and Cd were hydrothermally leached by oxidizing solutions. The results suggest that concentrations of iron, particularly specularhematite, devoid of precious metals, but containing elevated Hg, As, 'n, Te, Se, Bi and Sn in high-level argillically/advanced argillically altered rock can be used to infer the presenceof subjacentmineralization. PARAGENETIC SEQUENCE AND GEOCHEMICAL BUDGET AT PIERINA

Pierina is a newly-discovered world-class high-sulfidation type Au-Ag deposit of middle Miocene (ca. 14.5 Ma) age situated in the Cordillera Negra of northern Perf a short distance northwest of the city of Huaraz (Lowell, 1997). High-grade ore is hosted by intensely altered porous welded tuff (Huanqui and Calle, 1996) of early Miocene age. Based on reconnaissancesurface studies by Noble and Park-Li prior to drilling (Noble, 1996a), hydrothermal solutions may have ascended, at least in part, along steeply-dipping, generally NW-SE trending structures. The high-grade ore zone is overlain, and perhaps intruded and truncated by, breccias that were provisionally interpreted as filling a diatreme or breccia pipe and/or breccia dikes. Data subsequently obtained by American Barrick through intensive drilling and trenching will amplify, and perhaps contradict, someof theseearly observations and interpretations. Paragenesis A remarkable feature, first observed by Patrick Hillard, Freddy Huanqui and other Acuarios personnel, is the presence in the ore zone of irregular residual masses(cores) several cm to 0.5+ m in diameter of rock containing small amounts of fine-grained pyrite and variable, but commonly large, amounts of native sulfur in porous, completely silicified welded tuff. The sulfide-native sulfur bearing masses are surrounded by dark selvages (rims) several mm thick containing abundant covellite. The rims in turn are surrounded by rock containing iron oxides/hydroxides. In addition, there is rock with few or no visible iron oxides that contains considerable amounts of coarse barite. Some rocks contain grains and aggregates of a black mineral that we identified in polished section as acanthite, in part intergrown with barite. During field observations in May, 1996, of material taken from two exploration tunnels, we observed that in some rocks barite also occurs as irregular, mm to cm wide veins that cut not only oxidized rocks but also the pyrite plus native sulfur-bearing residual cores, with the veins being bordered by selvages of oxidized material. Our observationsled to the following paragenetic sequence, shortened and reworded from Noble (1996b):

1 Alteration of tuff to a mixture of quartz+aluniteOhematiteor pyrite. 2 Formationof vuggy silica rock by alunite-destructive solutions.

3.

Deposition of pyrite accompaniedby Cu, As and perhapsAu in the vuggy silica rock.

4.
5.

Depositionof native sulfur in at leastsomepartsof thepyritic vuggy silica rock

Ingress of relatively oxidizing and/or sulfur-poor solutions causing destruction of pyrite and dissolution of Cu-bearing minerals. The releasedFe formed hypogene hematite and perhaps other Fe oxide/hydroxide phases; the Cu in part migrated to zones with native sulfur, where covellite, chalcocite, enargite?, etc., were precipitated, in the local high aS2 environment to form Cu-rich rims around the native sulfur-bearing masses. Gold was either introduced at this time (perhaps during the latter part of this stage?), or(and?) remained where it had been deposited in stage three.

6. Depositionof acanthiteplus barite (in part intimately intergrownwith acanthite)in portions

of the mineralizedrock. The (chloride-rich?) solutionsthat broughtin Ag and Ba appearto haveremovedFe andCu. Alunite rock is porousand little or no silica wasintroduced;alterationmay have takenplace in a magmaticsteamenvironment. Gold-bearing friable silica rock was later recognized a distinct rock as type. Reflected-lightand electron-beam microscopyshowsmall amounts enargitewith pyrite in the of residual cores and small amountsof chalcocite as well as covellite in the rims, and confirm the
occurrence of acanthite. The paragenetic sequence is considerably more complicated than that recognized in deposits such as Julcani (Noble and Silberman, 1984) and other high-sulfidation type gold deposits (e.g., Arribas, 1995). Nevertheless, certain stages observed at other deposits, such as the deposition of late-stage aluniteOquartz, have not been seen.

TIMING OF ADDITION AND REMOVAL OF AU, AG AND OTHER ELEMENTS Multielementgeochemical analyses provide additionalinformationon the timing of introduction of Au, Ag and other elements, and demonstratethat a number of elements were hydrothermally remobiliziedand leachedduring oneor moreof theparagenetic stages.Based the field, petrographic on andgeochemical studies,the following stages recognized: are

1. Earlyalunite 2. Vuggy silica

3.

