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 probable 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 inthe 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 see- ‘ondary assemblage can, therefore, be used as one basis for interpretation ofthe nature ofthe 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 geo- chemistry, ore textures, and geologic inferences—may be used to predict the copper grade and sulfide 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 of the 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 (pO;), as shown in Figure 12.1 Role of Oxygen ‘The highest pO, obtained in nature is that of air, i., atmospheric p03. Oxidation potentials approaching this value ate 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 ( oxidation potentiot | LeseN P02 (otmospheres | ——> Figure 12.1. Diagram showing stability ranges of capper and iron com- Pounds with respect to oxidation potential and pH Stability of Sulfide Minerals ‘Changes in the oxidation potential (p03) ofa system are accompanied by changes in the stability of sulfide minerals (Gee Fig. 12:1. Sulides are stable in reducing environments, bbut they liberate metal and sulfate ions in oxidizing environ. ments. Figure 12,2 shows the effects of oxidation in high- and low-sulfide environments. Most ofthe 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) are precipitated as hydroxides, oxides, carbonates, sulfates, oF 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 suilides (chaleocite and covellite) form in the zone of reduction below the groundwater table (sce Figs 12.1, 12.2), but they also form in local reducing environ- ments that persist in the zone of capillary water above the water table (Fig, 12.20), Influence of Climate Climatic conditions infiuence 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 arid conditions are favorable for deep oxida- tion but do not promote rapid leaching and enrichment be- cause of the deficiency of recharge water. Oxidation 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 {actor in the effectiveness of enrichment 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 (see Fig. 12.28) or first-eycle oxidation without Jeaching and enrichment (see Fig. 12.2F) continues until the primary sulfides exposed to oxidizing environments above an established water table are completely oxidized. Second-cycle oxidation (see Figs. 12.2C, 12.2G) is initi- ated by a relative lowering of the groundwater table, which exposes additional sulfides to 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- ond-eycle oxidation attacks primary sulfides and frstcycle ‘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 commonly produce a zone of overlap between the first- and second-cycle chalcocite blankets. Second-cycle oxidation stops when oxidation of sulfides is complete above the new groundwater table. Repeated cycles of oxidation, leaching, and enrichment in porphyry copper deposits (related to repeated adjustments in the water table) produce increases in the copper content of successive enrichment zones (compare Figs. 12.28,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 ofthis chalco- site blanket produces in situ oxide ore (erosshatch pattern in Figs. 12.2C.D). This type of oxide ore commonly overliesonicinat. oeFostr HT eYELE oxioeTION LEACHING SUBSEQUENT OXIOATION -LEAcHING ‘OF CHALEOCITE BLANKET 1m situ oxioarion fF CuaLcoctre BLANKET cuauconynite, Onaimat C€PosIT 1 cYcur oxioariON reansivions TO PYRITE RATIO SUBSEQUENT OXIDATION SUBSEQUENT Ox1oKTION EXPLANATION CED) ce orate Pen LIne, scone [KX ost on Lett ne a sein 2 GD 2-o39% 0 04 19% te eas Figure 12.2 dealzed cross sections through typical porphyry copper deposits showing the evolution of oxidation, leaching, ‘and aarichmont in a mineralized system Containing 0.2 pereent copper and a 5 volumo percent total suide (4°2) and ‘a mineraiized system contain 0.5 percent copper and 1 volume percent total sulide (2). 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 sulfuric acid into capillary solutions. The amount of these com- inds available to the solution is a function of: (1) the total sulfide content, (2) the copper sulfide to iron sulfide ratio, and (3) the mineralogy of the copper sulfides. Effect of ‘Sulfide Oxidation. ‘Oxidation of rocks with a278 James A. ANDERSON high total sulfide content produces abundant sulfuric acd. ‘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: 4Fe8, + 71,0 + Ufo, HF eO; + 6H,SO, + 2FeSO, a 6CuFeS; + 12H,0 + 250; = 4HFeO) + Cu(OH),S0, + TH,SO, + 2CuS0, + 2FeSO, 2) ‘A lowering of the total sulfide content of the rock also de- ‘eases 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; it is, 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 ‘thatthe 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 increasing the pO 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 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. Osidation of rocks with low total sulfide content produces ‘high pH capillary solutions, which result in in situ precipita- tion of copper and iron compounds in the zone of oxidation. Because copper is more soluble than iron (see Figs. 12.3, 124), 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 enrichment. 