270 Henry R. CoRNwaLL percent in these rocks but does not show an appreciable trend with increasing D. In considering the trends of the oxides, it should be kept in mind that because the sum of the oxides in an analysis is constant, a large increase in one oxide (commonly SiOz) causes a proportionate decrease in the sum of the remaining ides. The true trends of individual oxides, though modified by this effect, still convey a general impression of relative increases and decreases, especially where marked. This prob- Jem has been discussed by Chayes (1967), Krauskopf (1967), and other workers. ‘The minor elements show similar tight grouping of data along differentiation trends within and between the individ ual plutons. The associations between minor elements and between minor elements and major elements and Dl are indicated in Table 11.1 by the Spearman non-parametric rank correlation coefficients for all the chemical data from the individual plutons and all the plutons, Strong positive correlations have been found between manganese (Mn), co- bolt (Co), scandium (Se), and vanadium (V) and between these elements and the major elements Al, Ti, Fe, Mg, Ca, P. (The Mn-P correlation, 0.54 isnot strong and is below the cutoff of 0.59 for this table). Strontium shows a similar strong, correlation for all the elements except Mn. Except for Sri, these elements show a strong negative correlation with D. Si, and K (Sr-Si coefficient -0.56), ‘Yetrium CY) correlates positively with Ti, Fe, Mg, Ca, P, and Yb (Yiterbiumm), and negatively with D.1. Gallium corre- lates positively with Fe and P and negatively with Si. Lead correlates positively with DI. and negatively with Fe, Mg, and Ca. Copper has poor correlation with other elements, the highest with Ti, Fe, Mg, P (coefficient 0.37-0.42). TABLE 11.1 Correlation of Minor Blements With Other Minor and Major ‘Blements and Differentiation Index D1.) Positive Conelations Coal Seal ‘Seal Vat cons Seti VR Corre | SezFe varre CoMe. Sone VMs Coca Seca v-ca Cor So ve CoMn VM Cov Senin Vico CoSe Seco SeBa vise Mav Se¥) Sev) vst ya DAP Gare YorFe Ye yce GaP ve Yb Negative Continent Dice Mnst Cosi GaSiSeSi VSI Disco Mak Cok SeK Se VK Dise — PhezFe Dist Pha bay Pbce DALY Eteents eater thar 0.59 significant at 9 Sad based on 76 minor va. in thent pois and 37 minor ve Dl pales ‘The correlations between elements within individual pla- tons, where there are sufficient element pairs to be significant, are similar to those shown in Table 11.1 and discussed for the combined data, except that in the Rattler Granodiorite there ‘are no negative correlations between Pb and Fe, Mg, or Ca. ‘These data suggest a common source for the magmas but do not distinguish between common-source partial melting in the upper mantle or lower crust and upper crustal batholithie differentiation. COMPARISON WITH OTHER IGNEOUS SUITES Chemistry ‘Laramide igneous rocks in the Ray porphyry copper district do not appear to be unique among other cale-alkaline suites. Using the criterion of Peacock (1931), the trend line ‘of NaxO + KO crosses the trend line of CaO at about D.I. 60, where the SiO, line is at 60 percent (see Fig. 11.14). This is in the cale-alkalic (calc-alkaline) range. These rocks also fall in the cale-alkaline field using the criteria of Irvine and Baragar (1971). The similarity of the Laramide igneous rocks at Ray to other cale-alkalic suites is probably best illustrated by the ternary plot of normative Or-Qtz-Ab + An (Fig. 11.15) for the rocks in the Ray district and by the trend lines for all available analyses of Laramide intrusives in southern ‘Arizona (S.C. Creasey, 1977, written communication), for the easter and western Sierra Nevada batholith Ross, 1972), and for five analyses of granodiorite related to a por- phyry copper deposit at Battle Mountain, Nevada (Theodore et al, 1973). The similarity of these diverse suites, some related to porphyry copper deposits and some barren of cop- per mineralization, is very striking and significant, though not a new observation, ‘The trends of the percentages of various oxides plotted against DL. of the Laramide igneous rocks at Ray are similar to igneous suites in general, as evident, for example, in the 5,000 igneous-rock analyses compiled by Washington (1917) and contoured by Thornton and Tuttle (1960); the igneous rocks of the Coast and Transverse Ranges, California (Ross, 1972); and the igneous rocks at Bingham, Utah (Moore, 1973). Volatile Content of the Magmas ‘As has been pointed out by Banks (1976), several petro- chemical features of the Laramide plutons in the Ray area suggest that they did not saturate early during their crystalli- zation nor evolve much water. The MgO content of the biotite decreases slightly with increasing D.1. but markedly with decreasing age of the intrusives, Wones and Eugster (1965) have suggested that such a trend indicates undersatu- ration of water in the melt. Low content of volatiles in the magmas is indicated by the following characteristics: scarcity of aplites and pegmatite in the plutons, only minor meta- morphic aureoles around all of the intrusive bodies, absence of miarolitic cavities, sparsity of fluid inclusions in quartz, and the fact that these inclusions are dilute, two-phase, and omogenious below 450°C (J. T. Nash, 1971, 1972, written communications; M. J. Logsdon, 1973, oral communication),AL ARATES rl ok Weight %. DIFFERENTIATION INDEX (Modified from Thornton and Tulle, 1960) ‘The water content of the magmas at their emplacement is indicated by the point during crystallization at which hy- drous minerals first formed. In the rhyodacite dikes, Teapot Mountain Porphyry, and a restricted porphyritic facies of the Rattler Granodiorite, phenocrysts of biotite and hornblende Petrology and Chemistry of Igneous Rocks 27} TEAFOT MIN, PORPHYRY (GRANITE MIN, PORPHYRY TEA CUP GRANODIORITE ATTUER GeANODIORITE TORTLLA QUARIZ DIORTE RHYODACTTE OME AANOESITE DKE senooes SiO, Novo Figure 11.14, Percentages of major oxides platted relative to the differantiation index {©1.) of Thorton and Tutte (1960). The D.. ‘was calculated trom molocular percentages fof the calanorms rather than GIPW norms. occur in a fine-grained groundmass that makes up 30 to 50 percent of the rock; this composition indicates that the hy- rous minerals started to form before the midpoint of erys- tallization. However, in the Granite Mountain Porphyry, ‘Tea Cup Granodiorite, Tortilla Quartz Diorite, and themain272 Henry R. Connwatt, Figure 11.15. Comparison of normative (weight 2%) Kefeldspar (Cr), quartz (Giz), and plaglociase (AB + An) of Ray invusives with other aramid intuaves in soulhom Arizona (64 analyses), wih the Siera Novada Batholith, and with itsives in the Baile Mountain mining dist, Nevada. facies of the Rattler Granodiorite the hydrous minerals are intergrown with quartz and K-feldspar and are interst plagioclase, which makes up about 50 percent of the rocks. Tn these rocks—which largely constitute the intrusive bodies ‘at Ray—tiotite and homblende probably did not start to form before the midpoint of solidification, ‘At their depths of emplacement, the intrusive rocks at Ray should have contained 2.5 to 3.0 weight percent H;0 ‘before biotite started to form (D. R. Wones, 1973, oral com- munication; Wones and Dodge, 1966). If as indicated, biotite first formed after the plutons were 50-percent crystallized, then the initial water content of the more mafic magma must Ihave been less than 1.5 percent and even less in the more felsic magma. These amounts approximate those now locked in the rocks in primary hydrous minerals and are less than the amounts required to saturate the magmas at the depth of, intrusion with water; this fact suggests that little water 0s- caped the magmas. Textural studies show that the hydrous ‘minerals have crosscutting, interstitial, and coeval relations with the late-forming anhydrous minerals (mainly quartz, K-feldspar, and plagioclase) and that they occur in late-stage aplitic differentiates of all the plutons. Therefore, the hydrous, phases would have continued to maintain the amount of ‘water present in the silicate melt at 2 to 3 percent, until only a small amount—if any—liquid remained. Banks (1976), in a study of the halogen contents of igne- ‘ous minerals in Laramide intrusive rocks at Ray, has found no indication that C1 or H,0 build up in individual melts or with development of the igneous suite as a whole, as required for the generation of magmatic ore solutions. He has revealed that the rocks in the Ray district cannot be distinguished from other cale-alkaline suites with respect to rock or min- eral contents of Cl, F, and H0 or with respect to the trends of these contents with indicators of rock differentiation. The results of his study can be summarized as follows (Banks, 1976, p. 91): 1. Apatite and biotite in younger, more silicic socks contain ‘more F but less Cl and H,0+ than apatite and biotite jn older, more mafic rock; the same relations hold for F and H0+ in sphene. 2, The contents of Cl, F, and HO+ in whole-rock samples decrease with increasing differentiation index and de- creasing age. 3. The data are satisfactorily although not exclusively ex- plained by postulating that the melts each contained progressively. less Cl, F, and H,0 and that the hydrous Ininerals consumed most of the Cl, F, and H,0 in the magmas. 4, The data are similar to those for plutons that are not associated with porphyry copper deposits. SOURCE OF COPPER IN THE RAY DEPOSIT In speculating on the source of the copper and the miner- alizing solutions that formed the Ray deposit, several factors should be considered. The age of mineralization has been determined by K-Ar dating of hydrothermal biotite inter- grown with ore minerals at 65 m.y. (Banks et a., 1972). This date is close to but anomalously older than the K-Ar age of 61 my. for the Granite Mountain Porphyry, which was min- eralized by the ore solutions at the deposit. The K-Ar age of the hydrothermal biotite is also close to but slightly older than the age of 63 my. (Benks et al, 1972) for the Tea- pot Mountain Porphyry, which crops out as @ northeast- trending zone of small stocks and dikes 0.8 km north of the Ray deposit. The Tortilla Quartz Diorite, dated at 70 may. (Banks et al., 1972), erops out in a small stock 0.8 km south of the deposit and in a large pluton 3 km to the southwest ‘These intrusives plus east-trending rhyodacite dikes in the area are the intrusive rocks that are spatially, and possi- bly genetically, closely related to the Ray copper deposit. Ore solutions may have emanated directly from one of these ig- neous bodies or from a common source beneath the area at shallow or great depth. The ore deposit and two of the intrusive bodies (Granite Mountain Porphyry and Teapot Mountain Porphyry) occur near the intersection of major northwest- and northeast-trending fault zones. ‘These intersecting shear zones provided access to the sur- face from great depth for both magmas and hydrothermal solutions, T favor a model of magmas and copper-bearing hydro- thermal solutions ascending from considerable depth, proba- bly from the upper mantle. Derivation of the copper-bearing solutions directly from one of the nearby plutons does not appear likely, in view of the probable small amounts of vola- tiles that could have evolved from these intrusives. Ifa local source directly from a pluton is postulated, the Granite Mountain Porphyry is the most likely one, The small stocks jn the area of the copper deposit should be underlain at shallow depth by a larger body from which the solutions could have emanated.ACKNOWLEDGMENTS Tam grateful to Norman G. Banks for his support in this study and for his suggestions concerning the significance of the data obtained. Critical review of this chapter by Norman G. Banks and Arthur S, Radtke is also acknowledged. Chem- 1 data presented here are based on rapid rock analyses by P. L. D. Elmore, Gillison Chloe, J. L. Glenn, Lowell Aris, John Kelsey, and Hezekiah Smith and on quantitative and semi-quantitative spectrographic analyses by R. E. Mays and Chris Heropoutos. REFERENCES CITED Banks, N. G., 1973, Botte as a source of some of the sulfur in porphiyry copper deposits: Econ. Geol, v. 68, p. 697-703. 1574, Distribution of copper in biotite and biotite alteration products in intrusive rocks near two Arizona porphyry copper Aeposits: US. Geol. Survey Jour. Research, v. 2, 80.2, p. 195-211. 1976, Halogen contents of igneous minerals as indicators of ‘magmatic evolution of rocks asociated with the Ray porphyry copper deposit, Arizona: U.S. Geol. Survey Jour. Research, v 4yn0. 1, p. 91-117 Banks, N. G.; Cornwall, H. Ry; Silberman, M. L; Creasey, 8. Cs and Marvia, R. F, 1972, Chronology of intrasion and ore deposition at Ray, Arizona—Part I, K-Ar ages: oon. Geol, v.67, p. 84-878 Banks, N: G, and Krieger, M. H., 1977, Geologic map of the Hayden quadrangle, Pinal and Gila Counties, Arizona: US. Geol. Survey Geologic Quad. Map GQ-1391, 1:24,000, 15 p. text Banks, N.G., and Stuckles, J ., 1973, Chronology of intrusion and ore deposition at Ray, Arizona—Part I Fision-track ages: Econ. Geol, v. 68, p- 657-664 Chayes, Felix, 1967, On the graphical appraisal of the strength of ‘associations in petrographic variation diagrams, in Abelson, P. H, ed, Researches in Geochemistry, v2: New York, John Witey and Sons, p, 322-329, ‘Cornwall, HR.; Banks, N. G.; and Phillips, C.H,, 1971, Geologic ‘map’ of the Sonora quatrangle, Pinal and’ Gila ‘Counties, ‘Anzona: US. Geal. Survey Quad. Map GQ-1021, 124,000. Comvall, H.R, and Krieger, M. H, 197Sa, Geologic map ofthe Kearny quadrangle, Pinal County, Arizons: U'S. Geol. Survey Geol. Quad. Map GQ-1188, 1:24,000, —1975b, Geologic map of the Grayback quadrangle, Pinal ‘County, Arizona: US. Geol. Survey Geol. Quad. Map GQ- 1206, 124,000. Creasey, 8. C., and Kistler, R. W., 1962, Age of some copper ‘eating porphyries and other igneous rocks in southeastern ‘Ariza Geological Survey Research, 1962: U.S. Geol. Sur- vey Prot. Paper 450-D, p. D1-DS. (Creasey, S.C; Peterson, D. W. and Gambell, NA, 1975, relimi- nary geologio map of the Teapot Mountain quadrangle, Pinal County, Arizona: US. Geol. Survey Open-fle Rept. 75-314, 124,000. Damon, P. E, 1970, New K-Ar dates for the southern Basin and Range province, i Annual Progress Reports to Research Di- vision: U.S. Atomic Energy Comm., June, p. 38. Petrology and Chemistry of Igneous Rocks 273 ‘Damon, P. E., and Mauger, P. E,, 1966, Epeirogeny-orogeny viewed from the Basin and Range province: Soc. Mining Engineers Trans, ¥. 235, p. 99-111. Gitluly, James, 1932. Geology and ore deposits ofthe Stockton and Fairfield quadrangles, Utah: U.S. Geol. Survey Prof. Paper 173, 171 p. 1046, The Ajo mining district, Arizona: U.S. Geol, Survey Prof. Paper 209, 112 p. Irvine, T-N., and Baragar, W.R. A., 1971, A guide to the chemical classifcation of the common voleanis rocks: Canadian Jour. Earth Sei, v. 6p. 523-548, Koski, R. A. and Cook, D. S., 1982, Geology of the Christmas porphyry copper deposit, Gila County, Arizona, in Titley, 8. » ed., Advances in Geology of the Porphyry Copper Depos- its, Southwestern North America: Tucson, Univ. Ariz. Press, ‘Chapter 17. Krauskopf, K. B., 1967. Introduction to Geochemistry: New York, MeGraw-Hill Book Co,, 721 p. Lowell, J.D., and Guilbert, J. M., 1970, Lateral and vertical altera- tion-mineralization zoning in porphyry ore deposits: Econ, Geol, 65,9 3734080 Metz, R.A.; Phillips, C. H.; and Caviness, C. R., 1968, Recent developments in the geology of the Ray area, i Southern Arizona Guidebook 3: Atiz. Geol. Soe, p. 137-146, Metz, R. A, and Rose, A. W., 1966, Geology of the Ray copper deposit, Ray, Arizona, Zn Title, S. R., and Hicks, C.L,,eds., Geology of the Porphyry Copper Deposits, Southwestern North America: Tucson, Univ. Arizona Press, p. 175-168, Moore, W. J,, 1973, Igneous rocks in the Bingham mining district, Utah: U'S. Geol. Survey Prof, Paper 629-B, 42 p. Peacock, M. A., 1931, Classification of igneous rock series: Jour. Geology, v. 39, p. St-67, Phillips, C. H.; Gambell, N. A.; and Fountain, D. 8, 1974, Hydro- ‘hetmal alteration, mineralization, and zoning in the Ray de- posit: Econ. Geol, v. 68, p. 1237-1250. Ransome, F. L., 1919, The copper deposits of Ray and Miami, ‘Atizona: US. Geol, Survey Prof. Paper 115, 192 p. 1923, Description of the Ray quadrangle, Arizona: US. Geol, Survey Geol. Atlas, Ray Folio, No. 217, 24 p. Ross, D. C., 1972, Petrographic and chemical reconnaissance study ‘of come granitic and gneissic rocks near the San Andrea fault from Bodega Head to Cajon Press, California: U.S. Geol. Sur- vey Prof. Paper 698, 92 p. ‘Theodore, T. G; Silberman, M. L; and Blake, D. W., 1973, Geo- chemistry and potessitim-argon ages of plutonic rocks in the Battle Mountain mining district, Lander County, Nevada: US. Geol. Survey Prof. Paper 798-A, 24 p. ‘Thornton, C. P., and Tuttle, 0. F, 1960, Chemistry of igneous rocks—l Differentiation index: Am. Jour. Sei, v. 258, p. 664 684. ‘Washington, H. S., 1917, Chemical analyses of igneous rocks pub- lished from 1884-1915 inclusive, with a eritcal discussion of the character and use of analyses: U.S. Geol. Survey Prof. Paper 99, 1201 p. Wones, D. R., and Dodge, F. C. W., 1966, On the stability of phlogopite: Geol. Soc. America, Ann. Mtg., Program, with Abstracts, p. 243 (abs), Wones, D. R., and Eugster, H. P., 1965, Stability of biotite— ‘experiment, theory, and application: Am. Mineralogist, v.50, p. 1228-1272,12 Characteristics of Leached Capping and Techniques of Appraisal James A. Anderson In detailing the characteristics of leached capping, this chap- ter examines the nature of mineralogical and chemical changes produced during the oxidation and enrichment of sulfide deposits. The research has been directed toward devel- oping an understanding of the nature and origin of various products of weathering, particularly as they may be related to the nature of former sulfide assemblages, to host rocks, and to variations in physiography and climate. As a result of these studies, it has become possible to assess the probuble history and implications of secondary mineral assemblages present in the zone of supergene effects as they may relate both to enriched copper grades and to the nature of primary sulfide assemblages. The results are broadly applicable and ‘can be used in the study of porphyry copper systems with different host rocks and with widely different sulfide contents and ratios. Interpretations of published experimental studies reveal that variations in the pH of waters, produced by acids derived from oxidation of primary and secondary sulfide minerals, exert a strong and predictable control on the resulting sec- ondary mineral assemblage. The characteristics of this sec- ondary assemblage can, therefore, be used as one basis for interpretation of the nature of the primary mineral suite. This concept has focused research on quantitative mineralogical and chemical studies of limonite and other oxide minerals, of sulfide mineralogy, and of silicate alteration assemblages, as ‘well as of copper content and distribution in the zones of capping, sulfide and oxide enrichment, and primary sulfides. ‘The data presented here consist primarily of theoretical, ‘empirical, and practical bases for the interpretation of sec- ondary mineral assemblages. Interpretation of various as- semblages of limonite minerals is particularly important because these minerals, taken together with other criteria— such as rock and alteration mineralogy, rock copper ge0- p73) chemistry, ore textures, and geologic inferences—may be used to predict the copper grade and sultide mineralogy of subjacent sulfide zones. These criteria, which have been tested in field studies in the western hemisphere, are illus- trated in the chapter by charts, nomographs, and composi- tional diagrams which relate mineral stabilities to limonite-copper correlations. FUNDAMENTALS OF OXIDATION AND ENRICHMENT OF SULFIDES ‘The oxidation and enrichment of sulfide minerals is de- pendent on the oxidation potential ofthe chemical environ- ment. This potential is a function of the availability of free oxygen and can be expressed in terms of the partial pressure of oxygen (p03), as shown in Figure 12.1 Role of Oxygen The highest pO, obtained in nature is that of air, ie, atmospheric pO;, Oxidation potentials approaching this value are found in air-saturated porous rocks in the zone of capillary