Pyrite-enargite

Native sulfur 5. Hypogene oxidation

6. Barite-precious metaVfriable silica Barite-precious metal ore consists of rock that contain visible acanthite (barite-ananthite on Fig. 1) and specimens with abundant go.1dbut no visible acanthite (barite-gold). Later stage(s) may be present: The breccias overlying and perhaps cutting high-grade ores have Agl Au ratios 100+ times higher than the ores, and local breaking of brittle high-grade ores into decimeter- to meter-sized blocks may have been caused by late hydrothermal explosions. Analytical data on matched pairs of pyrite-native sulfur and hypogene oxidized materials from five hand specimens demonstrate that Au and particularly Ag were mostly added during the hypogene oxidation and barite-precious metal stages (F. 1). Relatively small amounts of Au, and perhaps barite, probably were introduced during the pyrite-enargite stage,but virtually no silver was introduced prior to hypogene oxidation. Analyses of the covellite-rich rims show high concentrations of Ag as well as Cu, indicating introduction of significant amountsof silver during stage 5. Two samples of early alunite rock contain extremely low Au and Au, consistent with previous observations at many deposits and prospects that early quartz+alunite+pyritelhematite altered rock is almost devoid of precious metals.

A preliminary summaryof the geochemical budgetof hydrothermalalteratiol) is given below, with certain of the relations summarized Figure 1. Because the complicatedevolutionaryhistory, in of 122

Block Shawing residual pyrite.enargiter later native sulfur assemblagewithin vuggy silica rock surrounded by gold-rich hypogene oxidized ore. Note darlc silver-rich band containing abundanthypogenecovellite separatingsulfide + native sulfur-bearing and bariterich oxidizid rock@.

little covariance can be seen in multielement geochemical data obtained on systematically taken core or channel samples. Careful paragenetically controlled selective sampling was necessary to reveal geochemical patterns. Aluminum, the alkali and alkaline earth elements, Fe, Mn and P were largely removed during the formation of vuggy silica rock. A number of elements introduced with pyrite and enargite were leached during the hypogene oxidation and barite-precious metal/friable silica stages. Most obvious was the removal of iron. The elements Cu, Zn and Cd were almost completed leached, and Te, Se, and Tl were largely removed. Aluminum, almost entirely leached during the formation of vuggy silica rock, was further depleted. Highly variable 1i contents indicate hydrothermal leaching, transport and local deposition of this generally immobile element, as has been observed at the Paradise Peak (Nevada) high-sulfidation Au-Ag-Hg deposit (John et al., 1991). In contrast, significant amounts of lead were added during the last two stages.Appreciable amounts of Bi and As were introduced during the pyrite-enargite stage, and were both variously added to and removed from rock masses of handspecimen size during hydrothermal oxidation and the following barite-precious metal/friable silica stage. Highly variable Sn contents in the range 1 to 35 ppm suggest than Sn was variably introduced and leached. Although Sb contents likewise vary considerably in rocks of the hypogene oxidation and later stages, the generally higher Sb contents suggest that significant amounts were introduced during the late stages of mineralization. Mercury was introduced during the barite-precious metal/friable silica stage and perhaps during the preceding hypogene oxidation stage. Manganeseis 040 ppm in all rocks.

Rocks of the barite-preciousmetal stagehave highly variable Agl Au ratios, suggestingthe existenceof two or more substages. Although friable silica rock generally is very poor in iron, one specimencut by hematite veinlets containselevatedAu, Fe, Pb, Bi and Te and low Ba, Sr and Ag, indicating the presenceof a compositionally distinct mineralizing fluid that depositedAu and Fe. Although we suspectthat friable silica rock formed before barite-acanthiterock, these stagesor substages overlapor reflect multiple hydrothermal my pulses.Only detailedfield paragenetic studiesin mine workings will provide definitive answers.The fate of the large amounts of native sulfur is uncertain,althougha possibility, supported the barite-acanthite by intergrowths,is that someis present in the barite, having actedto precipitateBa from late reduced, sulfate-poorandpreciousmetal-bearing, hydrothermalsolutions.
123