water above the ground-water table, This zone peri- odically becomes saturated for short durations by oxygenated meteoric recharge waters derived from surface runoff. Be- ‘cause air does not readily gain access to rocks where the pore space is saturated with water, the pO, decreases rapidly at the groundwater table, ‘The decrease in pO, below the groundwater table marks the transition between oxidizing and reducing environments for copper and iron minerals (see Fig. 12.1). Local oxidizing conditions prevail along structures that conduct oxygenated recharge waters below the groundwater table. Also, reduc~ ing conditions may persist locally in the zone of capillary water above the groundwater table.276 James A. ANDERSON Eh ( oxiéetion potentio! } ——> ormospheres } ——> 202 Figure 121. Diagram showing stabitty ranges of copper and rn com- ‘pourds with respect to oxidation potental and pH. ‘Stability of Sulfide Minerals ‘Changes in the oxidation potential (p03) ofa system are accompanied by changes in the stability of sulfide minerals (Gece Fig, 12.1), Sulfides are stable in reducing environments, but they liberate metal and sulfate ions in oxidizing environ- ments. Figure 12.2 shows the effects of oxidation in high- and ow-sulfide environments. Most of the metal ions released by oxidation of deposits containing a high total sulfide content (Fig. 12.24) are carried away in solution from the site of oxidation during periodic flushing by meteoric recharge wa- ter (Fig. 12.28). Most of the metal ions liberated by oxida- tion of deposits containing a low total sulfide content (Fig. 12.28) ate precipitated as hydroxides, oxides, carbonates, sulfates, or silicates at the site of oxidation (Fig. 12.2% Metal ions (particularly copper) that migrate to reducing ‘environments precipitate by reaction with hypogene sulfides, to form a zone of supergene sulfide enrichment. Most super- gene copper sulfides (chaleocite and covellite) form in the zone of reduction below the groundwater table (see Figs. 12.1, 12.28), but they also form in local reducing environ- ‘ments that persist in the zone of capillary water above the water table (Fig. 12.2C). Influence of Climate Climatic conditions influence the oxidation of sulfide deposits by controlling chemical weathering, which is depen- dent on temperature and amount of precipitation. Tempera- ture influences the rate of chemical reactions: tropical climates promote rapid chemical reactions, temperate cli- mates produce moderate reaction rates, and polar climates prevent significant chemical reaction. Precipitation influences the rate of leaching of metal ions from the oxide zone. It also determines the depth of oxidation by controlling the level of the groundwater table. Humid climates have high water tables that prevent deep oxidation. Semiarid climates are favorable for deep oxidation, leaching, ‘and enrichment because low water tables allow periodic re- charge water to remove capillary solutions from the oxide zone, Extreme atid conditions are favorable for deep oxida- tion but do not promote rapid leaching and enrichment be- ‘cause of the deficiency of recharge water. COnxidation of sulfide minerals occurs to some extent in all but polar climates, but the chemical weathering that pro- duces deep oxidation, leaching, and enrichment of sulfide deposits is most strongly promoted by tropical, semiarid cli- ‘mates. The duration of the favorable climate is an important factor in the effectiveness of entichment by chemical weath- ering. Oxidation Cycles ‘Oxidation of sulfide deposits proceeds in cycles that are controlled by fluctuations in the groundwater table. These fluctuations are produced by changes in the base level or climate of the area. First-cycle oxidation with leaching and ‘enrichment (sce Fig. 12.28) or first-cycle oxidation without Teaching and enrichment (see Fig, 12.2) continues until the primary sulfides exposed to oxidizing environments above an established water table are completely oxidized. Second-cycle oxidation (see Figs. 12.2, 12.26) is initi- ated by a relative lowering of the groundwater table, which ‘exposes additional sulfides fo oxidizing environments. How- ever, this process can be terminated at any stage by a rise in the groundwater table to levels above the sulfide zone. Sec- cond-cycle oxidation attacks primary sulfides and first-cycle supergene chalcocite. A large drop in the water table (usually ‘caused by regional uplift) may produce a large gap between first-and second-cycle supergene enrichment zones, as shown by the arrow in Figure 12.2C. Minor drops in the water table cotnmonly produce a zone of overlap between the first- and seeond-cycle chalcocite blankets. Second-cycle oxidation stops when oxidation of sulfides is complete above the new groundwater table. Repeated eycles of oxidation, leaching, and enrichment in porphyry copper deposits (related to repeated adjustments in the water table) produce inereases in the copper content ‘of successive enrichment zones (compare Figs. 12.2B,C). ‘This increase in grade culminates in complete replacement of hhypogene sulfides by chalcocite (depicted by 2-3% copper values in Figs. 12.28,C). Subsequent oxidation of this chalco- cite blanket produces in situ oxide ore (crosshatch pattern in Figs. 12.2C.D). This type of oxide ore commonly overliesonictwat. DEPOSIT revere oxtoario ae SUBSEQUENT OXIDATION - LEACHING (OF CHALCOCITE BLANKET. IW situ oxioarion (OF CHALCOGITE aLaNieT TRANSITIONS wort ANOREASING cmaLcoPyRiTe: TO PYRITE RATIO omaINAL. DEPOSIT exCLE OXIDATION susseauewr oxtoaTion eater sussequenr oxtparion merece | [3 Graczonenre | HE) | cduon eer | aE Bm re] \ | | | L | | I | 1 | = dielstonanracica JZ os 19 tte omen Figure 12.2. Ideatzed cross sections theough typical porphyry copper deposits showing the evolution of oxidation, leaching, ‘and enrichment in a mineralized system contaring 0.2 porcent copper and a 5 volume peroent total sulfide /A:0) and in ‘a mineralized system contain 0.5 percent copper and t volume percent total sulfide (E+). zones of leaching and enrichment formed by oxidation of deeper primary sulfides. ‘The pH of Capillary Water Oxidation of copper and iron sulfides in the zone of oxidation above the groundwater table affects the pH balance of water by releasing copper sulfate, iron sulfate, and sulfuri acid into capillary solutions. The amount of these com pounds available fo the solution is a function of; (1) the tot: sulfide content, (2) the copper sulfide to iron sulfde ratio, an ©) the mineralogy of the copper sulides. Effect of Sulfide Oxidation, Oxidation of rocks with278 Tames A. ANDERSON hhigh total sulfide content produces abundant sulfuric acid, ‘An increase in the copper sulfide to iron sulfide ratio or in the ‘copper content of copper minerals lowers the amount of available sulfur and thus decreases the amount of sulfuric acid produced during oxidation. The factors controlling sul- furic acid generation are illustrated by the following possible reactions: 4FeS; + 7H,0 + 14102 2HFcO, + 6H,SO, + 2FeSO, a 6CuFeS; + 12H,0 + 250, = 4HFeO, + Cuy(OH),SO, + 7H;S0, + 2CvSO, + 2FeSO, 2) A lowering of the total sulfide content of the rock also de- creases the amount of sulfuric acid generated by oxidation, ‘Some of the acid generated by oxidation of sulfides is consumed by reactive gangue—such as calcite, feldspar, and mafic minerals—in the host rock. The pH of the oxidizing ‘capillary solution is a measure of the equilibrium attained between acid production and acid consumption; itis, there- fore, a “built-in” system of accounting for the variables that ‘control oxidation and leaching. Effect on Leaching of Copper and Iron, Experimental and thermodynamic data on equilibrium stability fields of ‘cupric ion (Fig. 12.3) and ferrous ion (Fig. 12.4) demonstrate that the solubility of copper and iron is determined by the pH and pO, of the solution. These data indicate that a decrease in the pH of capillary solutions leads to greater solubility of, copper and iron from the oxide zone; on the other hand, an increase in the pH of a saturated solution results in the precipitation of copper and iron, Copper and iron minerals are also precipitated from saturated capillary solutions by inereasing the pO2 of the system. ‘The pH control over the solubility of copper and iron indicates that the amount of leaching from the zone of oxida- tion is related to the sulfide content and to the reactive min- eral composition of the host rock. Oxidation of unreactive rocks with a high total sulfide content produces low pH capillary solutions which accomplish nearly complete leach- ing of copper and iron from the zone of oxidation. An in- crease in the reactivity of the rock or an increase in the copper sulfide to iron sulfide ratio raises the pH balance of the capillary water. This change reduces solubility and, therefore, lowers the amount of leaching of copper and iron, Oxidation of rocks with low total sulfide content produces high pH capillary sotutions, which result in én sitw precipita- tion of copper and iron compounds in the zone of exidation, Because copper is more soluble than iron (see Figs. 12.3, 12.4), oxidation results in the preferential leaching of copper in comparison to iron. Effect on Supergene Copper Mineralogy. Experimental, thermodynamic, and geologic data suggest that the pH value of capillary solutions controls the mineralogy of supergene ‘copper, iron, and silica compounds formed during oxidation and entichment. The pH control of supergene copper miner- als is illustrated in the stability field boundaries shown in Figure 12.3. Low pH supergene solutions are required for CHALCANTHITE ANTLERITE, @ROCHANTITE Vineet 7 & a TENORITE PO Figure 12.9. EhpH diagram showing the stability elds of copper miner alsin the systom Os SH, thorough leaching and ensichment of copper. The stability fields of cupric ion (Cu), chaleanthite (CuS0,5H,0), cchaloocite (Cu,S), and covellite (CuS) dominate this environ- ment. Since water soluble chalcanthite that precipitates from. ow pH capillary solutions is redissolved by dilute recharge ‘waters that periodically lush the oxide zone, the residual copper in most thoroughly leached cappings is present in some form other than stable copper minerals. Analytical data show that the residual copper in this type of capping is camouflaged (included) in co-precipitating limonite minerals and in copper-iron mineraloids, including pitch limonite (HFe,cuO,], neotocite [(CuFeMn)SiO;}, and, more rarely, turquoise (CuO:3A11,02P;059H,0). “Moderate pH solutions produce partial leaching of cop- per from the capping. The stability fields of antlerite {Cus (OH),S04), brochantite [Cu, (OH),SO4}, cuprite (Cu,0), na- tive copper (Cu®), and chalcocite (Cu,8) dominate this envi ronment. Co-precipitating limonite minerals are saturated with camouflaged residual copper. Geologic associations in- icate that chrysocolla (CuSiOs-24,0) forms instead of bro- chantite when capillary solutions are high in dissolved silica; malachite [Cu (OH),COs] forms instead of brochantite in ‘cappings containing highly reactive carbonate gangue mineralsBORGSTROMITE -GOETHITE + BORGSTROMITE Eh ( oxidation poten 0p (atmospheres) Figure 12.4. Eh-oH diagram showing the stably felés of some ion minerals in the system Fe-S-H40. Neutral to alkaline (high pH) solutions do not produce significant leaching of copper from the oxide zone, The pres- ‘ence of tenorite (CuO) and abundant malachite or azurite are diagnostic of this environment. Effect on Supergene Iron Mineralogy. The pH control over formation of supergene iron minerals is shown by the goethite (HFeO;) and borgstromite-jerosite [(K,H)Fey(S0,)2 (OH),) stability boundaries in Figure 12.4, Experimental data indicate that hematite does not precipitate from Fe-S- 11,0 solutions at temperatures below ~125°C—the dehy- aration temperature of goethite to hematite. The stability relations of borgstromite, goethite, and hematite have im- pportant implications in leached capping interpretations. The pH dependence of the borgstromite-goethite boundaries indicates that the ratio of these minerals is related to the ature and amount of sulfides that produce sulfuric acid during oxidation. The pH{ control over the solubility of cop- per and iton provides a correlation between the borgstromite- goethite ratio and the amount of leaching of these metals from the zone of oxidation. The occurrence of lnematite in oxidized, low temperature, sulfur-tich systems is anomalous from the standpoint of present experimental evidence. The abundance of this mineral in oxide zones formed by oxidation ‘of a sulfide zone containing chalcocite suggests tat the oxi- Leached Capping and Techniques of Appraisal 279 dation mechanism of chaleocite stabilizes the hematite struc- ture at low temperatures. The presence of borgstromite or jarosite implies that ‘oxygenated capillary water has a pH lower than 2.2, the lowest value recorded for recharge runoff waters. This anon. alous condition suggests that most sulfide oxidation is accom. plished by capillary waters. The recharge water, it appears, merely serves to flush the saturated acidic capillary water from the system and to replenish the system with new capi- Jary water which rejuvenates oxidation. Oxidation halts ‘when oxygenated solutions reach equilibrium with sulfides and reactive minerals. Influence on Supergene Silicate and Silica Alteration, Some of the variables controlling the stability of supergene silicate and silica minerals are summarized in Figures 12.5 ‘and 12.6. The pH of the solution is an important control on mineral stability, and the concentration of elements essential in silicate minerals exerts similar controls on mineral stabli- ties, For example, a decrease in either the pH or the potas- sium ion concentration of capillary solutions attacking orthoclase may produce identical alteration sequences (gee Fig. 12.6). As shown in Figure 12.5, the concentration of silica in the solution also appears to control the presence or absence of sericite and quartz in alteration assemblages. ‘Supergene silicate alteration is independent of the oxida- tion potential of the system because free oxygen is not re- ‘quired in silicate alteration reactions: 2KAISi;0, + HzSO, + H,0 = ALSi0(OH), + 45i0; + 2K*+ 807 @) This condition implies that supergene alteration is not ‘confined to the oxide and supergene chalcocite enrichment zones of an oxidizing sulfide deposit. Supergene silicate alter- ation commonly extends for considerable depths into the primary sulfide zones. The mineralogy of supergene silicate alteration gradually changes with increasing depth in the hypogene sulfide zone. This change is attributed to reactive ‘mineral acid consumption, which produces 2 downward in- crease in the pH of acid solutions originating in the oxide zone, Chlorite and biotite (magmatic or hypogenc) serve as a measure of the extent of supergene acid attack because they are only stable under neutral to alkaline conditions at low temperatures and pressure (see Fig, 12.6). The upper limit of chlorite, biotite, and possibly gypsum in the hypogene sullide zone may, therefore, mark the depth of supergene acid altera- tion. Supetgene gypsum precipitates from calcium-bearing sulfate solutions under neutral to alkaline conditions and may, therefore, occur with the chlorite or biotite. X-ray studies of leached capping samples have shown that Kaolinite is present in most leached cappings located over chalcocite enrichment ore. This observation of “unreae- tive lay” can be readily explained by considering the kaolin- ite to be the product of supergene acid attack on reactive gangue, including calcite, plagioclase, and mac minerals. Such an explanation is supported by experimental, thermo- ‘dynamic, empirical data (see Fig. 12.5) and by field observa-280 James A. ANDERSON | \_dvsare | ! | 1 | | KAOLINITE GIBBSITE | ! ! i | | =a5 t 1 | | | i | ORTHOCLASE ALBITE | | i —>p—AmorPHoUs — SILICA LEGEND | | I | | | PYROPHYLLITE 28°C, | etm. pra [reo]! toa [#44806] ———> Figure 128. Suggested supergene stably leis of silicate and sllca minerals shown as a funeton of alkali hydrogen ton and slica solves. tions showing that kaolinite is the product of supergene acid attack on feldspar and micas. ‘The combined influence of pH and compositional con- trols makes correlations between supergene silicate alteration and the nature and amount of original sulfides much less diagnostic than those for supergene copper and iron miner- als. The sensitivity of the correlation is further complicated by the presence of hypogene sericite and clay minerals in some deposits. CHARACTERISTICS OF SUPERGENE MINERALIZATION IN LEACHED CAPPINGS, ‘AND CORRELATIONS WITH FORMER SULFIDE MINERALIZATION Experimental, thermodynamic, empirical, and theoreti- cal data reviewed in the preceding sections suggest that some ‘quantitative correlations exist between supergene mineraliza~ tion and the former sulfide mineralization. The nature and significance of these correlations have been examined by min- cralogical and chemical research on samples collected from the oxide, enrichment, and primary zones of sulide deposits. Interpretation of the data indicate that variations in super- gene iron mineralogy, in supergene copper mineralogy, and in capping copper geochemistry show close correlations with nificant differences in the former sulfide mineralization, ‘These relationships are summarized in the following sections. ‘Sulfide Oxidation Control of Supergene Mineralization Oxidation of copper and iron sulfides in the zone of capillary water above the groundwater table produces copper sulfate, iron sulfate, and sulfuric acid. The pH (net acidity) of the capillary water is controlled by: (1) the total sulfide content of the rock, (2) the copper sulidesiron sulfide ratio, (@) copper sulfide mineralogy, and (4) the reactivity of the host rock. The pH of the capillary water in turn regulates the amount of leaching of copper and iron from the zone of8, Ss 2 I\a\ & NES 2 i = ° 1 a 2 I 4 S. 6 G Pe % . | a\ % ! o\ = sll oN 2 | PANE : o & {wl — 4% 15l gy go} sl kaounite a 3) ei =a ol 2 al z a S ! 2 a L 1 73 LEGEND weolar Hea Figure 12.6, Suggestes suporgeno stabilty fields of sfoate minerals shown a8 a function of pH and activity of alka ‘oxidation. The pH of the solution also determines the ‘mineralogy of the supergene compounds of copper, iron, and silica that are precipitated from saturated capillary waters in the oxide zone, ‘Supergene Iron and Copper Mineralogy Supergene ferric iron minerals, broadly referred to as ““imonites,” and supergene copper minerals are listed in Fig- ure 12,7. Mineralogic analyses of samples from cappings over sulfide deposits demonstrate that the common limonite and oxidized copper minerals include goethite, jarosite-borgstro- mite, hematite, neotocite, pitch limonite, chrysocolla, tur- quoise, antlerite, brochantite, cuprite, and native copper. Significant quantities of copper are also camouilaged in co- precipitating limonite minerals. Leached Capping and Techniques of Appraisal 28) Tenorite is rare in cappings over sulfide deposits. This situation is explained by the neutral to alkaline conditions required for its stability field (sce Fig, 12.3). Tenorite does, however, commonly accompany malachite (or, locally, azu. rite) which occurs in cappings that contain abundant carbon ates, because the carbonates neutralize most of the sulfuric acid generated by sulfide oxidation. Chaleanthite is common in the mixed oxide-sulfide zone of most copper deposits. This mineral is rarely encountered in oxide cappings, since it is water soluble and is readily dissolved by dilute recharge waters that periodically flash the zone of oxidation ‘The hydrated ferric sulfates shown by solid triangles in Figure 12.7 are rarely found in cappings because of the ex- treme arid conditions required for their formation. They are, however, reported in the oxide zone of sulfide deposits in the Atacama Desert of northern Chile. Lepidocrocite is a com- mon limonite mineral in sulfur deficient, weathered zones, eg» most soils. Martite, the octahedral hematite pseudo- morph after magnetite, has not been observed in capping samples. As shown in Figure 12.7, a number of hydrous iron oxide minerals described in the literature have been discred- ited by X-ray studies by Posnjak and Merwin (1922) Alunite is common in certain types of cappings. It is included with the limonite minerals because ofthe solid solu- tion series it forms with jarosite. Jarosite may also form a solid solution series with the mineral borestromite (compare formulas in Fig. 12.7). Correlation of Limonite and Copper Oxide Mineralogy With Former Sulfide Content and Mineralogy Quantitative data on the limonite and oxide copper mineralogy of cappings and on the underlying sulfide miner- alization have been obtained on approximately 4,500 surface ‘and drill core samples from 85 properties. Empirical correla- tions of limonite and copper mineralogy with the former sulfide mineralization, made in areas where vertical zoning in the upper part of the primary sulfide zone is negligible are summarized in the three-dimensional diagram shown in Figure 12.8 illustrated in Figure 12.8 and, in more detail, in the sections in Figures 12.9 and 12.10 emonstrate that the limonite and copper mineralogy of a capping ate sensitive indicators of the total sulfide content and sulfide mineralogy of the former sulfide zone. The per- goethite, A= hematite, and J = jarosite), is diagnostic of the {otal sulfide content ofthe former sullide zone (curved planes in Fig, 12.8 or contours of goethite composition in Figs. 12.9 and 12.10). The percent hematite in limonite is related to the ‘amount and relative proportions of chalcocite in the former sulfide zone (dashed contours in Fig, 12.10). Jarosite does not form with copper sulfates in the capping (see Fig, 12.8). Supergene copper minerals form in a capping when the mole ratios of chalcopyrite:pyrite end chalcocitespyrite are greater than 0.5 in the sulfide zone (see Figs. 12.8, 12.9, and 12.10) ‘The mineralogy of the copper precipitates is controlled by the282 JAMES A. ANDERSON IRON MINERALS HEMATITE—Fea0s GOETHITE-HFeos BORGSTROMITE§(Hs0) Fests0412(0Hs JAROSITE=(x1Fe3(504)2(0H)g ALUNITE-(10At3(50))0M)e HOMMANNITE SERIES ~Fe203-2805-1440 COPIAPITE (W.S.)©2Feg03°5S03:7#20 COQUINGITE SERIES req0s 3805-20 RHOMBOCLASE SERIES Fep05"4804 rhz0 MARTITE=Fe,0y Leptoocracire -Feoton) % (WS) water souble discredited minerals a 2 3) @ 6 «s) turgite—Fez03 *ZoMe0 hydrogoetbite=Feg0s 1/sHe0 TimoniteFex03 Hz ranthosiderite~Feg03 24-0 imaite~Fe—03: 3He tcomerldaite-Fez05:4He0 AMORPHOUS COPPER é AND IRON COMPOUNDS PITCH LIMONITE -HtFe,61109 NEOTOGITE ~cur Fe si0g CHRYSOCOLLA~Cu5 Oy:20,0 TURQUOISE cv0-5Alg0-2F,05-9H20 COPPER MINERALS cUPRITE-cu0 NATIVE COPPER-cv° ANTLERITE~Gu (04504 BROCHANTITE-cuglOrIgs0, CHALCANTHITE=cuso, 5420 MALACHITE~cug(Om),605 ALURITE=Cas(OHgCO3) TeNORITE-coO -+ee a ; i 20 a) STROMITE Sis) ° ‘ ; ‘ied i GOETHITE; ° yarosite- \tEPIDOCROCITE ALUNITE # e HEMATITE (MARTITE) Fe,03 LEGEND Common Minerals Projected from K-AL Compositions H30* substitution for K* x) discredited limonite minerals Rare sulfates Figure 12.7. Compositions of supergone fei ron and copper minerals shown as functions of H:0-S0,-Fe0s, abundance and mineralogy of iron and copper sulfides. The intensity of iron staining in a goethite capping (100% goeth- ite in limonite) is proportional to the sulfie-iron content of the former sulfide zone, because significant leaching of iron from a capping does not occur until solutions have sufficient acidity to form jarosite or hematite. ‘The empirical correlations summarized in Figures 12.8, 12.9, and 12.10 demonstrate that the limonite and copper mineralogy of a capping provide sufficient evidence to make field estimates of the approximate sulfide mineralogy and total sulfide content of the former sulfide zone at each out- crop examined. The maximum and minimum limits of cop- per grade of the former sulfide zone can be calculated from these estimates by the use of the nomograph shown in Figure 12.11. This method of reconstructing the grade of the former sulfide zones results in low estimates in the case of cappings in limestone, dolomite, or other reactive host rocks. This, condition is explained by carbonate neutralization of sulfuric acid, which increases the goethite content of limonite and results in lower total sulfide estimates. Limonite Compositions, Copper Geochemistry, and Copper Leaching Empirical correlations of fimonite mineralogy and cap- ping copper geochemistry with copper leaching are summa- rized on the primary-grade prediction chart in Figure 12.12. ‘The primary-grade contours in this chart demonstrate that the percent of goethite in limonite is equal to the percent of, the original copper that is retained in the capping. Thus, for example, 50 percent of the copper originally present in sulfides is retained in a capping that contains 50 percent goethite in limonite. This correlation of the percent of goeth- ite in limonite with the residual copper content of the capping. is valid for all degrees of rock reactivity, because the pH of the capillary solutions influences the ratios of limonite| | q UNESKL ABBREVIATIONS ey SHE fave B-arocwantine OrreR ANTLERITE~ BROCHANTITE sanosite HewaTiTE CAPPING CLASSIFICATION Figure 128. Cotteaton of monte and copper mineralogy wih former sulle mineralization.284 James A. ANDERSON CHALCOPYRITE 100: seins SOD hana Sts Mole percent cheleopyrite in sulfides PYRITE 0 ja seger & Volume % Sulfides (decreasing pH) —> = 75— coarite in Liosite (1998/6 444) FE] « LEGEND Figure 12.9. Correlation dagram of limorite and copper mineralogy wih former pyrite and chalcopyrite in various copper deposits, precipitates (sce Fig 12.4) and, therefore, automatically ac- counts for differences in the reactivity of rock. The above correlations demonstrate that solutions derived from the oxidation of sulfide deposits with a low total sulfide content or high proportion of chalcocite (see white copper or iron. The oxide zone is, therefore, characterized by moderate to strong ion staining, predominantly goethite. Conversely, highly acid solutions detived from the oxidation of sulfide deposits with a high total sulfide content or low proportion of chaleocite (area with dark shading in Fig. 12,10) are eapable of leaching most of the copper and iron from the oxide zone. These cappings are characterized by ‘weak iron oxide staining, predominantly jerosite or hematite, In both examples, most of the copper in the capping is ‘camouflaged in the limonite minerals when the chalcopyrite: pyrite ratio (see Fig. 12.9) or the chalcocite:pyrite ratio (see Fig, 12.10) is ess than 0.5 (ie, less than 33 mole %). In these figures it may be seen that diagnostic copper minerals—e g., antlerite, brochantite, pitch limonite, neotocite—occur in cappings over deposits with chalcopyritespyrite or chal- cocitespyrite ratios greater than 0.5 (ie, greater than 33 mole %). ‘The grade predictions obtained from the chart in Figure 12.12 represent the grade of the primary sulfide assemblages which have been oxidized for most deposits. If, however, either antlerite, brochantite, cuprite, native copper, or resid- ual chalcécite occurs in the capping, the values obtained from the chart represent the grade of the former chalcocite enrich- ment zone at the point of observation. This correlation of Jimonite composition and rock copper geochemistry with the srade of the former enrichment zone for this type of cappingis explained by the marked reduction in acidity, and, thus, in copper leaching produced by oxidation of chalcocitespyzite cor chalcocite:chalcopyrite ratios greater than 0.5 (refer to the ‘marked inflection in percent goethite contours shown in Fig 12.10) Limonite Compositions, Copper Geochemistry, and Copper Enrichment Empricial data summarized in Figures 12.8, 12.9, and 12.10 demonstrate that the percent of hematite in limonite in ccappings over sulfide deposits shows a direct correlation with the percent of chaleocite in the former sullide zone. Addi- tional empirical correlations demonstrate that the percent of hematite in limonite and the residual eopper content of the capping are related to the amount of copper entichment at depth; the relationship between these parameters is shown on CHALCOCITE 100. Leached Capping and Techniques of Appraisal 285 the chalcocite-enrichment prediction chart in Figuie 12.13, The contour lines on this chart represent values of feet percent copper enrichment in the sulfide zone~ie, the amount of secondary enrichment copper added to the pri- mary grade. Methods of evaluating the amount of chalcocite enrichment included plotting: (1) the average grade of the chaleocite enrichment zone, (2) the enrichment factor (ratio of enrichment grade to primary grade), and (3) the feet- percent copper enrichment. This third method was the only one yielding satisfactory results. The values obtained (V)cor- respond to the equation (in ft. % Ca) = (EG - PG)T; where £G is the average grade of the enrichment zone, PG is the average grade of the primary zone (the average grade ‘of the upper part ofthe primary sulfide zone is used if vertical sulfide zoning occurs), and T"is the thickness of the enrich- ‘ment zone. The average grade of the chaleocite enrichment 504 33, 30. 20. Mole percent cholcocite in sulfides ——> PYRITE © SK ~~ RL ea 509 25% bf = me wee at mst mt st 0% fm oe 5 8 7 8 8 Volume % Sulfides (decreasing pi) ——> Tenorite ~ +cuprte —N Brochantite~ cup LEGEND Figure 12:10. Conelation of imonite and copper mineralogy wit former pyrite, chalcoclte, and chaloopytte mineralization.286 JAMES A. ANDERSON FoRMER MOLE PERCENT CHALCOPYRITE FORMER MOLE PERCENT CHALCOCITE in SULFIDES TN SULFIOES ° eo woh 7 \ © wt \ » * © ” % \ ao * N oe 0 a} \ \ : ® 0 ° 0 EXAMPLE OF NOMOBRAPH USE ven LLimorite ond copper minerology of capping indicate that the former sulfide zone containe 1 10 Mole percent Chalcopyrite in Sulfides (point A) 2-30 Mole percent Chalcocite in Sulfides (point B) “ee percent foe utiaas aes oh Procedure: T~Project line A-B to determine point ¢ IL-Project line CD to point & ond read the percent copper in the former sulfide zone PERCENT COPPER iN FORMER SULFIDE ZONE 005 on oe os 04 as os ar os 20 Figure 12.11. Nemograph for converting volume percent sulfide to weight percent copper in rook. zone can be predicted from calculations using the primary grade and feet-percent copper enrichment predictions if the thickness of the enrichment zone is known, can be estimated, ‘or can be assigned a set of possible limits. These methods of estimating the amount of chalcocite enrichment are valid for all degrecs of rock reactivity because of the pH (net acidity) control on limonite mineralogy. ‘The chalcocite-enrichment grade predictions obtained from the chart in Figure 12.13 represent the amount of en- richment expected in the chalcocite zone below the cap- ping of most deposits. Chaleocite enrichment predictions for cappings containing either cuprite, native copper, antlerite, brochantite, or residual chalcocite represent the enrichment, value of the former blanket at the point of observation, sincePPM COPPER IN LEACHED CAPPING (ROCK) Ps % GOETRITE IN LIMONITE LeseNo lreRpnevarive DATA 1=1500~ Minimum predited Figute 12:12. Gade prediction chart shows orginal grad of primary mineralization or, ether anterite, brochantie, cup, ‘native copper, or retidual chalcocit is presert, the grade of secondary sulde enrichment orginally present atthe point of obsarvation.PPM COPPER IN LEACHED CAPPING (ROCK) 2009, = + “ae 2 70 140% 130 wool — 1009} 70% +100 | ‘00 40} x 300 ov 6 Se mt ‘Se MEWATITE WW LNONITE LEGEND INTERPRETATIVE OXTA Feet % Coppa InCheteoite one Figure 12.19. Chalcocte-enrichment prediction chart based upon Hematite and copper contents of capping. If anllerte, ‘brochantite, cuprte, naive copper, cr residual chalcocio is prosont in the sample, the chart gives the grade ol the sulle enrichment bine orginay present atthe point of observation.most of the copper is retained in this type of capping and is ot available to produce further enrichment. The small amount of leaching from cappings of this type is explained by the marked reduction in acidity and, thus, in copper leach- ing, produced by oxidation of chalcocite:pyrite or chal- cecite:chalcopyrite ratios greater than 0.5 (refer to goethite contours in Fig. 12.10). Enrichment possibilities below cappings derived from the oxidation of sulfide zones containing pyrite and chaleopy- rite, but not chaleocite, cannot be evaluated by the above methods because of the lack of hematite, so more indirect qualitative methods—such as applying commonly observed enrichment ratios to estimated primary grades or evaluating the entichment indications of local isolated “pods” of hema- tite formed by scvond-cycle oxidation of local zones of prior chaleocite entichment—are the only techniques available. APPLICATION OF CONCEPTS OF CAPPING APPRAISAL ‘The data and interpretations concerning supergene mine cralization and former sulfide mineralization summarized in the preceding sections were developed for the purpose of applying the results to the exploration evaluation of leached ‘capping, The basic purpose of such evaluation is to predict the copper grade and the nature of sulfide mineralization that may lic beneath the surface. The field evaluation procedures necessary to accomplish these objectives are summarized in the following sections. These procedures utilize capping classification, limonite mineralogy, supergene copper min- eralogy, and residual copper content of the capping in pre- dicting primary copper grade, chalcocite enrichment grade, id characteristics and intensity of the underlying sulfide ‘mineralization. Vertical primary sulfide zoning, lateral downward migration of supergene solutions, and changes in rock type or structure must be anticipated by geologic inter- pretations. Classification of Capping Capping classification is based on limonite mineralogy, copper mineralogy, and oxidation cycles. Six types of cap- pings are recognized: (1) goethite, (2) jarosite, (3) hematite, (@ pitch limonite-neotocite, (5) antlerite-brochantite, and (6) malachite. A summary of the distribution and characteristics ‘of each type of capping is depicted in the idealized cross sections through typical porphyry copper deposits shown in Figure 12.14, Field verifications of some of these examples are shown in the color photographs in Figures 12.15, 12.16, and 12.17. Grade predictions for each type of capping utilize empirical correlations of the primary grade and chalcocite ‘enrichment grade of the sulfide zone with the (a) percent goethite in limonite, (b) percent hematite in limonite, (e) percent jarosite in limonite, (d) diagnostic copper min- eralogy, and (e) residual copper content of the capping. Recognition and Interpretation of Cappings First-cycle oxidation-leaching of the pyrite-chalcopyrite deposit in Figure 12.144 produces a chaleocite enrichment blanket overlain by an oxide capping containing goethite and Leached Capping and Techniques of Appraisal 28 Jarosite (ee Fig. 12.148), The capping formed over the py ritic halo containing 0.5 volume percent pyrite contains ge cthite and may, therefore, be classified as a goethitic cappin (represented by classification type 1 in Fig. 12.14). No cope or iron is leached from this type of capping. Limonite in the capping formed over the pyritic hab containing 4 volume percent pyrite consists of jarosite wit! minor goethite, while limonite in the capping over the or zone containing 5 volume percent total sulfides consists ¢ pure jarosite. Both of these cappings are classified as th Jarositic type (see the upper jarosite capping at Toquepal shown in Fig. 12,15; represented by classification type 2 in Fig. 12.14.). Most of the copper and iron has been leacher from these cappings. The primary grade of the sulfide zon beneath each of these cappings may be reconstructed by th: tse of the prediction chart in Fig. 12.12. The amount 0 chaleocite enrichment in the sulfide zone below these jarositit cappings must be evaluated by qualitative indirect methods such as applying a range of probable enrichment factors t the primary-grade prediction values. Enrichment factors ob served in similar deposits range from 1.5x to > 10x. The mos common range is 2x to 6x. ‘Oxidation of sulfides in the limestone inclusion shown it Figure 12.14 4—D is not accompanied by leaching of coppe or iron, because the acid is consumed by the reactive carbon fate minerals. A goethitic capping is formed in the limeston inclusion in the pyritic halo. Trace amounts of malachite ma, bbe observed in the capping over a pyritic halo that contain 0.02 percent copper. A malachite capping (represented b, classification type 3 in Fig. 12.14), which consists of malach ite (local azurite) and goethite, is formed in the limeston inclusion over the copper zone. Successive cycles of oxidation-leaching of the pyrite chalcopyrite deposit in Figure 12.144—D produce progres sively higher-grade chaleocite enrichment blankets (Compar Figs, 12.14B and 12.14C) that are overlain by one or mor of the following eappings: 1. original jarositc capping formed by oxidation of a pyrite chalcopyrite zone (see upper jarosite capping in Fi, 12°15; epresented by clasieation type 2 it Fig. 12.14 2, hematitic capping, containing hematite, jarosite, and gc ethite, formed by oxidation of the former chalcocite er richment blanket (see hematite capping at Chino in Fig 12.16 and hematite layer in capping at Toquepala 1 ig 1215; resented by Classifcation type 4 in Fi 3. lower jarositic capping, containing small zones of chalec cite enrichment or subsequent small zones of hematiti capping, formed by oxidation of pyrte-chaleopyril ‘zone occupying a gap between two enrichment zones (Se lower jars capping at Toguepale in Fi. 12.15 sp jarosite capping at Butte in Fig. 12.17; represented b classification type 2A in Fig. 12.14, 4, antlerite-brochaatite capping, containing antlerite or bre chantite with hematite, goethite, and occasionally ct prite, native copper, or residual chalcocite, formed b ‘the in situ oxidation of multi- epee, high-grade, chalec cite enrichment blankets in which chalcocite:pyrite ¢ chalcocite:chalcopyrite mole ratios are greater than 0. (represented by classification ‘type 5 capping shown ¢ the crosshatch pattern in Fig, 12.14C,D).290 James A. ANDERSON Gaps are commonly present between successive chaleo- cite blankets. These gaps form as a result of large, rapid, downward adjustments of the groundwater table produced by sudden uplift or lowering of the base level, Subsequent ‘oxidation of these deposits produces layered jarosite and hematite cappings, such as those at Toquepala, Peru (see Fig, 12.15). Minor downward adjustments in the groundwater table that take place over prolonged periods of time com- monly produce a zone of overlap between downward migrat- ing enrichment zones. Subsequent oxidation of these deposits produces a hematite capping such as that at Chino, New ‘Mexico (see Fig. 12.16). ‘The primary grade of the sulfide zone underlying jaros- itic and hematitic cappings may be estimated by using the prediction chart shown in Figure 12.12. Chaleocite enrich- ‘ment gradcs for the sulfide zone below jercsitic cappings must be estimated by indirect methods, such as applying probable enrichment factors to primary-grade estimates or by evaluating the enrichment indications of local isolated pods ‘of hematitic cappings formed by oxidation of local zones of chalcocite enrichment (see Figs. 12.14C.D and 12.17). Bs- timates of chalcocite enrichment indicated by hematitic cappings may be obtained from the prediction chart in Figure 12.13. Note that the irregular nature of the grade in the chaleocite enrichment zone in Figure 12.14 is pre- served by the distribution of hematite in the capping shown in Figure 12.14C. This relationship may also be observed in the photograph of the layered hematite capping in Figure 12.15, ‘Only minor leaching of copper occurs from in situ oxida~ tion of antlerite-brochantite capping (classification type $ in Fig. 12.14). The limonite and copper mineralogy and the residual copper content of this eapping can be used to recon- struct the grade and the feet-percent copper enrichment value of the former enrichment zone by referring to the grade prediction charts in Figures 12.12 end 12.13. The grade of the primary sulfide zone below this sulfate capping can then be ‘calculated by the formula V = (EG - PG) T, where V = feet-percent enrichment copper from Figure 12.13, EG = average grade of enrichment zone from Figure 12.12, PG = the average primary grade that is being sought, and 'T = thickness of the zone, known or reasonably estimated. Al transitions from primary pyrite-chaleopyrite miner- alization (see Fig. 12.144) to primary mineralization con- sisting only of chalcopyrite (see Fig. 12.142) are found in nature, A common occurrence of the chalcopyrite type is dopicted in Figure 12.142, wherein the sulfide mineralization consists of approximately 1 volume percent chalcopyrite. First-cycle oxidation of this chalcopyrite deposit produces a pitch limonite-neotocite capping (classification type 6 in Fig, 12.14£-H) consisting of oxide ore containing pitch limonite, neotocite, chrysocolla, gocthite, and occasionally residual chalcopyrite. No copper or iron is leached from this capping. except in local areas of higher sulfide content. Successive cycles of oxidation produce similar cappings (sce Fig. 12.14 GH). Neotocite cappings form over deposits with chal- ‘copyrite:pyrite ratios ranging from 9.0 to 0.5 (see Figs. 12.8, and 129). Oxidation of chalcopyrite deposits with higher total sulfide content produces oxidation-leaching-enrichment zones equivalent to those portrayed in Figure 12.144-D, ‘with the exception that pitch limonite or neotocte is present in each type of capping over the ore zone, Primary-grade and chaloocite-grade prediction techniques outlined above for the ceappings shown in Figure 12.145-A1 also apply for these ccappings. Field observations at Chuquicamata, Chile, and Cuajone, Peru, have confirmed that antlerite-brochamtite, neotocite, and neotocite-antlerite-bronchantite cappings overlie zones of ensichment formed by oxidation and leach- ing of deeper primary sulfides (refer to chalcocite enrichment zone shown in Figure 12.14D), This relationship in oxide ore zones has important exploration implications. “The indiscriminate use of hematite as indication of the presence of chalcocite should be avoided because of the oc- currence of hematite as thin layers of “desert varnish” result- ing from dehydration of limonite minerals by high surface temperatures caused by forest fires or by sun action. (This phenomenon has been observed in northem climates, eg., British Columbia, as well as in desert areas.) Other common ‘occurrences of hematite that are unrelated to chalcocite in- clude solfataric alteration, compacted “red bed” sediments, hhot spring deposits, iron formations, lateritic and desert soils, etc, Deposits of this type are normally low in copper. Grade predictions from the chart in Figure 12.12 do not indicate chalcocite enrichment. Note also that oxide copper values (rather than totals) must be used for the residual copper values to determine the amount of copper leaching from cappings containing visible sulfide minerals. Field Applications and Techniques Field estimates of the limonite and copper mineralogy of 1 capping provide sufficient evidence for capping classifica- tion and for estimates of the maximum and minimun copper grades of the former sulfide zone. Semi-quantitative predic- tions of the primary grade and chaleocite enrichment grade ‘of the sulfide zone below the capping require geochemical analyses for copper in rock end detailed mapping of the limonite and copper mineralogy. ‘The empiricial correlations summarized in Figures 12.8, 129, and 12,10 demonstrate that field estimates of the per- cent goethite in limonite (100 X G/G + H + J), of the percent hematite in limonite, of the percent jerosite in limo- nite, and of the copper mineralogy of a capping can be used to make semi-quantitative estimates of the approximate sulfide mineralogy and the total sulfide content of the former sulfide zone. This information can be used in conjunction ‘with the nomograph in Figure 12.11 to calculate the maxi- mum and minimum limits of copper grade in the former sulfide zone for each outerop examined. ‘The limonite and copper mineralogy of areas dcemed ‘worthy of further interest should be mapped in detail. Zones with 0, 0 to 10, 10 to 25, 25 to 50, 50 to 75, 75 to 100, and 100 percent gocthite, hematite, and jarosite in limonite, as well as areas of specific copper minerals, should each be outlined. Generally, these zones are easily recognized and ‘mapped ata rapid rate (much fester than alteration zones, foronicimat oEPostT MeveLe oxtoarion -LExcHNs SUBSEQUENT OxIOATION ~LEacHiNe tw situ oxtoarion OF chaLcociTe SLANKET fF chaucocite eLanveT ‘Teansitions ‘omiGinaL oeFOsIT evcue oxioarion Sead Pes smelly twinon eveirey | | ! i omanmners rane CHALCOPYRITE.TO PYRITE RATIO SUBSEQUENT oxiosrion EXPLANATION LASaIFICATION oF carPING ook TPES EB merce wenn LMDUITE MINERALOGY (EB crete nent concen nent noon sie tsa es ens Figure 12.14. Idealzed cross section: through typical porphyry copper deposit showing oxdation cycles, capping olassfioa tion, and ante charactoristes Inierprta tions shown fora system with 0.2 percen ‘primary copper and 5 volume percent tote Sulfides (4:0) and for a system wih 0.5 por ‘ent primary capper and 1 volume peroon lolal sulides (E-9.292 JAMES A. ANDERSON Prd Figure 12.16. Layered jarosie and hematite capping overying chalcacte ore at Toquopala, Peru. Upper jarasite capping {eaunad by oxisaton of pyite-chalcopyrte. Hemaita capping formed by oxdaton ofa chalcocito onvichment blanket (ayer (Cons: arose eapping formed by oxialion a apyite-chalcopyi zone between two chaloocite onrichmert blankets, Te (gan belwoon te former and present chalcocteorvichment blankets isthe result of a marked drop inthe groundwater able produced by sudden upit and tng, Pe ear) Figure 12.16. Hematite capping overying chaleacite ore at Chino (Santa ita), New Mexico, The hematite capping formed De oniwalcn ofa chalocate enechmont blanket. Continuous fowering ofthe groundwater table produced vertical continuity Of Ghaleoelte emichmont zones with eubsoquent continuous davelepment of a hematite capping,Leached Capping and Techniques of Appraisal 292 Figure 12.17. Jarosite capping with ocal zones of hematite capping over chalcocite reat Bulle, Montana. Jarosite cepping formed by oxiéation of pyrite-chalcopyrite. Hematite capping formed from destruction of local zones of chalcocte ervich- ment example). The size, shape, and control of these limonite map units provide the measure for the distribution of former sulfide mineralization. Brief experience with this type of map- ping soon shows, in some areas, the inadequacy of grid samn- pling for capping appraisal purposes in porphyry copper Prospects Representative rock samples from each type of capping and each mappable unit should be collected during the map- ping program. Visual estimates of the limonite and copper ‘mineralogy should be completed and recorded at the time of sample collection. The rock samples should then be submit- ted for geochemical copper analyses. Grade predictions for ‘each sample site can then be obtained from the empirical correlations summarized in Figures 12.12 and 12.13. Verif- cations of visual limonite mapping should be obtained by X-ray on limonite concentrates prepared from a few of the ‘more critical samples. The lowest detection limit of goethite in limonite by X-ray techniques is approximately 4 percent. This value corresponds to the visual detection limit for the ‘writer, but visual limits are not consistent forall observers. The above-described procedure of capping appraisal pro- vides a method of predicting primary and chaleocite enrich- ‘ment grades that is suitable for reconnaissance, examination, and project decisions. Identification of Limonite Mixtures and Copper Miner- als. The observed colors of limonite mineral mixtures are influenced by grain size, surface weathering (“desert var- nish”), nature of illumination, impurities, and the color sen- sitivity ofthe viewer. Most of these variables can be compen sated for by scratching the limonite in the rock sample anc comparing the color of the resulting powder (streak) wit! standard powders, A limonite color chart, containing stan dard mixtures of actual mineral powders, is @ useful aid it the field identification of mixtures of goethite, jarosite, anc hematite. Neotocite [(Cu,Mun,Fe)SiO,] and pitch limonite (H(Fe ‘Cu)0;] ) may sometimes be confused with manganese oxic: and goethite, respectively. Neotocite is distinguished fron ‘manganese oxide by its vitreous black to drab black appear ance and by a black to dark olive, waxy streak whet scratched; fine-grained mixtures of goethite in a sample com ‘monly impart a brownish tint to the streak. Neotocite, whic! ‘may contain up to 21. percent copper, can also be distin guished by a simple field test for copper. This test consists 0 applying 10 percent sulfuric acid to the mineral surface; rub ‘bing the acid-wetted surface with metalic iron, such as : knife blade; and examining the blade for an obvious coatin; of metallic copper. Pitch limonite may be distinguished from goethite in th field by its brown resinous appearance and shining blac! conchoidal fractures, which commonly show red interna reflection when viewed with a hand lens. It can also be identi fied by the field test for copper described above; this testi particularly useful for fine-grained occurrences, since th color of the powder (streak) is identical to that of goethite ‘This similarity to goethite is explained by X-ray studies294 JaMps A. ANDERSON which indicate that pitch limonite is a copper-bearing hy- drous iron oxide mineraloid that occasionally gives weak ‘X-ray reflections similar to those of goethit. Limitations of Capping Interpretations ‘The grade prediction techniques summarized in this chapter are by no means a panacea for porphysy copper ‘outcrop evaluation. On the contrary, the validity of this ap- proach to capping appraisal (outcrops or sub-outcrops) relies heavily on cortect interpretations of structure and petrology. Supergene solutions, for example, may show lateral down- ‘ward migration because of shallow dipping contacts fracture systems, or faults, such as those illustrated in Figure 12.14 ‘A-D. Pre-ore of post-ore structures may control or produce ‘offsets in sulfide mineralization. Rock types commonly have 1 marked influence on the distribution of primary sulfides. Highly reactive eardonate rocks below the outcrop may in- hibit copper migration, as shown in Figure 12.144~D. The possibility of vertical sulfide zoning must be evaluated by geological concepts and tested by geophysical techniques or drilling. The above considerations, and many more, must be used in conjunction with the grade prediction techniques in order to properly evaluate the potential of a capping. These factors must also be considered when evaluating the grade predictions in light of subsequent drilling results. SUMMARY ‘The characteristics of leached capping can be used to predict copper grades and the nature of sulfide mineralization that may lie beneath the surface. The procedures involved include the use of capping classifications, limonite min- ceralogy, supergene copper mineralogy, and the residual cop- per content of the capping. Capping classifications are based ‘upon limonite mineralogy, copper mineralogy, and oxidation cycles. Six types of cappings are recognized: (1) goethite, 2) jarosite, (3) hematite, (4) pitch limonite-neotocit, (5) antler- ite-bronchantite, and (6) malachite. Grade predictions for each type of capping utilize empirical correlations of the primary grade and chalcocite enrichment grade of the sulfide zone with (a) percent goethite in limonite, (b) percent hema- tite in limonite,(€) percent jarosite in limonite, 2) diagnostic. copper mineralogy, and (¢) and the residual copper content of the capping. Visual estimates of the limonite and copper mineralogy of the capping provide sufficient data for capping classfica- juantitative field estimates of the maxi- mum and minimum copper grades ofthe former sulfide zone at each outcrop examined. Quantitative predictions of the primary grade and chalcocite enrichment grade of the sulfide zone below capping require geochemical analyses for copper in rock and detailed mapping of limonite and copper mineralogy. ‘As a part of the study reported here, copper grade pre- fons were completed at 9 properties prior to drilling and post-mortem eapping appraisals were made at 9 other prop- erties, Drilling results available demonstrate that over 75 percent of the primary-grade predictions (in % Cu) agreed within 30 percent of the actual values encountered in drilling ‘Over 80 percent of the chalcocite enrichment predictions (in f. % Cu) agreed within 20 percent of the values obtained by driling ACKNOWLEDGMENTS: ‘The author wishes to ackuowledge the assistance and cooperation of Kennecott Copper Corporation, particularly personnel at Bear Creek Mining Company. The writer is especially indebted to D. R. Cook, P, A. Bailly, T. W. Mitcham, D. L. Norton, F. F. Clark, Annan Cook, R. E, Gilbert, J. A. Gower, A. H. James, R. E. Lehner, J. D. Mancuso, G. J. Stathis, T. N. Walthier, Alfred Weiss, J. C Wilson, and J. R. Woodcock for their interest and support, {deas, suggestions, and aid in data interpretation and presen- tation; to R. J. Broadhead, D. B. Roberts, W. M. Tudden- ham, and J. D. Stephens for their contributions to the development of new analytical techniques and for carrying out the work; and to D. H. Adair, G. Aguilar, W. W. Bal- tosser, H. E. Bauer, A. R. Grant, R. A, Metz, T. A. Netel- beck, G. C. Reed, M. D. Regan, W. M. Shepard, David Snyder, R. R. Weaver, and J. E, Worthington for their assis- tance in colleetion, interpretation, ficid application, and eval- uation of research data. SELECTED REFERENCES ‘Boas Becking, L. G. M Kaplan, I. Rand Moore, D., 1960, Limits ‘of the natural eavironments in terms of pH and oxidation- reduction potentials: Jour. Geol, v. 68, p. 243-284. Bladh, K. W., 1978, The weathering of sullide-bearing rocks asso- ated with porphyry-type copper deposits: Unpub. Ph.D. Diss, Univ. Ariz, 98 p. Blanchard, Roland, 1968, Interpretation of leached outcrops: ‘Nevada Bur. Mines Bull. 66, 196 p. Brown, J. B., 1971, Terosite goethite stabilities at 25°C, 1 atm: ‘Mineral Deposit, v. 6, p- 245-252. Emmons, W. H., 1917, The enrichment of ore deposits: U.S. Geol Survey Bull, 625, 530 p. Garrels, R, M., and Christ, C. L., 1965, Solutions, Minerals and Equilibria’ San Francico, Freeman, Copper and Co., 450 p. Garrels, R, M,, and MacKenzie, F.T., 1971, Evolution of Sedimen- tary Rocks: New York, W. W. Norton and Co., 397 p. Garrels, R, M,, and Thompson, M. E., 1960, Oxidation of pyrite by iron sulfate solutions: Amer. Jour. Sei. v. 258A, p. 57-67. Hodge, E.T,, 1915, The compositions of water in mines of sulphide ‘ores; Econ. Geol, v. 10, p. 123-139. Latimer, W. M., 1952, The Oxidation States of the Elements and. “Their Potentials in Aqueous Solutions, 2nd ed.: Englewood Cillls, N.., PrenticesHall, Inc, 392 p. Locke, Augustis, 1926, Leached Outerops As Guides to Copper ‘Ores: Baltimore, Williams and) Wilkins Co., 166 p. Lovering, T. S,, 1948, Geothermal gradients, recent climatic ‘changes, and rate of sulide oxidation in the San Manuel dis- triet, Arizona: Econ, Geol, v. 43, p. 1-20. Merwin, H. E,, and Posajak, E., 1937, Sulphate incrustations in the ‘Copper Queen Mine, Bisbee, Arizona: Am. Mineral, v.22, p. 567-371, Posnjak, E., and Merwin, H. E., 1922, the system Fe,0,-SOy-H,0: Tour. Amer. Chem. Soc.,¥. 44, p. 1965-1994, Posnjak, E., and Tuell, G., 1929, The system cupric oxidesulphur trioxide-water: Amer. Jour. Sci., Fifth Ser, v. 18, no. 103, p. 134.Ransome, F. L, 1919, The copper deposits of Ray andl Miami, Arizona: U. $. Geol. Survey Prof. Paper 115, 192 p. Sato, M,, 1960, Oxidation of sulfide ore bodies: 1, Geochemical ‘environments in terms of Eh and pH: Econ. Geol, v. 5, p. 928-961 Sillman, J. F. B., 1958, The stabilities of some oxidized copper ‘minerals in aqueous solutions at 25°C and | atm total pres- sures: Unpub, Ph.D. Diss., Harvard Univ., 98 p. Leached Capping and Techniques of Appraisal 29 ‘Tunell, George, 1930, The oxidation of disseminated copper ores i ‘altered porphyry: Unpub. PhD. Diss, Harvard Univ, 105 ‘Tunell, George, and Posnjak, E,, 1931, A portion of the systea ferric oxide cupric oxide-sulphur trioxide-water: Jour, Phy Chem, ¥. 35, p. 929-946. White, D. E; Hem, J. D3 and Waring, G. A., 1963, Chemie composition of sub-surface water: U'S. Geol” Survey Prof. Pi per MOF, 67 p,Geochemical Prospecting Techniques for Porphyry Copper Deposits SOUTHWESTERN UNITED STATES AND NORTHERN MEXICO Maurice A, Chaffee ‘The porphyry copper province of the southwestern United States and northern Mexico contains the highest density of known major copper deposits of any area in the world, Be- ‘cause this region has been so well endowed, exploration activ- ity, especially during the years 1960 to 1980, was quite intense, and most of the exposed deposits have probably now ‘been found. The region may still contain undiscovered cop- per deposits that are present beneath a thin layer of post~ ‘mineralization pediment gravels or volcanic rocks or that are present at depth within rock bodies that are exposed at the surface. Finding such blind deposits requires the use of indi- rect exploration techniques. To this end, geophysical tech- ‘niques have been successful in finding several deposits buried under post-mineralization pediment gravels. Geochemical prospecting techniques should also be use- ful in finding new blind porphyry copper deposits. A review of geochemical exploration techniques applicable in the search for copper deposits (Chaffee, 1975) described both proved and untried geochemical prospecting techniques. ‘Some of these techniques are particularly well suited to geo- chemical prospecting in the semi-arid climate of the south- western United States and northern Mexico. This chapter discusses some of the more useful sampling techniques for this region and describes the results of several investigations Undertaken to learn more about how geochemical prospect- ing can be used, ROCK SAMPLING The possible levels of erosion for porphyry copper sys- tems vary from those that expose the deepest root level of an actual copper deposit, or deeper (Fig. 13.1, level A), to those that expose the pyrite halo level (Fig. 13.1, level B), to those [297] ‘that expose only hypogene altered rock or apparently una, tered rock (Fig. 13.1, levels C and D). (A. porphyry cope system includes the copper deposit as well as the surroundin rock that has been affected by the mineralizing processes, Alteration-mineralization zoning, which has long been rec ‘ognized around porphyry deposits, has been very useful i the discovery of a number of copper deposits, including man whose copper-rich zone was not exposed at the surface. Ble ment zoning, based on analysis of whole-rock and (or) soi samples, should also be useful in locating copper deposit that are present deep within exposed rock bodies—pethap even those buried 50 deep that no alteration is apparent (Fig 13.1, level D). Element zoning has been investigated using analyses 0 whole-rock samples from the deeply buried and zoned Kala mazoo porphyry copper deposit near San Manuel, Arizon: (Gee location map in Fig. 13.2), The orebody is found within both a Precambrian quartz monzonite batholith and a Creta ceous quartz monzonite porphyry stock that intruded th Precambrian unit (Lowell, 1968). The top of the ore zon (059% Cu) occurs as deep as 1,130 m (3,700 ft). Results 0 the investigation are shown in Figure 13.3. They indicate tha intervals of high or low concentrations of at least 21 element are spatially related to the known ore zone (Chaffee, 19764 1982), The elements boron, barium, strontium, and lithiun are most concentrated in the lower part of the copper oF zone and below the ore zone in the barren, or low-grade, cor of the deposit. Surrounding the zone containing these fou elements is the ore zone, in which copper, molybdenum silver, and gold are concentrated. Outside of the ore zone are successively, aureoles of (1) cobalt, vanadium, and selenium @) iron (pyrite-related) and sulfur; (3) rubidium; and (4 {ellurium, gold, and iron (in the root zone only). The aurecle for rubidium and for tellurium, gold, and root-zone iron artErosion level © Hypogene alteration aurecle ‘Only waco aurecies exposed Several thousane Pyrite halo exposed Root zane exposed Figure 18.4. Schematic ciagram of a porphyry copper system, showing hypothetical lovels of eresion. Mocitiod after Lowell and Guilbort (1970), present well out into the propylitic zone; the auteoles for cobalt, vanadium, and selenium and for sulfur and pyrite- related iron also occur well outside the ore zone. Information presently available suggests that