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The evolutionaryhistory of hydrothermal solutionsseenat Pierinais in all probability not unique. Vuggy silica rock containing pyrite and native sulfur separated from oxidized rock by covellite-rich selvages beenobserved theTantahuatay has at district, andlate barite-goldparagenetic stages have been describedor observedat a numberof districts. Pierinahasa numberof geological, mineralogical and chemical similarities to, and some differencesfrom, the ParadisePeak high-level high-sulfidation deposit(Johnet al., 1991).
Constraints on Temperatureand Pressureof Mineralization Pierina appearsto have been formed at unusually low temperatures,probably well below 200~ C. Geological relations suggest a moderately, but not extremely, shallow depth of mineralization. Distribution of native sulfur within cavities and the local movement of native sulfur outside the remnant pyrite+enargite zones indicates temperaturesabove the melting temperature (113~ C). Consistently low temperatures of hydrothermal activity are supported by the virtual absenceof secondary fluid inclusions of any type in quartz phenocrysts within the host dacite tuff. The intense, relatively high-temperature early quartz-alunite-pyrite alteration by relatively saline fluids recognized at such districts at Julcani, Goldfield, Sumrnitville and Ccarhuaraso(Bruha and Noble, 1983) is conspicuously absent.

EvidenceFor H.,'pogene Oxidation At Pierina, Yanacocha And Other Districts The breakdownand removalof sulfide and sulfosaltmineralsby hydrothermalsolutions in vein and relateddepositsis a long andwell established geological process (e.g.,Lacy and Hosmer,1956). At Pierina, introduction and profound depletion of various elementsconcurrentwith and later than the breakdownof pyrite, enargite and native sulfur strongly arguesthat their destruction was causedby hypogenesolutions. It would havebeenvery difficult, if not impossible, have addedthe amountsof to Au, Ag, Ba, Sr and Pb presentin both the oxide-bearing and iron-leached silicaObarite rock, and to remove one or more weight percentof iron, by supergene processes, particularly in the absenceof overlying rocks that were originally rich in precious metals and sulfides. Moreover, the irregular veinlets filled with barite andhematiteindicatea late stage fracturingbestexplainedby hydrothermal of processes. Hypogeneconversionof pyrite andother sulfide/sulfosalt mineralsto hematite(oxidation) canbe brought aboutby somecombinationof: 1) increase the f02 and 2) decrease total dissolvedsulfur in in content of a solution initially in equilibrium with pyrite. The presence highly oxidized/low total of sulfur hypogenefluids at the Yanacocha district is shownby the local presence alternatingbandsof of quartz and coarse(as much as 2-3 mm) specularite crystalsasopen-space fillings within high-gradeore zonesof the Carachugo deposit.Additional evidencefor hypogene oxidation is provided by the great depthsof oxidation observedin severaldistricts. Perhaps bestexampleis provided by the middle the Miocene Yanacocha deposit,in which oxidationextends a depthof at least 350 m below the surSur to face. Although supergene oxidationis present depths greater 400 m in pipesof polymetallic ore to of of of limestone replacement origin at the even younger(ca. 7.5 Ma) Yauricochadistrict of central Perf (Lacy, 1949;Alvarez et al., 1989),the district is in a regionof extremetopography,which would have facilitated downwardmovement oxygenated of groundwater.
Although oxidized sedimentary rock-hosted gold ores at the Carlin mine, Nevada, have been interpreted to have formed by hypogene processes(Radtke et al., 1980), other workers (e.g., Kuehn and Rose, 1992) have argued strongly for a supergeneorigin. There has been similar controversy at the Paradise Peak deposit (John et al., 1991; Sillitoe and Lorson, 1994). However, other partly oxidized sedimentary rock-hosted deposits in Nevada, such as Rain (Williams, 1992), possess geometric, nuneralogical and textural features suggestive of hypogene oxidation. Relict blocks of sulfide-bearing rock are locally present in sandstone-hosted gold ores exposedin the Tentadoraopen pit of COMARSA in the Angasmarca district, northern Perf (Montoya et al., 1995; D. C. Noble, unpub. data). At Tentadora, oxidation is deep and hematite is common, and a hypogeneorigin for the oxidation is a definite possibility.