some additional elements (manganese, zinc, lead, thalliura, and possibly some others) may be concentrated in aureoles that are even farther from the ore zone than those shown in Figure 13.3. Element suites need to be determined in rock samples from other known deposits to determine whether common suites of elements exist for most porphyry copper deposits. ‘The results of the study at Kslamazoo suggest that analysis, of suites of ore-related elements in rock samples should be a useful method for evaluating exposed rock bodies for buried copper deposits The Kalamazoo study utilized whole-rock samples. ‘Many specialized samples derived from rock samples may also be useful in geochemical exploration for porphyry cop- pet deposits. Mineral separates, which tond to concentrate certain elements, may further enhance the widths and ele- ‘ment concentrations of aureoles of various elements present in the outer zones of a porphyry system. The element con- tents of biotite, magnetite, pyrite, and other minerals have Deen discussed in a number of studies cited in Chaffee (1975). ‘An investigation by Williams (1976) suggests that physical parameters, as well as the trace-element content, of accessory minerals such as apatite and rutile may be important in evaluating exposed rock bodies for their possible relation to Prosi: sol 4 ARIZONA eho! Kalamazoo Tucson validation tucson site ite, San in Tee Red Mountai ~~ ete | soNoRA ‘ Lacaridas ee Ncorn® X Eo a oo a00 LONETERG fe too0 wae Figure 19.2. Map showing locations of reas acuteed in chaptor (298)Geochemical Prospecting Techniques Potassic f+-10 99m mo + 510 pom Me Ferree ec Geochemical Prospecting Techniques 4 anomaly that extended the farthest downstream—a distam of at least 32 kilometers (about 20 miles). The distribution, molybdenum is shown in Figure 13.6 In another study regional stzeam-sediment sampling w: conducted in the Patagonia Mountains of southern Arizor (see Fig. 13.2) to learn more about the regional geochemic: features of a portion of the Arizona copper province and { determine which elements best define the known large, dee ly buried porphyry copper system at Red Mountain. Tt results of this investigation (Chaffee etal. in press) indicat that samples containing a combination of high concentrt tions of molybdenum, lead, and tellurium and low concent: tions of manganese best define the location of the Re Mountain system. The results also indicate that, relative t other parts of southem Arizona, much of the entire Pate gonia Mountain area contains high concentrations of leat copper, and tellurium; such high concentrations suggest the these elements may be especially useful in defining the limit of areas that may contain undiscovered porphyry coppe Geposits in southern Arizona or elsewhere. Concentrates panned from raw stream sediment hav also been widely used in reconnaissance geochemical surveys however, little published information has been available con cerning their use in prospecting for porphyry copper deposit in arid regions. In order to provide such informatics smavomerens Figure 13.6 Distibution of malyodenum in samples of steam sediment collected Inthe vicinity ofthe La Carded copper ‘deposit. Modified after Chafoo and others (1976).302 MAURICE A. CHAFFEE panned concentrates were prepared from splits of the stream-sediment samples collected for the geochemical sur- vey of the La Caridad deposit. Evaluation of the chemical analyses of these concentrates indicated that only copper, molybdenum, and tungsten produced anomalies related to the deposit (Chaffee et al, 1976a) Figure 13.7 shows the distribution of tungsten anomalies revealed by analyses of the panned concentrates. The anom- aly related to the La Caridad deposit continues for about 11 Kilometers (about 7 miles) below outcrops of the deposit—an impressive distance for an element not commonly studied in connection with porphyry copper deposits. Because of the relatively high (100 ppm) lower limit of detection for tung- sten in the concentrates, the actual content of this element could not be determined in many of the samples collected downstream from the deposit. If a more sensitive lower limit could have been used, the tungsten anomaly related to the deposit would probably have extended much farther down- stream. The anomaly for molybdenum in panned concen- trates extends about as far as that determined for molybdenum in the samples of stream sediment (see Fig. 13.6,and a more sensitive measurement of tungsten in panned con-centrates might reveal that the tungsten anomaly is equally extensive. Thus, the results of this study at La Caridad indicate that surveys using either stream sediments, © 2100 50m w eel +2100 gem or panned concentrates would have readily discovered the deposit. Copper anomalies can be found in sediments collected in ‘many stream channels in the southwestern United States and northern Mexico. Most of these anomalies, however, are probably not associated with porphyry copper deposits. The study at La Caridad found significant anomalies of molyb- ‘denum, zinc, silver, and tungsten in addition to anomalies of, copper. These results suggest that the determination of ele- ments in addition to copper shou’ help in evaluating other areas for their potential for porphyry copper deposits. If one assumes that most of the exposed porphyry copper deposits in this part of the United States and Mexico have already been discovered, then most stream-sediment surveys proba- bly should emphasize such elements as gold, lead, zinc, tel- lurium, selenium, and rubidium, which may be concentrated in aureoles outside of the copper-rich zone of a porphyry system, The presence of anomalies of some of these pathfinder elements in stream sediments may help to identify areas with exposed rock bodies containing blind porphyry copper deposits. VEGETATION SAMPLING ‘Both geobotanical and biogeochemical prospecting tech- niques have been used in the search for new porphyry copper Figure 19.7. Ditibution of tungsten in samples of panned concentrate prepared from material collected inthe viciity of te La Caridad copper depesit Modified after Chaftes and others (18764).deposits; however, only a few reports dealing with applica tions of these techniques in the southwestern United States, or northern Mexico have been published, Geobotanical Sampling Geobotanical surveys applied to the search for porphyry copper deposits in the southwestern United States have not been very successful. To date only one copper-indicator plant species has been found that demonstrates any relationship to concentrations of copper in surficial materials. This species, ‘the California poppy (Eschscholtcia mexicana), has been rec- ognized growing in copper-rich soils near many porphyry deposits (Lovering et a., 1950; Warren et al., 1951; Cannon, 1960; and Chaffee and Gale, 1976). One deposit where this species has been recognized is at Mineral Butte, Arizona (sce location map, Fig, 13.2). A generalized geologic map (Fi 13.84) shows a small copper deposit associated with a bio- tite-quartz monzonite stock of Cretaceous age that has in- truded Precambrian granite (Chaffee, 19765). Concen- trations of copper were determined for rock and soil samples collected over nd around this deposit. The abundance of poppy plants was also mapped in this area (Fig. 13.88), tseas Geochemical Prospecting Techniques 302 Mapping revealed a close relationship between the area of high copper content in soil samples and the area contain. ing the highest density of poppy plants (Chaffee and Gale, 1976). In spite of the apparent success of the geobotanical method at Mineral Butte, the technique probably has only limited value for exploration in the southwestern United States and northemm Mexico, Many areas of copper-rich soil in this region do not seem to support poppy plants. Also, wild Poppy populations have been observed growing in areas where only a normal concentration of copper is present in the soil. Residual soil is usually available for sampling in desert ‘areas where geobotanical surveys would be effective, so that geobotanical prospecting, which requires someone trained in botany to be effective, might not be justilied. In addition, the ‘method is not very practical in arid regions because during years of low rainfall, many species of desert plants simply do not germinate, do not flower, or are stunted; such conditions make identification of a given species dificult or impossible. Tnspite of these drawbacks, 2 geobotanical survey can be 8 rapid, inexpensive, and effective prospecting technique. Such surveys may prove useful in locating blind porphyry 1 os: A EXPLANATION Fou] Active stream alluvium |} (Quatemary) Yam | Biotite quartz: monzonite (Cretaceous) FE crante (Precambrian) === Approximate limits of copper deposit as determined from driling -——2 3s EXPLANATION Poppies abundant Poppies prosont 1000 ppm copper in soils 800 ppm copper in soils 600 weTERS 1500 FEET CONTOUR INTERVAL 90 FEET Figure 19.8. The Mineral Bute copper deposit. 4, generalizes geologic map and approximate location of the deposit 6, a2 4 Pes LARAMIDE Pe PSOE LARAMIDE Popa ete PORPHYRY 6 >ieavea (opeiam totals OM] fee eee LARAMIDE To Granite Figure 15.2. Geologic mep of the Tyrone deposit surrounding the quartz monzonite laccolith are associated ‘with faults that cut middle to late Tertiary volcanic rocks. Fluorite in the district has also been noted in fractures within the Gila Conglomerate. A hinge-type movement for the en- tire block southeast of the fault is plausible. The latest move- ‘ment on the fault tilted the ore deposit 5 to 8° northwesterly. The area of major displacement is located at or near the intersection of the Burro Chief and Mangas faults ‘The Racket-Virginia hinge-line fault zone extends east- ward from the Candlestick fault near Deadman Canyon and can be traced for almost two miles. Major copper mineralization occurs within the arca cir- cumseribed by the structures mentioned above; however, there are three notable occurrences of oxide copper outside these limits. Several occurrences of copper oxides are found west of the Burro Chief fault. The most prominent is the copper oxide mineralization at the Copper Leach property (formeriy the Ohio mine area). In this area, a mineralized dike of quartz, monzonite porphyry intrudes into Precam- brian granite and strikes northeasterly through California Gulch and Deadman Canyon. Less prominent oxide copper ‘mineralization occurs in areas south of the Racket-Virginia fault zone and less then ¥4 mile west of New Mexico High- way 90 and 34 mile south of the Gettysburg extension. ECONOMIC GEOLOGY Deseription of Orebody ‘The Tyrone orebody occurs within the Tyrone quartz monzonite laccolith and the underlying Precambrian granite. ‘The quartz monzonite porphyry is a deeply eroded remnant ‘of the original intrusion. The major portion of the laccolith ‘was removed by erosion, and only the many dikes and plugs which invade the Precambrian basement were left (see Fig. 15.2), The orebody consists of a supergene blanket of erratic ‘chaleocite coating on pytite mineralization. The blanket var- ies from a few feet to over 300 ft. in thickness. The orebody slopes northeasterly and tilts 8° northwesterly toward the Burro Chief fault. The top of the enrichment blanket is very regular, with sporadic remnants of sulfide ore in the oxi dized capping.332 Jose KoLEssar “More copper ore occurs in the granite at Tyrone than in the porphyry. The granitic rocks, intruded by dikes and plugs ‘of quartz monzonite porphyry, are exposed prevalently in the north half of the pit. Molybdenum content is also greater in the granite. Within the mine area, there are at least 20 par~ tially mined-out high-grade areas of chaleocite ore averaging 2 to 3 percent copper. These deposits were the principal mining areas at the time underground operations closed down in 1921; they trend roughly northeasterly along the larger fractures, most of which parallel the Burro Chief fault, ‘Aside from minute amounts of gold and silver recovered from the ore, copper is the only product resulting from the ‘mining. ‘An old water table, evident at the top of the sulfide zone, sharply differs from the location of the 1980 water level. Ore is found above the 1980 water table in the southern sector of the pit boundary and below it (from the 5,700-f. elevation) in the northern part of the orebody. The outline of the top of the orebody corresponds reasonably with the topography. Ore occurs within afew feet of the surface in the West Racket ‘extension near the St. Louis shaft and at $00 to 600 ft. below the surface in the northeast sector of the orebody. The bot- tom of the orebody is also irregular and grades into protore averaging approximately 0.10 percent copper. Ultimately, the pit may reach a depth of 1,300, with lateral dimensions of approximately 2 miles along the north-south axis and about 2 miles along the east-west axis. Mineralization ‘Although erratic and limited in distribution, chrysocolla is the most abundant copper mincral in the oxidized zone. ‘Tenorite, malachite, and azurite, together with rare cuprite, native copper, brochantite, and chalcanthite, are present in capping and near the Burro Chief fault zone. The ore miner- als occur in fractures, as disseminations in the country rock adjacent to fractures, and as matrix in breccias, Most of these fractures are ess than an inch wide and only rarely range up to a foot in width. Chaleocite, the most important ore mineral, and covel- lite ate the supergene sulfide minerals that replace pyrite, chalcopyrite, and sphalerite. Chalcocite occurs most often as a thin coating on pyrite grains, although in some siliceous breccias it occurs as almost pure blebs, possibly as a replace- ment of chalcopyrite or sphalerite. The pyrite:chaleocite ratio is approximately 6: ‘The primary sulfide minerals are pyrite, chalcopyrite, and sphalerite, with occurrences of molybdenite and trace quantities of bornite in the granitic (northern) part of the orebody, Pyrite, which contains small inclusions of quartz and chalcopyrite, is the most abundant sulfide mineral and commonly is partially replaced by chalcocite at its margins or along veinlets. Chaleopyrite is generally observed as parti- cles in quartz and is also present as small inclusions in pyrite and sphalerite. Sphalerite is commonly associated with pyrite and has replaced it in part. Molybdenite, which appears as curved shreds unas- sociated with other sulfide minerals, occurs as a thin coating ‘on joints and fractures in the porphyry and as veins (with quartz) in the granite. Of very minor significance, bornite ‘occurs as sparse remnants of crystals largely replaced by chalcocite. Sulfide content in the protore is less than 6 per- cent by weight, Of the six species of copper phosphates found in porphyry copper deposits, at least four occur at Tyrone: libethenite, torbernite, pseudomalachite, and turquoise. Lead rmeta-autunite has been identified in the West Racket vicinity. Hydrothermal Alteration Hydrothermal alteration and associated processes may contribute to preparation of the rock for enrichment by de- velopment of porosity and permeability in addition to intro- ducing the necessary primary sulfides. In some areas the porous, carthy, altered porphyries serve as host rocks for the supergene enrichment process, but there are enriched areas that do not conform to this description. Sericite is the most abundant hydrothermal alteration product. Hypogene clay ‘minerals occur in the younger porphyries and in the area below the bottom of enrichment. Argillic alteration occurs erratically, but quartz-sericite is the dominant form of alteration, Propyltic alteration oc- ccurs peripherally to the northeast on the edge of the Gettys- burg extension, along the Burro Chief fault zone in the northwest part of the West Racket extension, and near the ‘geographic center of the orebody between the original pit and the West Racket extension at the 1,600-f. level. The younger porphyries exhibit chloritization of biotite, with feldspar al- tering to montmorillonite, and development of pyrite in the Racket areas only biotite, chloritization, and meager pyritiza~ tion occur in the Gettysburg area. ‘The poikilite orthoclase feldspars for the most part ap- pear relatively fresh, occasionally exhibiting a thin alteration zone on the periphery of the phenocrysts, although in some areas the phenocrysts are completely altered. Some of the ‘most important chemical changes in the porphyry at Tyrone can be noted by the free quartz content, which may range from less than 15 percent in the fresh rocks to 40 to 70 percent in the altered varieties. The Na,O content, which may vary from 2 to 5 percent in fresh rocks, is invariably reduced to less than 1 percent in the orebody with the de- struction of the plagioclase feldspars. ‘The fact that enormous amounts of water have been added to hydrothermally altered rocks is evident in ignition loss, which is measurably significant because of the abun- dance of sericite. There has not been any significant change in the K,O content in the altered and fresh varieties. The ‘chemical comparisons are based on analyses of fresh rocks from the surrounding barren porphyries and on altered rocks sampled from within the orebody. Silicification is prevalent in the Precambrian granite- ‘quartz monzonite contact zone, a phenomenon repeated in at least one other southwestern porphyry copper deposit. The zrone of silicfication meanders midway across the narrower expanse of the main orebody outline and then moves along the extreme northeastern pit limits. Slicification also prevails around granite apophyses in the lower levels of the southeast sector of the main orebody (the Racket area). Nontronite occurs in the transition zone between the bottom of the capping and the top of sulfides. Alunite occurs in localized veins in the granite-porphyry contact zone andhas been observed as matrix in a breccia in the area between the Gettysburg extension and the main orebody. In the pro- tore, the preponderance of a yellowish brown montmerillo- nite immediately below the chalcocite zone suggests that the normal hypogene alteration is obscured by supergene effets; the bleached appearance of enriched sulfide zones is absent. Leached Capping ‘The appearance of conditions in the supergene cap rock at Tyrone does not vary significantly with rock type; granites display the same general appearance as porphyries and breceias. The cap rock over the Tyrone copper deposit is a classic example of all stages, from extremely immature to well-defined, mature, supergene capping. The most impor- tant constituent—and certainly one of the most abundant minerals in capping over Tyrone and other disseminated cop- per deposits—is supergene hematite, Supergene hematite is present as the principal mineral filling the cavities vacated by the sulfides. As a filling, it has a finely fibrous appearance, while as a crust, the surface is made up of tiny spherules. Supergene hematite, which is gencrally of a porous mature, also forms narrow seams and veinlets, and stains the surrounding rock a prominent ma- oon, To be of economic significance at Tyrone the area must exhibit supergene hematite in both veins and disseminations; rarely does a preponderance of one form or the other indicate ore-grade, enriched sulfides, In the northwest area of the mine site, the fissure out- crops exhibit considerable hematite, and chalcedony is stained deep maroon with hematite. In the southwest sector —issure outcrops consist of hematite, granular quartz, and irregular deposits of chrysocolla. Tenorite has been noted in ‘outcrops above areas of thorough oxidation, and neotocite ‘occurs around the periphery of economically important areas. GEOLOGIC HISTORY The geologic environment prior to Laramide intrusion consisted of Precambrian granite overlain by Cretaceous vol- ccanics and sediments. During the Laramide Revolution, the ‘Tyrone laccolith intruded the area as a multiple intrusion north of the Big Burro range. In early Tertiary time following Laramide intrusion, an uplift then tilted this area to the northeast, and at approximately the same time the Burro ‘The Tyrone Copper Deposit 333, Chief fault bisected the laccolith. Displacement of the area cast ofthe fault limited mineralization to the northwest. The uplift accelerated erosion and removed the Cretacous cover ‘over the laccolith, exposing the porphyry. During uplif, the entire vicinity north of the Mangas fault scasp was essentially ‘an area of moderate relief, with fat-lying Cretaceous and Tertiary flows. If any barren Tertiary volcanics were depos- ited above the site of the Tyrone orebody, their removal by erosion probably contributed to an intensified supergene pro- cess in the area, ‘Several movements oceured along the Burro Chief fault; the last occurred during Pleistocene time and tilted the de- posit into its present position. The same era of faul sulted in tilting of the entire Little Burro mountain range northeasterly, creating the present land forms. SUMMARY ‘The Burro Mountains District has progressed from a minor turquoise and copper producer in the 1870s to a major United States copper producer a century later. Mining prior to and during World War I concentrated on developing en- riched sulfide veins and breccias. The orebody is a classical example of supergene enrichment of a disseminated pyrite- chalcopyrite protore in a host rock of quartz monzonite por- phyry and granite. The protore, averaging about 0.10 percent copper, has been enriched to a grade averaging less than 1 percent copper, The thickness of the enriched ore varies from a few feet to over 300 ft. Leached capping varies from several feet to 500 ft. in thickness. The laccolith of quartz monzonite porphyry was intruded between Precambrian granite and overlying volcanics and sediments. Most of the volcanics hhave been removed by erosion. The laccolith wes invaded by many scattered dikes and plugs of various textured porphy- ries intruded at several times; usually finer-grained rocks were followed by varieties which cooled slowly and resulted in coarser textures. Uplift and deep erosion of the laccolith then resulted in an enriched orebody with a large volume of leached cap rock. REFERENCES CITED Gillerman, Elliot, 1964, Mineral deposits of westem Grant County, ‘New Mexica: N. Mex. Bur. Mines Bull. 3, p. 41-48. Paige, Sidney, 1922, Copper deposits of the Tyrone district, New ‘Mexico: U.S. Geol. Survey Prof. Paper 122, 53 p. : Somers, R. E., 1915, Geology of the Burro Mountains copper dis- ‘ict, New Mexico: AIME Trans. v. 52, p. 604-656.