Leyenda pag. 124 Figura 1. Diagrams summarizing certain minor-element relations of in ores from Pierina. All values have been recalculated free of S, Ba. Sr and associated oxygen, with the exceptionof the Ba-Au plot, for which the data have been recalculated free of sulfur. A = alunite rock; closed circle = pyrite+enargite+native sulfur rock; open diamond = covellite-rich rim; open square = oxidized rock associatedwith pyrite+enargite+nativesulfur cores; cross = oxidized friable silica rock with minor barite; inverted triangle = barite-goldrock; triangle = barite-rich rock with visible acanthite. Dashedlines connect samplesof different ore types from samespecimen. Note that logarithmic scale.s used for both are axesof aU the plots.

125

TIMING

OF PRECIOUS-METAL

DEPOSITION

At Pierina, copper was transported and deposited before, and by markedly different hydrothermal solutions than, most of the gold. A similar timing appears to hold for most, and perhaps the great majority of high-sulfidation deposits in which gold is the main economic metal. In some cases, for example EI Indio, deposition of enargite accompanied by modest amounts of gold was followed by a gold bonanza stage (Jannas et al., 1990). In the Angasmarca district, gold is late in a multistage hydrothermal history, being associated with Fe-oxides that fill fractures. In many deposits, late deposition of gold can be inferred from the rapid rates and high percentagesof gold recovery in cyanide column tests and heap-leach operations. The situation is very different from the strong coherence between Cu and Au observed in porphyry Au-Cu deposits. The very late deposition of gold and the complete or partial separation in time of late Au, Ag, Ba, Hg, Sb, etc. from earlier deposited Cu, Zn, Te, TI, Bi, As, etc., have important implications for the timing and mechanismsof extraction and transport of these elements in high-level high-sulfidation mineral systems. ECONOMIC CONSIDERATIONS

The existence of hypogene oxidation processes has implications for mining and exploration. Hypogene oxidation can be expected to extend to considerably greater depths than supergeneoxidation, increasing the tonnage potential for more economically treatable oxide (non-refractory) ores. Indeed, in some cases the intensity and pervasivness of hypogene oxidation processesmay increase with depth. Because hypogene oxidation and leaching can take place at depth beneath rock that has been relatively little affected by oxidation and/or other types of alteration, care must be taken in discarding prospects that have weak surface geochemical and alteration signatures. Moreover, the demonstrated mobilization of certain elements during the deposition of Au and Ag suggeststhat concentrations of hematite with elevated contents of Hg, As, n, Se, Te. Bi and Sn, may serve, in the absenceof a significant preciousmetal signature, as a geochemical guide to buried gold mineralization. SUMMARY OF CONCLUSIONS The results at Pierina, Yanacocha, Tantahuatay and other Peruvian systems confirm and extend knowledge of high-sulfidation Au-Ag deposits. Significant observations and conclusions include the following:

The evolution of high-sulfidation gold systems can be appreciably more complicated than commonly stated, involving multiple stagesof addition, mobilization and/or removal of metals and other elements; this conclusion is consistent with observations at Pierina and Paradise Peak.

. Hypogeneoxidation may take place in high-sulfidationsystems, hematiteis a common and

mineralin ore of high-sulfidationAu-Ag deposits. . Iron and also Ti, Zn, Cu, Se, Sn, Te, and Tl, may be leachedduring and after oxidation, particularlyduring the formationof high-grade ores. (refractory) and spatially associatedoxidized rock provide strong evidence for hypogene oxidation at Pierina, and has the potential of confirming or ruling out hypogeneoxidation processes other volcanicandsedimentary-rock in hosted deposits. . Iron, transportedupward by vapors and depositedas hematiteat higher levels, provides a useful exploration guide for buried high-sulfidation gold deposits,and particularly when accompanied elevated by concentrations Hg, As, n, Te, Se,Bi andSn. of not be discarded without a carefulevaluation the full geochemical of signature. . . Ore-gradeconcentrations gold are formed very late, althoughgold somemay have been of
introduced earlier during the formation of pyrite+enargite.

. Major differencesin the concentrations variousmajor and minor elementsin unoxidized of

. Prospects with weakand/orhigh-levelalterationfeatures precious-metal and anomalies should

Vuggy silica rock, althougha much better samplingmediathan early-stagealunitized rock, commonly containslittle gold, even if pyrite and enargiteare presentin cavities; oxidized vuggy silica rock is preferable.

1'/\

. The highestAu and Ag contentscommonlyare associated with abundantbarite the Ba-AuAg association very important. is . Solutionscontaininghigh concentrations preciousmetalsdevelopvery late in the evolution of of high-sulfidationsystems, gold mobilizationanddepositionis largely separated time and in from that of copper.