| : t i Structural, Petrological and Mineralogical Controls for the Dos Pobres Orebody LONE STAR MINING DISTRICT, GRAHAM COUNTY, ARIZONA Jackson M. Langton and Sidney A. Williams The Des Pobres orebody is one of the four known porphyry copper deposits discovered in the Lone Star mining district, situated on the southwest slope of the Gila Mountains in Graham County, Arizona. This ore deposit is located ap- proximately nine miles north of Safford, the county seat (Fig. 16.1), Surface elevations over the orebody range between 3,900 and 4,200 ft Phelps Dodge Corporation optioned the property in the fall of 1957 and commenced drilling on November 21, 1957 By early 1960 sufficient economic mineralization hiad been delineated to warrant purchase of the optioned claims (Rich- ard Moolick, 1968, personal communication). Exploratory dcilling continued intermittently after 1959 and the first ex- ploration ond development shaft was begun in November, 1968. AAs of July 1, 1979, approximately 189,000 feet of ro- tary drilling and diamond coring had been completed in the immediate vicinity of the orebody and more than 79,100 feet of shaft sinking, crosscutting and drifting had also been ac- ‘complished (K. C. Bennett, 1979, personal communication), Alll exploratory drilling and development work has con- firmed reserves of approximately 400 million tons of 0.72 percent copper sulfide ore The early phase of exploratory drilling indicated that the ore geometry resembled an inverted funnel, with the minable copper values draped over a relatively barren granodiorite stock at depth. The second phase of delineation, which con- sisted of diamond coring on a 400-f. grid and underground development work, provided sufficient information to me- Jiorate previous concepts and to ascertain several facts that were pertinent to localizing the orebody. Extensive petro- graphic studies correlated with computerized whole-rock chemical analyses and geologic mapping were an integral part of the research conducted on the Phelps Dodge ore- body. [335] DISTRICT GEOLOGY ‘The Dos Pobres orebody occurs in folded, consanguit ous metavoleanics and metavolcaniclastics that are gen ically related to Laramide diorite, tonalite, qua: monzonite, granodiorite, and andesite intrusives. The Cre: ceous-Tertiary kindred locally crops out from beneath v per Tertiary volcanics and Pliocene to Recent pedime ‘gravels along a regional, northwest-trending structural b (Fig. 16.2). Hornblende and pyroxene andesite Bows a1 agglomerates dominate the kindred, but are often inte calated with latites, glassy dacites, dacite tuls, and voloar conglomerates, wackes, and breccias, The volcaniclast members generally dip and thicken away from the centt belt of principally voleanie rocks. This enormous thickness of older andesites was deriv from an underlying parental tonalite-granodiorite pluton(: interpreted as Late Cretaceous to Paleocene in age (Tat 16.1). Two outerops of the pluton(s) have been observed | the authors and a third one has been described by Robinsc and Cook (1966); Figure 16.2 shows the location of the uterops. Several localities where apophyses of the pluton( are relatively close to the surface have been observed. O1 hole actually penetrated the Laramide metavoleanics at intrusives and encountered an amphibolite derived from se¢ ‘ments of probable Precambrian age. Xenoliths of Precambrian gneiss, schist, quartzite, ar granite in the metavolcanics, quartz diotite pluton(s), an: ‘occasionally, in the quartz monzonite porphyries have bee recognized on the surface and in numerous drill hole san ples. The nearest outcrops of Precambrian gneisses an schists, however, are south of Safford on Graham Mounta at elevations up to 10,700 ft. Since more than 5,000 ft. a allowed for Miocene uplift, it appears that the narrow belt336 JACKSON M, LANGTON AND Sipney A. WILLIAMS Figure 16.4. Index map of the Lone Star mining dstict Laramide andesites were extruded in a structural trough with more than 10,000 ft. of topographic relief. The andesites that ‘have been drilled are sub-zerial in character, and deep explo- ration throughout the district has failed to find voleanics of spilitic afinity. ‘The Dos Pobres orebody is remarkably similar to some cof the porphyry copper deposits in British Columbia (Carson and Jambor, 1974), the Philippines (Saegart and Lewis, 1976), the Solomon Istands (Fountain, 1972), and the Andes ‘Hollister, 1973; Camus, 1975; Gustafson and Hunt, 1975). ‘A rather subtle unconformity exists between the Terti ary-Cretaceous Safford andesites and Tertiary Baboon ag- glomerates (see Table 16.1). The agglomerates are intruded by non-produetive hornblende andesite dikes, sills, and plugs,soesjoneow plojeg ouso09(eg-snosoeie.D EE] swowons tee ap (Guoind owop zsonb-2wopoue® juaied euscosjeg-sno228I20 ESO (j8019 wyu0g s9m0) weoas fedudieg —— yseM 0 won. 010g LM JED wn ‘s20}U00 eNsaNXS pue ONEiNy) —— AporoHin seu0e says pazjeieuy =a pojesouco suey peniop ‘peweju siayn peusep ‘SNe; oFUE YB. NOLLWNVTExa338 JACKSON M, LANGTON AND SupNey A, WILLIAMS TABLE 16.1 ‘The Geologic Column at the Dos Pobres Orebody a Thickness a Rock Type Composition niches Age Symbot iam, Tenrace Sands, claybeds, raves slkstones, 5 > ogg eer Gravee, Basin il conglomerates Seen es ica Unconformity Basalt & shyolite dikes, sil, plugs; basalt flows, tuts, shyolites, 25° F EEL-iaainteas pss . Gilt Mounisin Veleanics —glomerates, vent debi, basa oe ee ? conglomerate ‘Unconformity Horablonde andesite dikes, sls, im ee a logs Baboon Metavateanics: Motavoleusislasics Propylitized andesive agalomersts, flow breccias, mod flows, Htle O-1,500" —Bocene Tm ‘ifs, conglomerates Unconformity “Tonalite-quastz monzonite- Productive Forphyries sionzonitegranodionive porphyry - Paleocene Bocene Ling Stock(), dikes, and sills Quartz diortegranodiorite io ‘Upper Cretaceous- arene batho Paleocene fee Metamorphosed hornblende and Safford Metavoteanict- pyroxene andesite flows, breccias, Upper Cretaceous: oan Metavolcaniclastics agglomerates, wackes,& rand ae Pleccene i lows Unconformity “Amphibole, gis, granite, a aa ie ‘quaieite, schist ‘most of which are clearly younger than the productive por- phyries and appear to be genetically related to the flows. The productive quartz, monzonite porphyties do not intrude the Tertiary Baboon sequence, but the agglomerates are often well mineralized along the hornblende andesite dikes and shear zones. These agglomerates crop out northwest, north, and northeast of the Dos Pobres orebody (Fig. 16.3) Analogous to the large Morenci-Metcalf district, 20 tiles to the northeast, the major fault zones of the Lone Star district strike north-south, east-northeast-west-southwest, and northwest-southeast. The north-south faults are poorly defined and appear to have had older left-lateral movement; they may possibly have offset the pluton(s) and Precambrian basement for thousands of feet in some cases. The northwest- southeast en echelon faults are the most pronounced features in the district. Although they were conceivably part of an older, regional, right-lateral system, gravity movement since, Miocene time characterized the displacements along most of these structures. Hiinge- and scissor-type slippage has been delineated along several of the faults. Basalts, tus, rhyolite, and agglomerates of Miocene to Late Pliocene age cap the Gila Mountains and attain thick- nesses of more than 3,000 ft (see Table 16.1). Preceding and contemporaneous with this volcanism, a pediment was devel- oping along the southwest Ganks of the Tertiary-Cretaceous volcanic belt. This pediment is principally composed of eroded propylitized volcanic debris cemented with clays and pyroclastic debris; it is covered with clay beds that thicken to the southwest and that crop out locally near the Gila River north of Safford. A younger pediment, developed on the clays and younger volcanics, is in turn, locally covered with recent basin fll, terrace gravels, and alluvium, OREBODY GEOLOGY ‘The surface geologic map in Figure 16.3 portrays the principal rock types, structure, and hydrothermal alteration associated with the ore and may be compared to the geologic ‘map of the 2,500-ft. level (Fig. 16.4), which is approximately 1,500 ft. below the surface. Below the surface to a depth of 800 ft. the ore is pipe-like in shape, partially leached and thoroughly oxidized. The ore pipe persists toa depth of 1,200 ft., but oxidation is accompanied by moderately enriched sulfide mineralization. Below the 2,900-f. elevation the hypogene ore expands rapidly, achieving a diameter of ap- proximately 3,000 ft. in a northwest-southeast direction, Rock Types Safford Metavoleanics. More than 75 percent of the ore at Dos Pobres occurs in the Safford metavolcanies, a meta- morphosed Cretaceous-Tertiary sequence. The bulk of the volcanic pile is andesitic in composition, but dacites, dacite tuffs, and latites have been recognized. Specifically, the ma- jority of the flows and breccias are hornblende or pyroxenecoos pepuntossp pus vopesye ape oUEKEY sei sa nas pst pereoouoe oyn popop pou oma pisap "i evens 7 fa nada Sa Panache y=340 JACKSON M. LaNGTON AND StpNEY A, Wittiams EXPLANATION peor mire, LE ay Scie ‘Alteration Facies Boundary —~ Percent Copper Contours ip Tey Corp, 1969-1875. Figure 18.4. Geologie map of 2,500- level Based on mapping by W. Bowen, R, Boatman, and J. Langton, Phelps Dodge “andesites that have been pervasively altered in the vicinity of the orebody. The fragmental nature of the flow breccias is often obscured by metamorphism or hydrothermal altera- tion, but it may be accentuated by crackling. Contact metam- orphism by the parental granodiorite has been clearly dated at 69.8 2.7 my. Productive Porphyries. Some of the higher-grade cop- per values occur in the dikes or phacoliths in the upper levels of the mine, but with depth the porphyries become progres- sively lower-grade and relatively barren. It is possible that 2 intrusions invaded the Safford metavolcanies between 47 and 58 my. ago, but sufficient information has not beenStructural, Petrological, and Mineralogical Controls for the Dos Pobres Orebody obtained in order to discuss them separately. It will suffice to state that the principal productive porphyry is generally a quartz monzonite, ranging in composition to tonalite or sranodiorite. Six drill holes have encountered an apparent stock below the 1,800-f. elevation in the northwest portion of the orebody (Fig. 16.5), although mapping on the 2,500-ft level suggests that many of the dikes are detached from this stock (see Fig. 16.4). Hornblende Andesite Dikes and Sills, Intrusions in the form of hornblende andesite dikes and sills are most obvious in the east-northeast-west-southwest shear zones away from the ore, and most of them are clearly consanguineous with the Baboon voleanics. Large titaniferous hornblende pheno- crysts, offen more than 1 em long, suggest that these non- productive intrusions were saturated with water. The dikes, which are evidently late-and post-mineral, acted as dilutents to the ore. Ore grade in their vicinity is invariably lower than in the core of the orebody, where no dikes or sills have been recognized. These intrusions are generally only a few feet thick in the Safford metavolcanics, but they may reach thick- nesses of more than 200 ft. in the lower Baboon sequence. Baboon Metavoleanies. The propylitized andesitic ag- glomerates, Low breccias, mud flows, and lithic tuffs of the Baboon metavoleanies crop out northeast, north, and north- ‘west ofthe orebody and thicken to more than 1,500 ft. north- westerly. The sequence has been hydrothermally altered locally, but has not been metamorphosed by either the pro ductive porphyries or the parental pluton(s). Propylitization appears to be autometamorphic away from the east- northeast-west-southwest shear zones, but is cleatly hydro- thermal toward the orebody. Lower members of these volcanics are intruded by the aforementioned hornblende andesite dikes of late- or post-mineral age, and the upper units contain large xenoliths of the same intrusions, with coronas that indicate the dike fragments were cooling with the flows. Structure ‘Two of the most important structures that infiuence the geometry of the orebody are the Foothill fault and the Dos Pobres anticline (see Fig. 16.3). It was initially thought that folding resulted from older lateral movement along the Foot- hill fault, but more recent evidence clearly suggests that the drag fold isa secondary feature related to the Valley and Red Dyke faults (see Fig. 16.3). A northwest-southeast eross sec- tion parallel to the Foothill fault, demonstrates fold control for the core (see Fig. 16.5). Low angle faults are present in the orebody, but the significance of these structures has yet to be determined. The strike varies from N4O°W to N6O°W; dips range between 10° and 40°NE; and the rake is typically NSO°E. Several east-northeast-west-southwest faults have had ‘considerable post-mineral displacement, but these structures Were the principal channels for productive porphyries and ore-bearing fluids, Bssentially contemporaneous with the ma- Jer down-throw of the Foothill fault, these veins had recur- Fent movement and down-faulted the ore in a step-like pattern from southeast to northwest (see Fig. 16.5). Crackle brecciation constitntes the dominant fracturing in the mine and is most extensive in the metavoleanies, not in the productive porphyries. All of the crackling or fract ing not related to post-mineral faulting appears to be hyd ‘thermal in origin. Simple parting across fragments and la phenocrysts, with virtually no displacement ofthe respect boundaries, is typical ofthe character of this fracturing ¢ is seen throughout the orebody. Contact breccias intimately associated with the porpi ries often host the highest-grade ore; these features are mn important in the upper portions of the deposit and must bi formed early during incrusion. Typically, the upper extre1 ties of dikes grade into the breccias, which ere character by numerous fragments of metavolcanics embedded in porphyry. A later event was the development of a megabrecc which was apparently related to the de-gassing of the prod tive rest-magma. This breceia incorporates huge fragments meta-andesite, productive porphyry, and contact breec The overall appearance of the megabreccia suggests “flo ing” blocks of the porphyry in a crackle breccia (see Fi 164 and 16.5). Alteration of Porphyry The productive porphyry at Dos Pobres is generally quartz monzonite by mode; however, the freshest samp seen tend to be granodioritic, as attested by phenocrysts embayed 8 quartz, plagioclase, hornblende, and dark brow biotite. The matrix carries 8 quartz, plagioclase, hornblent ‘quartz, and orthoclase. It seems likely that the porphyry w indeed a granodiorite originally, and that it was modi8 locelly and erratically by late magmatic effects, ‘The productive porphyry is generally seen in the form Gikes or fragments of dikes in the center of the oreboc These dikes have dated at 52.2 * 2.0 my. A more cohere stock of the porphyry, which has been dated at 47.8 & | m.y., occurs at depth in the northwest part of the deposit (¢ Fig. 16.5), and deep drilling here shows a gradual impov. ishment in copper values, accompanied by an increase ‘magnetite and the appearance of pyrrhotite. A downwa increase of grain size also has been observed in this drill ‘The earliest change to occur is the replacement of hor blende by biotite flakes, which appear identical in charact to the biotite phenocrysts, but which may also crystallize frilly rings or overgrowths on the larger books themselv« This alteration is surely of late magmatic age. Coarse prima biotite has been deformed by Howage, whereas this new bi tite has not. It is probable that, when this biotite alterati ‘vas taking place, the wall rocks were undergoing mesozon ‘metamorphism, With continued cooling, late magmatic biotite ceased form and a new assemblage began to crystallize: quartz orthoclase + magnetite ++ bornite. Quartz and orthocla grow in the matrix at the expense of plagioclase and Ia ‘magmatic biotite. The orthoclase thus formed is clear a1 generally non-perthitic. At this stage the rock seems qui normal, and one might not suspect any alteration, but t) ‘mode is that of quattz monzonite. This metamorphosis pro ably began as late magmatic but continued into the deutet stage, fr it is often fracture-controlled as well as pervasis Bornite is seen most often in fractures, with quartz and © thoclase; these veinlets have a distinctly hydrotherm‘se)04 ip Jo SuOBCO| HHL eOBUNS ey WOH CuIpUBOSEP SaUI eOReN ~3.CBN BUDO0} sDOq=L0 Se1G0d 80 84} Jo YONDOS SSOID “FBL ANBLS sourdjoneioy) poyeg ‘fuking onuoruoyy 2y0r6 ‘souueajonzyayy woodeg ‘soqeayon uiiunoyt BHO Jedd, ADOTOHLN 280g FROME PU TEINEZOH sp‘Structural, Petrological, and Mineralogical Controls for the Dos Pobres Orebody 34 aspect. This stage of alteration doubtless coincided with the main pulse of mineralization in the wall rocks and with the period of intense K-metasomatism seen in them. In most places this episode ended, as cooling continued, with simple deuteric alteration. Any biotite surviving, usu- ally the phenocrysts, was partially replaced by coarse clino- chlore and blebs of epidote with accessory rutile; the chlorite may be accompanied by minute platelets of hematite. Plagio- clase is altered mildly to shreddy sericite and some earthy epidote. Usually only the cores of phenoerysts are so aflicted, and sodic rims remain unchanged. Sulfides remained mobile in veins at this time, with chalcopyrite joining bornite in a gangue of quartz, carbonates, and chlorite. The larger miner- alized quartz veins (ca, 1 in.) seen in the mine are closely associated with porphyry dikes and die out away from them. Zeolites may also appear, and some samples have been seen With laumontite attacking plagioclase along the walls of zeo- lite-sulfide-calcite veins. In some places, however, the porphyry shows incipient alteration to a quarte-sericite assemblage. This alteration is of deuteric age and occurs in areas where more sulfur was available. While such alteration is seldom complete, the ten- dency is for groundmass quartz to grow to the point of