REFERENCES
ALVAREZ A., A., BONELLI A., J., and NOBLE, D. C., 1989, Sedimentary-rock-hosted precious-metaldepositsof the Yauricochadistrict, central Per: 28th International Geological Congress, Washington,D.C., Abstracts, v. I, p. 137 - 1-38. ARRmAS, A., Jr., 1995, Characteristicsof high-sulfidation epithermal deposits,and their relation to magmatic fluid, in Thompson, J. F. H., ed., Magmas. fluids and ore deposits: Mineralogical Association of CanadaShort Course Volume 23, p. 419-452. BRUHA, D. J., and NOBLE, D. C., 1983, Hypogene quartz-aluniteOpyrite alteration formed by moderately saline, ascendant hydrothermalsolutions: Geological Society of America Abstractswith Programs,v. 15, p. 325. HUANQUI. F., and CALLE, R., 1996, Pierina gold prospect: Lima, Unpublishedreport, Acuarios Minera y Exploradora S.A., 3 Volumes.including appendices maps. and JANNAS, R. R., BEANE, R. E., Ahler, B. A., and Brosnahan,D. R., 1990,Gold and copper mineralization at the El Indio deposit,Chile: Journalof GeochemicalExploration, v. 36, p. 233-267. JOHN, D. A., NASH, J. T., CLARK, C. W., and Wulftange, W. H., 1991, Geology, hydrothermal alteration, and mineralization at the ParadisePeak gold-silver-mercurydeposit, Nye County, Nevada, in Raines, G. L., Lisle, R. E., Schafer,R. W., and Wilkinson, W. H., eds., Geology and ore depositsof the Great Basin: Geological Society of Nevada,Reno,Nevada,p. 1020-1050. KUEHN, C. A., and ROSE, A. W., 1992, Geology and geochemistryof wall-rock alteration at the Carlin gold deposit, Nevada: Economic Geology,v. 87, p. 1697-1721. LACY, W. C., 1949,Oxidation processes and formation of oxide ore at Yauricocha: SociedadGeol~gica del Per, Volumen Jubilar, XXV Aniversario, ParteII, Fasc.8, 15 p. LACY, W. C., and HOSMER, H. L., 1956, Hydrothermalleachingin Central Per: Economic Geology, v 51, p. 69-79. LANGMUIR, D., 1971, Particle size effect on the reaction goethite = hematite+ water: American Journal of Science,v. 271, p. 147-156. LOWELL, J. D., 1997, Discovery of the Pierina, Peru, gold deposit by Arequipa Resources: 1997 SME Annual Meeting & Exhibit, February24-27, Denver,Colorado, Supplement Mining Engineering,p. 53. to MONTOYA, D. E., NOBLE, D. C., EYZAGUIRRE, V. R., and DESROSIERS, D. F., 1995, Sandstone-hosted gold deposits: A new exploration target is recognized in Per: Engineering and Mining Journal, v. 196, no. 6, p.34-41. NOBLE, D. C., 1996a,Outline of the geology and mineral potential of the Pierina prospect: Lima, Unpublished report for Arequipa Resources, Inc., 4 p. NOBLE, D. C., 1996b,Paragenetic relations in the high-gradeores and their possible relation to the distribution of gold and silver at Pierina: Lima, Unpublishedmemorandum Brian Park-Li, P. Hillard and D. Lowell. 3 p. to NOBLE, D. C., and SILBERMAN, M. L., 1984, Evoluci~n volc-nica y hidrotermal y cronologOa K/Ar del Distrito de Minero de Julcani: SocidadGeol~gicadel Per,VolumenJubilar LX Aniversario, Fasc.5, 35 p. RADTKE, A. S., RYE, R. 0., and DICKSON, F. W., 1980,Geology and stableisotope studiesof the Carlin gold deposit, Nevada: EconomicGeology, v. 75, p. 641-672. SILUTOE, R. H., and LORSON, R. C., 1994, Epithermal gold-silver-mercurydeposits at ParadisePeak, Nevada: Ore controls, porphyry gold association,detachmentfaulting. and supergene oxidation: Economic Geology, v. 89, p. 1228-1248. WILLIAMS, C. L., 1992, Breccia bodies in the Carlin trend, Nevada; Classification, interpretation and role in ore formation: UnpublishedM.S. thesis,Colorado StateUniversity, Fort Collins, 213 p.

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