coa- lescing, while all remaining feldspars and altered matites are partially replaced by sericite. Any chlorite that survives is highly magnesian, and even amesite may be present. Pyrite ‘may appear and bornite yields to chalcopyrite, These sulfides occur in quartz veinlets or may be disseminated in sites of former mafites. Alteration of this nature is uncommon and seldom complete, as is typical of low-sulfur porphyry copper systems elsewhere. The best example of such alteration is locally observed on the southeast side of the orebody. It is also in such an alteration assemblage that molybdenum reaches maximum values (0.005-0.015% MoS;) as shown in Figure 16.6, Molybdenum values are invariably less than 0.005 percent MoS) in the core of the orebody. Chemical analyses for the productive porphyry are pre- sented in Table 162. During the series of alteration steps from fresh to deuteric to new biotite, SiO, decreases, while Ti, Na, Al, and Fe increase; these changes are due in large measure to the appearance of abundant new biotite. The lack of important changes in KO reflects the loss of orthoclase uring biotite crystallization and implies no real K- ‘metasomatism within the intrusive. The large amounts of K,0 found introduced in the intrusive walls must have es- caped before late magmatic crystallization; otherwise, the in- trusive could not have remained so homogenous in this respect. Caleium, on the other hand, is a fugitive of deuteric and late magmatic age and is unique in its strong depen- dence for mobility on the abundance of species such 2s COs? and PO;*. The low sum of the second column in Table 16.2 reflects the lack of data for CO, Note the relatively similar analyses for the third and fourth colurans, with respect to Al, Fe, and K, and the great disparity into Ca values. The elements that show consider- able change are those whose mobility is closely tied to the presence of sulfur. Calcium is the best example, for it is ly removed when sulfur is available; elements such 2s Si and Al increase only because they are residual, and there is a corresponding decrease in the volume of the origint rock. The assemblage quartz-sericiteutile derives read from plagioclase-sphene in the presence of sulfur, and the loc of Ca from plagioclase is inevitably the major change. Alteration of Wall Rocks The history of events in the andesite pile that hosts th productive porphyries and most of the copper values ha been somewhat more complex. The pile exhibits an epizone ‘metamorphic (alteration) event of almost regional extent the is believed to be the composite effect of two processes, On process was undoubtedly the slow cooling of such a thick rapidly extruded pile that yielded an autometamorphism 0 “stewing” in the epizone. We suggest a slowly cooling hea source below as the second cause for the abnormally stron; epizonal effects in the volcanic rocks ofthe district, which ar in contrast to those effects in many other thick piles of mats voleanies. This source of heat must have been the granodior ite or parent pluton of batholithic dimensions (the Lone Sta: pluton) underlying the district Asa result of prolonged cooling, the andesites demon strate an alteration characterized by stability of epidote anc Pennine. Both minerals may replace mafic minerals com pletely as coarse-grained epidote prisms embedded in pen nine. Epidote singularly replaces plagioclase in part, and the surviving plagioclase is abitic in nature. Excess iron, derivee from mafic minerals and accessory magnetite, appears as tiny hematite tablets in situ. Although calcite is not abundant, its presence in the volcanics is commonplace, and it may form patchy erystalloblasts in the matrix. In contrast to the domi- hhant andesites in the pile, dacites responded somewhat differently: they were altered to an assemblage of quartz- sericite-caleite-pennine with epidote rare or absent. ‘The second alteration event, imposed on the voleanics in the aureole around the Dos Pobres deposit, was identical to the first and was due to rising temperatures that resulted from intrusion of the productive magma. Again epidote and pennine formed, often merely as continued development of the same earlier-formed minerals, but with exaggerated growth, Plagioclase may be totally destroyed, and clots or pods of coarse epidote, with interstitial calcite and pennine, spread crystalloblastically and invade the surrounding ma- trix. It has been observed that any nucleus might have initi- ated this process, such as a large plagioclase phenocryst or perhaps an especially reactive xenolith or merely a fracture tersection. Some clots do show epidote veinlets leading away in one or two directions, This early zone dies out away from the productive porphyry and merges insensibly into the ‘more regional propylitization of identical mineralogy. Effects cannot be seen with any certainty beyond about 2,000 ft from the periphery of the orebody. With continued rising in temperature and final emplace- ment of the productive magma, mesozonal metamorphism began. The earlicr assemblage vanishes and the andesites exhibit abundant secondary actinolitic hornblende and brown biotite, which has been dated at 56.9 2.2 my. Both ‘minerals occur as stall crystals that vigorously attack both relict plagioclase and hornblende. The new, actinolitic horn- blende is not Fe-rich, and disseminated dust-like magnetite1 Dos Pobres orebody Figure 16.6. Distribution of MoS; inthe upper lit of thStrvetural, Pevologeel, and Mineralogieal Controls forthe Dos Pobres Orebody TABLE 16.2 Chemical Analysis of Productive Porphyry in the Dos Pobres Orebody. Semple | Sanpe? | Sampo | Somme Femi] Poness? Deatiealy | "i | RRL? fren | eed” | setatasy | «fies, componene | rory | romiy | Sener |e Qvace $0, 64aas 695% S644 — Sone to, “OS” “G3 GIR Sa ahd, S69 ats 98S nr ne a & iB Meo os) is AAS Meo 356 43h Heo aaa ttt ase stetiitae vitae Wes 08s ahaa BR, a cosa aan ho BB fe Gos = Baz ggs, SE 3 Oar Bae gy 0+ 2.22 223 2.10 2.92 tel at NOTE: Analyses performed by A. Duncihorat of the Phalps Dodge Corporation, es have not been covtected for chlorine enteal to oxyen, isa common accessory in this assemblage, Ia many samples the disseminated magnetite is concentrated in hazily defined areas suggestive of the outlines of former cognate xenoliths, Early mesozonal metamorphism was merely a transient Stage, for as more K,0 was added during mesozonal condi- tions, the assemblage yielded to a metasomatic one. The most obvious result of this subtle change was the disappearance of actinolitic hornblende, while ever paler brown biotite contin- ued to crystallize. Ultimately the andesite may consist of some 30 percent by volume of biotite, with tiny crystals scattered evenly in the matrix and more sparingly in pheno- crysts. The associated disseminated magnetite is accom- panied by bornite, minor chalcopyrite, apatite, rutile, and, cccasionally, granular orthoclase. This alteration represents the main pulse of K-metasomatism and mineralization, and, where most intense, it may affect even the productive por. phyry dikes. As an end result, these dikes may be so heavily replaced by secondary biotite that they are indistinguishable from the andesites, except for the ghost of biotite pheno- ‘erysts, The effect of this strong K-metasomatism is well illus- trated by @ comparison of Figures 16.7 and 16.8, which suggests enrichment in KO and a neutral behavior of SiO. Free silica seen in the zone is evidently locally derived from other minerals Crackling appears to have been an important mechanism ing the mesozonal K-metasomatism, while it was rela- tively unimportant during the preceding mesozonal metam- omphism, The wall rocks were laced with fractures that are now veinlets carrying quartz, orthoclase, apatite, bornite, and chalcopyrite, The bornite: chaleopyrite ratio decreases Outward in the mesozonal core; throughout this zone the copper content averages 0.83 percent, while the total content of sulfides is 3 percent by weight. These veinlets probably carry the bulk of the deposit’s precious metal content; distri- bution maps for silver and gold in the Dos Pobres orsbody are shown in Figures 16.9 and 16.10, respectively. Both gold and silver show highest values in the central zone of orebody and both show @ relation to bornite distribu! Studies of polished sections reveal minute, smooth, cor blebs ofsylvanite and hessite in the bornite. They seem t centrally located with bornite masses, shunning the bot that is intimately intergrown with chalcopyrite, ‘The biotite zone may be seen up to 1,600 ft. from center of the orebody; then it gradually fades and merges the surrounding propylitic assemblage. Toward the o Parts of the zone biotite becomes notably paler and ass 2 green color. The effect is frst shown by biotite former the expense of plagioclase, whilst biotite developed in ‘matrix is still brown; but eventually this, too, assumes a gr color. Chemical analyses of meta-andesites from the core, tt ition, and outer zones (Table 16,3) reflect a clear oss of C in the interior with an enrichment of K;0. In the zone of percent Cu, KO averages 2.09 percent; in the range of © 0.0.59 percent Cu, K,O averages 2.29 percent; and in the percent zone, K,O averages 2.41 percent. These values for the 1,500-to 1,800-ft. elevations and are relatively hig for KO at higher elevations for comparable grades of cop (Gee Fig. 16.7). As the thermal gradients about the product Stock collapsed, retrograde alteration commenced and other principal stage of metallization evolved. The result this new mineralization was further enrichment of init copper values. {In those portions of the wall rocks whick show biotit: tion but which are not fully purged of CaO, epidote reappe in biotite and in remnants of plagioclase. Biotite show: tendency to alter to clinochlore, in contrast to the me Ferich pennines of earlier propylitic assemblages. Thx effects are only slight to moderate in the biotite zone if t rock mass is devoid of fractures, but the effects are strong fractures and veins; some of these are clearly reused veins ‘mesozonal age and others are apparently newly formed this time, ‘The veins often carry quartz and important amounts both chalcopyrite and bornite, Pyrite is rare, but in veins ri in sulfur, it may occur with chalcopyrite. Sericite is apt form a selvage at the expense of biotite and feldspar rex nants, More typically, however, bornite occurs with chi copyrite, montmorillonite and a myriad of zeolites. Stilbi laumontite, heulandite, and analcite are most commonly 1 ported. Traces of other minerals have also been observed, a1 these include barite, fluorite, pumpellyite, and thuringite. is important to note that these retrograde veins abound in t metasomatic biotite zone but die out, and are rare in beyond the propylitic zone. As noted previously, howeve these veins do extend into the productive porphyry itse although they are less common there than in its immedia walls. PETROGENESIS Considering all available facts from exploratory dri holes and geologic mapping, we propose an orthotect: model for the metavoleanics and an orthomagmatic mods for the orebody at Dos Pobres, Although radiometric dat«EXPLANATION % |~040%-Perceat copper isapach contours (2500-3000 fvels) % 230 |—s.co—Fecent_ K 20 Isopoch contours (2500-3000 levels) % ac 373 Percent KO composia dota point \ etl; Cane? eal inter Contour terval #0.20°% Keo Figure 167. Distribution of K,0 in the upper lit of the Dos Pobres orebody [346]sos gor EXPLANATION F-0.40%—-Fercent copper isopach contours (2500-3000 levels) f-o1wo— O2/ten god izopach eonteurs(2500-3000 levels) 0032 Ox/ten gold compost data pat Seale; Sem BPP nt fH Ee metre Figure 16.10. Gold dstibution Inthe upper tit of the Des Pobres orabedy B49]350 Jackson M. LANGTON AND SIDNEY A. WILLIAMS TABLE 163 Average Chemieal Analysis of MetaAndesites, at the Dos Pobres Orebody Biotitized — Biotitepidote Outer Prop Core Zone Transition Zone Aureole Zone Component (40.50% Ca) _(020-0.59% Cu) _(100-2,000 ppm Cup SiO) 583% 35.4% 54.0% Als 180 204 113 Fey03° 45 49 60 x0 256 5.76 142 MgO. 192 335 1a. Naz0 20 332 3.46 K30 307 250 202 “Total ron reported 8 Fog03 are too few to establish firmly the sequence of events, dates that have been obtained and correlated with discernible field relationships provide convincing evidence for establishing a relatively simple geochronology (Table 16.4). ‘The previously discussed Precambrian xenoliths and the rill-hole intercept of an amphibolite derived from Precam- brian(?) sediments furnish the best evidence that Late Cret ceous to Paleocene magma(s) of intermediate composition TABLE, penetrated the crystalline basement and extruded andesitic lavas on a Precambrian surface. Farther northwest along the Gila Mountain front, however, Middle Tertiary volcanics rest on Paleozoic limestones and occasionally contain rafted blocks of cherty limestone. These phenomena suggest exten- sive uplift and subsequent erosion which cut through and removed the Paleozoic rocks and exposed the Precambrian basement in the vicinity of the orebody during Mesozoic time. ‘The parental magma continued rising until it passively intruded its thick andesitic pile and crystallized during Late Cretaceous to Early Paleocene time. The pluton was con- trolled by north- and northeast-striking shear zones. A broad contact metamorphic aureole that developed around the plu- ton rendered the Safford volcanic pile into hornfelsic ande- sites, which vary from an inward amphibolite facies to an outward albite-actinolite-chlorite-epidote facies. Much of the ambiguous, widespread propylitization in the Safford Meta- ‘volcanics can be attributed to the quartz diorite-granodiorite pluton or to simple autometamorphism, and it is entirely possible that most of the metavoleanics overlie a single, faulted, tonalitic batholith. An interesting explanation for the 164 Geochronology of Major Geologie vents in the Lone Star Mining District ‘Order of Geologie Events ‘Geologie Age Dates Gay) 1. Opi, fauting, erosion Mezorole = 2. Ingusion of Lone Star magma(a into Precambrian metas os and subsequent contact metamorphism ‘Upper Cretaceous rae ixtrusion of Safford voleanies eens ys ~ 602 4. xtrason of Salford vol Boer cre 102-60 4, Intrusion of Lone Star magials) inte Safford volcanic and Upper Cretaceour~ ono #beequent contact metamorphism Paleocene : 5. Crytaliztion of Lone Star pluton) Unger Cetacons- ont 60s 6, Upht, faulting, northeast folding, erosion, deposition of ‘volcaniclastic sediments peenres, oo 1. Intrusion of productive magmas) Raleccene-Rocene 92-472 8. Ey pave meron eonse metorphien nhytbermal yer Ease ace 9. Crystaiation of productive porphyry dikes Lowe: Bocene sant 20 Uplift, faulting, minor folding, continued volcanism Lowe: Bocsne - De-gasing and subsequent crystallization of productive rest * ‘magma(s) with accompanying hydrothermal phase a ea 12, Intsusion of hornblende andesite magma() Middle Bocene 414-368 13. Extasion of Lower Baboon voleaes and pyrocasties Mie Eocene oe 46 14. Late, pattie etroptade ening Middle Eocene 46 15. Extrusion of Upper Baboon agglomerates Upper Eocene 452~36 16. ‘ats, faulting, minor Folding and ting Upper Bocene-Lower a a eee ae Oligocene 17, Incisionextzusion of Gila Mountain Voleancx contemporaneous ieee ‘with development of older pediment eee eee 7 18, Major Basin and Rags ayn, ioe ing 80m ARE age Pcs : 19, Baste volcanism Late Pocene # 20. Younger pediment bain fl, and gravel development Pestocene-Recent fle Kar a performed by Geochron Labs of Krasger Enterprise Inezall other ater” ate merely inferred rom‘Structural, Petrological, and Mineralogical Controls for the Dos Pobres Orebody 3 proposed stress in the southwest portion of the Morenci- Metcalf district is northeast-southwest dilation resulting from emplacement of this speculated, northwest-trending batholith in the Precambrian basement (Langton, 1973). Subsequent to crystallization in the upper reaches of the pluton, a drag fold developed in the Safford Metavolcanics along the N60 to 70°W, en echelon Red Dyke, Valley, and Foothill faults (see Fig, 16.2). This type of structural pattern, with different orientation, has also been recognized in the vicinity of the North Newman, Bell Copper, South Newman, and Granisle porphyry deposits in British Columbia (Carson and Jambor, 1974), The axial plane of the fold at the Dos Pobres deposit strikes N35 to 40°E, and this secondary struc- ture appears to be the major component for localizing the orebody. Although the productive tonalite-quartz monzonite~ granodiorite porphyry dikes are genetically related to the productive stock and parental pluton, itis doubtful that the productive stocks had an extrusive kindred. Mild folding continued during intrusion and crystallization of the produc- tive dikes and sills, and distribution of the porphyties throughout the Dos Pobres orebody (sce Fig. 16.5) provides evidence of this phenomenon. During this time of folding, the first copper protore was formed at Dos Pobres and was evenly disseminated in the porphyries and adjacent meta- andesites. Contemporaneous with, and subsequent to, the final crystallization of the deeper portion of the productive stock, the Baboon volcanics were derived from homblende andesite magmas that spread over portions ofthe district and covered the embryonic porphyry copper cell. The consan- guinity of the hornblende andesite dikes and sills with the Baboon agglomerates and flow breccias may be easily demon- strated in the field or in drill hole samples. The oldest mem- bers of the Baboon flows occasionally contain sub-angular to rounded fragments of the parental pluton, productive por- Phyries, and biotitized Saford metavolcanics, whereas the upper members contain large xenoliths of the hornblende andesite intrusives. ‘The first stages of copper mineralization were complete by the time of extrusion of the Baboon voleanies, The addi- tional maturation at the Dos Pobres deposit, culminating in a late period of copper enrichement by virtue of veining, resulted from de-gassing during the middle megabreccia stage. Rejuvenated movement along the east-northeast- southwest shear zones apparently facilitated alization. The Baboon volcanics alone probably sufliced as a relatively impermeable cap that controlled the rate of de- gassing during retrograde alteration and mineralization. POST-ORE EVENTS Arguments can be made for tilting and low-angle fault- ing in the Lone Star mining district, especially at the Dos Pobres deposit. However, any significant tilting that did oc- cur must necessarily have preceded the Miocene extrusive period, as these younger voleanics have an average dip of approximately 12°NE near the orebody. Until further infor- mation is obtained, it must be assumed that the Dos Pobres, orebody has been tilted between 12 and 25°NE. Subsequent to tilting, oxidation and erosion were dominant forces at work during Oligocene and early Mioce times. Also at this time minor supergene enrichment w superimposed on the hypogene ore in the Dos Pobres depot ‘The central portion of the Dos Pobres chaleopyrite-bomn ore pipe was partially leached, throughly oxidized, and cally enriched to depths of approximately 1,200 fe. (2,900. level. Sulfides in the petiphery of the marginal zone and the pyritic aureole, however, are often within 300 ft, of t surface on the southeast side ofthe orebody. Chrysocclla a! cuprite are the dominant copper oxides for depths of 1,0 ft, over the center ofthe sulfide ore, but subordinate amour of tenorite and brochantite have been recognized. Nati copper, chaleocite, and covellite are abundant in the mix oxide-sulfide zone between the 2,900- and 3,300-ft. elev tions. Oxide ore averages 0.62 percent Cu, compared to 0: percent for the sulfide ores. Hematite, jarosite, and limoni capping on the southeast side of the orebody also reflec minor chaleocite enrichment in the vicinity of the producti porphyries. Erosion appears to have been more extensive southea of the Dos Pobres orebody. The Baboon volcanics are m present 4 miles southeast of the deposit, but they thicken at least 1,500 ft. northwest of the orebody. Low-angle faulting has been recognized at the Dc Pobres orebody, but itis most difficult to trace the structun, for any distance along strike. This faulting apparent preceded or was contemporaneous with the early stages « Miocene volcanism. As previously mentioned, the signit ‘cance of these faults is too speculative to pursue in th chapter. ‘The Oligocene-Pliocene Gila Mountain Volcanies wer extruded on an erosional surface that had exposed all of th Laramie intrusives and consanguineous metavoleanies. Th source of these volcanics was to the northeast along Bonit ‘Creek, and this arcuate voleanic chain may be mapped in th Peloncillo Mountains as far southeast as Stein's Pass, Net Mexico. Contemporaneous with this volcanism, a pedimer was forming along the southwest front of the Gila Mour tains, and the gravels derived from it thicken rapidly towan. the center of the Safford Valley. Basin and Range block faulting represented the last me Jor tectonic event in the district. The northwest-southess faults were particularly active, and gravity displacements i excess of 2,000 ft. have been recognized on several of th high-angle structures. Additional adjustments on north south and northeast-southwest faults also occurred, but ap parently they were not of the magnitude of those in th Foothill, Red Dyke, Valley and Butte faults, District tiltin, of at least 12°NE can be justified during these adjustments Finally erosion and oxidation of the orebody and develop ‘ment of extensive thicknesses of clay beds, basin fill, terrae gravels, and alluvium during Pliocene and Recent period established the environment as it now appears. ACKNOWLEDGMENTS We are grateful to Phelps Dodge Corporation for per ‘mission to publish this esearch and especially for the oppor352 Jackson M, LANGTON AND SIDNEY A. WILLIAMS tunity to pursue the study to completion. On a project of such magnitude, numerous people are naturally involved, and we have benefited from prior studies by the following Phelps Dodge geologists: R. W. Ludden, R. E. Geer, and N. J. Theis. OF particular assistance has been the prior work of, and discussion with, R. L. Boatman. During early stages of map- ping R. T. Moolick and J. J. Durek were especially helpful, and editorial assistance was obtained from K. C. Bennett and E. M, Schern during preparation of the manuscript REFERENCES CITED ‘Camus, Francisco, 1975, Geology of the El Teniente orebody with ‘omphasis on wallrock alteration: Eeon, Geol, v.70, p. 1341— 1372, Carson, D. J."T., and Jambor, J. L., 1974, Mineralogy, zonal rela~ tionships and economic significance of hydrothermal alteration ‘at porphyry copper depasits, Babine Lake area, British Colum- bia: Can, Min. and Met. Bulletin, Feb. 1974, 24 p, Fountain, R.J. 1972, Geological relationships in the Panguna por- ‘phyry copper deposit, Bougainville Island, New Guinea: Econ. Geol, v.61, p. 1049-1068. Gustafson, L. B, and Hunt, J. P., 1975, The porphyry copper deposit at Ej Salvador, Chile: Econ. Geol, v. 70, p. 857-912, Hollister, V. F., 1973, Regional characterises of porphyry copper ‘deposits of South America: Min. Eng., Aug. p. 51-56. Langton, J. M., 1973, Ore genesis in the Morenci-Metcalf district ‘SME Trans, v. 254, p. 247-257, Robinson, R. F, and Cook, Annan, 1966, The Sefford copper dis- trict, Lone Star mining district, Graham County, Arizona: in Titley, 8, R, and Hioks, C. L, eds., Geology of the Porphyry Copper Deposits, Southwestern North America: Tucson, Univ. Ariz. Press, p. 251-266, Saegart, W. E,, and Lewis, D. E, 1976, Characteristics of Philippine porphyry copper deposits and summary of current production and reserves: SME Preprint, 761-79, 47 p.Geology of the Christmas Porphyry Copper Deposit GILA COUNTY, ARIZONA Randolph A. Koski and David S. Cook The Christmas deposit, part of the major porphyry copper province of southeastern Arizona, is located in a steep-sided canyon at the southeast end of the Dripping Spring Moun- tains in southern Gila County. The closest major porphyry copper deposit is at Ray, approximately 27 km to the north ‘west. The nearest communities, Winkelman and Hayden, are 8 km to the south, and Globe is 37 km to the north, The mine is accessible by paved secondary road from State Highway 77, which follows the Gila River canyon north of Winkel- man, Most of the open-pit mine and support facilities at Christmas are located in the west-central part of the Christ- mas 7.5-minute quadrangle, but the total area discussed in this study is in the Christmas and Hayden quadrangles (Fig, 1). ‘The colorful, copper-bearing skams cropping out at the surface in an isolated canyon along the Gila River presented an inviting target for early prospectors. The first mining ‘activity took place in the early 1800s, but territorial land use disputes prevented any substantial development until the en- ing G. B. Chittendon staked the property for the Sad- Bs 1902, the day for which the property was named, Under ground mining activity by a succession of small and short- lived companies was intermittent during the early 1900s, largely due to unstable economic conditions, low copper prices, lack of sufficient working capital, and geographic iso- lation. After the depression, produetion stabilized with the shipment of high-lime fuxing ore to the nearby Asarco smelter at Hayden. Ore mined through 1940 came mainly from replacement beds in the Naco Limestone above the 800-8. mine level. During World War II the U.S. Bureau of Mines and the US. Geological Survey conducted detailed studies of the skarn orebodies. Deep drilling — below the 800-ft. level— (353) revealed extensive ore horizons in the Escabrosa and Marti limestones. Development of deeper levels, however, did no begin until the property was purchased by the Inspiratio: ‘Consolidated Copper Company in 1955. Additional explora tion by Inspiration confirmed the presence of significant or reserves at depth, particularly in the rich “O’Carroll bed” a the base of the Martin Limestone. Underground working were extended to the 1,600-f. level by 1962. Inspiration be gan surface mining above the site of the old undergroum ‘workings in 1965, and shortly afterward underground opera tions were terminated; by 1981, all production came from a elongate open pit centered on the Naco Limestone-Christma stock contact. From the eatly 1900s through 1966 underground minin: of the skarn orebodies at Christmas produced 4.6 millio: tons of ore yielding 144.5 million pounds of copper. The oper pit produced 17.7 million tons of ore and 184.0 million pounds of copper in the period 1966-1979, Small amounts ¢ ‘g0l6, silver, and selenium were also recovered. In early 1981 production averaged 6,000 tons per day with a stripping rati: of 3.25:1. The open-pit ore, a mixture of 95 percent sedimen tary and 5 percent intrusive rock, averaged 0.70 percent Cv Copper concentrates milled at Christmas were trucked t Inspiration’s smelter in Miami, Arizona. ‘The Inspiration Consolidated Copper Company Annus Report for 1980 listed reserves totalling 701 million pound ‘of copper, 80 percent of which remained unmined undet ground, Inspiration also announced (Annual Report, 1974 p. 6) the discovery of a “large low-grade ore body” locate: “close tothe present Christmas open pit mine.” The prineipe host rocks are intrusive and mafic volcanic rocks east of th Christmas-Joker fault system. ‘The geology, ore deposits, and mining activity of th Ray-Christmas region were first reported by Ransome (1915354 RaNbotpst A. Koski aNp Davin 8. Cook Quoternory and Teriory sedimentary racks Tertiary volcanic rocks Tertiary one Cretaceous invrusive rocks EXYST] Cretaceous volcanic ond Secimentory rocks Poleozeie sedimentary rocks Precambrion rocks ° Normel Feutt sseoo'00" Ea a oe HAYOEN QUADRANGLE CHRISTMAS QUADRANGLE nee farzon 34% 3g km = sH0* 4am af visfalnan fom, 32" oo “fe Figure 17.1. Generalied regional geology near Christmas. Geology ofthe Hayden quadrangle ftom Banks and Krieger (4977); géciogy of the Chistmas quadrangle from Willden (1964) 1923) and Ross (1925). A mapping program conducted by the U.S. Geological Survey in the Ray-Winkelman-San Man- ‘uel area provides a regional geologic framework. Willden (1964) mapped the 15-minute Christmas quadrangle, which includes the Christmas mine and the contiguous Saddle ‘Mountain mining district to the southeast. Near Christmas several 7.5-minute quadrangles have been mapped, including. Hayden (Banks and Krieger, 1977), El Capitan (Cornwall and Krieger, 1978), Sonora (Cornwall ct al, 1971), Winkel- rman (Krieger, 1974), and Saddle Mountain (Krieger, 1968), In a detailed field study of the Saddle Mountain mining district, Barrett (1972) established alteration and sulfide min- cexalization patterns along Laramide dikes intruding Creta- ceous volcanic rocks. The Christmas copper deposit has been described in published reports by Peterson and Swanson (1956), Bastlick (1968), and Perry (1969), and in an unpub- lished thesis by McCurry (1971). These studies have empha- sized aspects of mineralization in carbonate wall rocks. Much additional information on the Christmas deposit exists in the form of unpublished maps and reports prepared by the gco- logic staff ofthe Inspiration Consolidated Copper Company. REGIONAL GEOLOGY ‘The Christmas mine occurs in a zone of topographic transition within the Mountain sub-province ofthe Basin and Range physiographic province (Ransome, 1923). To the west and north upraised Precambrian and Paleozoic strata form the sharply etched Dripping Spring and Mescal ranges, ‘whereas rolling, subdued topography is characteristic of the terrane developed on overlapping Cretaceous volcanic rocks to the east, south, and southeast. The narrow Gila River canyon is cut perpendicular to the northwest-trending axes of the Dripping Spring and Mescal Mountains and the inter- vening Dripping Spring Wash. Elevations in the two quac- rangles shown in Figure 17.1 range from 1,850 ft. (560 m) at the Gila River to 4,700 ft. (1,430 m) along the crest of the Dripping Spring Mountains. ‘A. composite geologic section for the region is shown diagrammatically in Figure 17.2, Neat Christmas only Penn- sylvanian and younger rocks are present at the surface; hence, older rocks are treated here briefly. The Precambrian core of the Dripping Spring Mountains and adjacent ranges is composed of the highly deformed Pinal Schist and plutons of batholithic proportions, principally the Ruin Granite. Conglomerate, shale, quartzite, limestone, and basalt Bows ‘belonging to the younger Precambrian Apache Group, and the Troy Quartzite unconformably overlie the crystalline basement rocks. Diabase, the youngest rock type of Precam- brian age, intrudes all of the previously mentioned rocks, ‘commonly occurring as sills dilating the Apache Group ot as tabular masses in the Ruin Granite ‘A. depositional hiatus of approximately 500 m.y. sepa- rates Precambrian rocks from the largely conformable se- ‘quence of Paleozoic limestone, dolomite, and sandstone, East of Christmas, Paleozoie rocks are overlain by shallow-water marine sedimentary rocks of the Pinkard Formation, Plant and invertebrate fossils are tentatively assigned an early Late ‘Cretaceous age (Ross, 1925; Hayes, 1970). A diamond drill hole located on the Gila River 1.5 km east of the Christmas| | Williamson Canyon Volcanics Tertiary sedimentary rocks / Tertiary volcanic rocks Upper (faa * * Pinkdrd Formation __|) 0-600m Cretaceous {| “xx 75 ET} 0-345 Pennsylvanian Mississippian 360-610m Upper Devonian Upper ané wmiadle Cambrian (pase eee 0-100m Troy Quarizite 300m Precambrian ae Late Cretaceous intrusive rocks Early Tertiary intrusive rocks Figure 17.2. Diagrammatic geologic section for the region around Christmas mine intersected only 12 m of conglomerate above the Naco Limestone, and Pinkard-equivalent sedimentary rocks appear to be absent within, and west of, the Christ- ‘mas open pit. ‘The Pinkard Formation or, where the Pinkard is absent, the Naco Limestone is overlain by the Williamson Canyon Voleanics, a thick vent- or cone-complex-facies accumulation of basaltic flows and volcanic breccia with subordinate gray- wacke and siltstone. Covering approximately 230 km?, the voleanic sequence ranges in thickness between 750 to 950 m in the Klondyke area (Simons, 1964) and 450 to 600 m where downfaulted at Christmas, but it thins rapidly westward from the Christmas mine. K-Ar ages presented in this report in cate a minimum age for the Williamson Canyon Voleanics of 75 to 80 my. before present. This transition from shallow marine sedimentation to subserial(?) volcanism in Late ‘Cretaceous time is recognized in many areas of southeastern Arizona (Hayes, 1970), and such successions are spatially correlative on a broad regional scale with porphyry copper deposits (Titley, 1972). The post-Laramide rocks shown in Figures 17.1 and 17.2 consist largely of Tertiary basalt-ande- site-rhyolite sequences, Miocene and younger basin-iling alluvial and lacustrine deposits, and alluvium deposited along the Gila River drain, Precambrian and Paleozoic strata in the Dripping Spring Mountains are folded into @ northwest-trending anticline plunging gently to the southeast (Eastlick, 1968; Banks and Krieger, 1977). The Dripping Spring Mountains arch appar- cntly evolved during a period of Laramide compression with ‘maximum stress along an east-west to northeast-southwest axis (Banks and Krieger, 1977; Rehrig and Heidrick, 1972, 1976). Differential uplift and northwest-directed tensional stress resulted in a system of east- to northeast-trending frac- tures, These extensional structures served as avenues for em- placement of Cretaceous and Paleocene cale-alkaline intrusions, several of which are spatially associated with por- phyry-type copper mineralization. The development of thick Miocene valley-fill deposits indicates a shift from Laramide to basin-and-range tectonics by middle Tertiary time. Although Banks and Krieger (1977) cite evidence for Precambrian, Laramide, and post-Laramide movernent along normal range-front faults in the Dripping Spring Mountains, modern basin-and-range physiography in the region reflects, in large part, post-middle Tertiary block faulting. GEOLOGY OF THE CHRISTMAS MINE AREA ‘The gently tilted, upper Paleozoic Naco Limestone and the overlying, westward-thinning Williamson Canyon Vol- canics of Cretaceous age are intruded by numerous Lara- mide stocks, sills, and dikes ranging in composition from hornblende andesite porphyry to quartz latite porphyry (Fig. 17.3). The unconformity between limestone and volcanic rocks is occupied in most places by a 5-to-15-m-thick sill of hornblende andesite porphyry. Offsets along high-angle nor- ral faults in the northwest-trending Christmas-Joker fault system combine to downdrop the Williamson Canyon Vol- canics nearly 1 km into juxtaposition with the Naco Lime- stone within the open pit and along the front of the Dripping Spring range, northwest of Christmas (see eross section, Fig, 17.3). Approximately 25 percent of the map area is covered by surficial deposits. Stratified, partly consolidated gravel of Dripping Spring Wash overlies bedrock north of the mine area. On gentle slopes a thin veneer of volcanic rubble thick- ‘ens toward, and merges with, alluvial deposits in the major drainages. Man-made overburden includes mine dumps, tail- ings ponds, and road fill. Naco Limestone ‘The oldest rock unit exposed at the surface in the mine area, the Naco Limestone, is characterized by thin to me~ dium beds of fossiliferous cherty gray limestone and thin but persistent interbeds of finely laminated calcareous shale and356 RANDOLPH A. Koskr AND Davin §. Cook siltstone. Elongate nodules and discontinuous layers of gray, black, and red chert help to define bedding planes where beds are massive. Strata generally strike northeast to east-west and dip 12 to 25° to the southeast or south. Locally, however, minor flexures and drag induced by faulting and small-scale parasitic folding have resulted in steeper dips. Detailed li- thologic and paleontologic descriptions of the Naco Lime- stone in the southern Dripping Spring Mountains can be found in Reid (1966) and Banks and Krieger (1977). Sections of the Naco Limestone measured by previous workers along the prominent cliffs 1 to 1.5 km northwest of the mine range from 260 to 330 m. Assuming a thickness of 300 m for the highly altered Pennsylvanian limestone in the ‘ore deposit would place the contact between the Naco Lime- stone and the underlying Escabrosa Limestone at approxi ‘mately 150 m below the pit bottom in early 1980. Within the metamorphic aureole adjacent to the Christ- ‘mas stock, relatively pure limestone beds in the Naco are recrystallized to white marble or converted to andradite ‘exoskarn; shale and siltstone are thermally metamorphosed to diopsidic hornfels. Garnetization of favorable beds extends northwest in the footwall of the Christmas fault fora distance of 750 to 775 m from the Christmas stock. Individual orebodies in the Naco are typically thin- bedded replacements of limestone, 0.5 to 18 m thick, sand- wiched between layers of hornfels and granodioritic sills (Perry, 1969). The principal hypogene sulfide minerals in Naco skarn are chalcopyrite, bornite, pyrite, and sphalerite, with lesser amounts of molybdenite and galena; magnetite is often abundant in garnet-sulfide-rich zones near the intrusive contact. For details of skarn mineralogy and genesis the reader should consult previous publications by Eastlick (1968) and Perry (1969). Williamson Canyon Volcanies The Williamson Canyon Volcanics is a monotonous, westward-thinning sequence of dark gray to greenish gray basaltic volcanic breccia and flows and subordinate clastic Ht GEOLOGY OF THE = 3 CHRISTMAS MINE AREAsedimentary rocks. The voleanie pile is 450 to 600 m thick east of the Joker fault and 250 to 350m thick along the ridge south of the mine, but it wedges out due to erosion 1.5 km ‘west of the Christmas open pit. Although the details of an internal stratigraphy are ob- scured by alteration and poor exposure, pyroclastic rocks appear to be more abundant than lava flows in the voleanic section at Christmas. Thoroughly indurated pyroclastic rocks are generally poorly sorted, unstratified lapili-tuff' and tuff-breceia. Sub-angular to sub-rounded blocks and lapilli, mostly of accessory volcanic origin, are enclosed in a crystal- rich tulfaceous matrix. Typically, the fragments have por- phyritic or pilotaxitictextares in which 2-mm-long subhedral calcic plagioclase, rounded equant grains and cumulophyric clusters of clinopyroxene (or uralitic amphibole), and granu- Jar magnetite are embedded in an intergranular or isotropic brown to black glassy matris. Fragments with diabasic tex- tures are common. Brown hornblende is a frequent constt- uuent of rock fragments and also occurs as corroded and cembayed crystal fraginents, occasionally with opacitic rims. Basalt flows are generally holocrystalline rocks with par- phiyritic textures. Phenocrysis are well formed and consist Geology of the Christmas Porphyry Copper Deposit. 3 largely of rectangular to blocky 1- to 3-mm grains of labs dorite and equant grains and glomeroporphyritic agarega of pale yellow augite set into an intergranular matrix randomly oriented calcic plagioclase laths (0.1-0.2 mm), terstitial monoclinic pyroxene, and magnetite grant Plagioclase exhibits normal to oscillatory zoning betwe core (Ansy.m2) and rim (Ang: 4s). Some samples contain 01 lines of olivine phenocrysts which have decomposed to agg gates of chlorite.quartz-epidote-sphene or mixtures epidote, hematite, and smectite. Vesicular horizons sugg tive of flow tops or bottoms are not prevalent near Christin Locally, however, circular to irregular cavities and gashes made conspicuous by amygdules of epidote, chlorite, act lite, calcite, or zeolite (laumontite). Beyond the halo of s: ondary biotite, the least altered samples of basalt cont: ‘weakly saussuritized plagioclase and partially chloritized a epidotized pyroxene, ‘According to chemical analyses (Table 17.1), the me voleanic rocks are quartz-normative, high-alumina (A1;03 17 percent, sub-alkeline basalt, with compositions that p in the cale-alkaline field of an AFM diagram (Fig. 17.42) defined by Irvine and Baragar (1971). The compositions a CROSS SECTION A-A’ ————— 3000 SEDMENTARY AND VOLCANIC ROCKS Momace suri «he "sme ond rool 41; tallns ponds | Sie posts 5) Willamson Canyon Voters Nema fou, doshos wna 1, epteowe oct, dvted where coneaed INTRUSIVE ROCKS fp, petoeene sorry Chrsias ive Complex elo perry ob te pray (ates) oy emntende ehyodacite porghyry he, temntlence ondece sorry 19 ae IZ sanplalocaons conoeeind downtown side Figure 17, Geologie mp (of) and cross section (above for tho Chvistmas mine area