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 Figure 12.9. Ehipl ciagram showing the stabil fields of copper miner- al in the systom Cu-SH.0. thorough leaching and enrichment of capper. The stability fields of cupric ion (Cu), chaleanthite (CuSO,SH;0), chaleocite (Cu,8), and covellite (CuS) dominate this environ- ‘ment. Since water soluble chalcanthite that precipitates from low pH capillary solutions is redissolved by dilute recharge ‘waters that periodically flush 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 [H(Fe,Cu)O;], neotocite [(Cu,Fe,Mn)SiO,}, and, more rarely, turquoise (CuO+3A 1;0y2P;0;9H;0). Moderate pH solutions produce partial leaching of cop- per from the capping, The stability fields of antlerite [Cus (OH),804}, brochantite [Cus (OH),SOq), cuprite (Cu;0), na- tive copper (Cu), and chaleocite (Cu;$) dominate this envi- ronment. Co-precipitating limonite minerals are saturated with camouflaged residual copper. Geologic associations in- dicate that chrysocolla (CuSiOy-2H,0) forms instead of bro- chantite when capillary solutions are high in dissolved silica; malachite [Cu; (OH);COs] forms instead of brochantite in cappings conning, highly reactive carbonate gungue minerals.BORGSTROMITE GOETHITE + BORGSTROMITE Eh ( oxiga 0, ( atmospneres)—e s PYRRHOTITESS Leseno SS Figure 12:4. EivpH dlagram showing tha stability fields of some ion minerals inthe system Fo-S-H.0, 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-jarosite ((K,H)Fes(SO,)s (OM stability boundaries in Figure 12.4. Experimental data indicate that hematite does not precipitate from Fe-S- HO solutions at temperatures below ~125°C—the dehy- Gration temperature of goethite to hematite. The stability relations of borgstromite, gocthite, and hematite have im- Portant implications in leached capping interpretations. The PH dependence of the borgstromite-goethite boundaries indicates that the ratio of these minerals is related to the nature and amount of sulfides that produce sulfuric acid during oxidation. The pH control over the solubility of cop- per and iron provides a correlation between the borgstromite- ‘goethite ratio and the amount of leaching of these metals from the zone of oxidation. The occurrence of hematite in oxidized, low temperature, sulfur-rich systems is anomalous from the standpoint of present experimental evidence. The abundance ofthis mineral in oxide Zones formed by oxidation, of a sulfide zone containing chalcocite suggests that 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 anom- 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 capil- lary 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 silicate minerals exerts similar controls on mineral stabili- 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 (see 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: 2K AISI); + H)SO, + H,0 = A1;Si,0(OH), + 4810; + 2K* + soz @ This condition implies that supergene alteration is not confined to the oxide and supergene chaleocite 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 react mineral acid consumption, which produces a downward in- crease in the pH of acid solutions originating in the oxide zone. Chlorite and biotite (magmatic or hypogene) serve as ‘measure ofthe 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 sulfide zone may, therefore, mark the depth of supergene acid altera- tion. Supergene 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 “unreac- tive clay” can be readily explained by considering the kaolin- ite to be the product of supergene acid attack on reactive gangue, including calcite, plagioclase, and mafic minerals. ‘Such an explanation is supported by experimental, thermo- ‘dynamic, empirical data (see Fig. 12.5) and by field observa-280 Tames A. ANDERSON 65 I l f ! 1 | | | | KAOLINITE GIBBSITE I | | | 1 | =a0 | ORTHOCLASE ALBITE | quartz —>l<.amorpuous— ae SILICA LEGEND PYROPHYLLITE “*°™'tins. Stevitity boundary Creo}ar aa [iti] ee Figure 12:5, Suggested supergene stably fisds of silicate and sca minorals shown as a function of alkal-tydrogen ion and silica actives. 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- 4 tha formar enlfide minaralizatinn. "Th 9 significance of these correlations have been examined by min- cralogical and chemical research on samples collected from the oxide, enrichment, and primary zones of sulfide 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 significant 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 sulfide:iron sulfide ratio, G) copper sulfide mineralogy, and (4) the reactivity of the xy water in turn regulates thecan neers PYROPHYLLITE Leseno Dro} Constant [45i09,F4* 4a 8144] Figure 12.6. Suggestod supergone stably fields of slicate minerals shown as a functon of pH and activity of alkali, 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 “limonites,” and supergene copper minerals are listed in Fig~ lure 12.7. Mineralogie analyses of samples from eappings over sulfide deposits demonstrate that the common limonite and oxidized copper minerals include goethte, jarosite-borgstro- mite, hematite, neotocite, pitch limonite, chrysocolla, tur- quoise, antlerite, brochantite, cuprite, and native copper. Signiticant quantities of copper are also camouflaged in co- precipitating fimonite minerals Leached Capping and Techniques of Appraisal 281 Tenorite is rare in eappings over sulfide deposits. This situation is explained by the neutral to alkaline conditions Fequited for its stability field (see Fig. 12.3). Tenorite docs, however, commonly accompany malachite (or, locally, azu- Site) which occurs in cappings that contain abundant earbon- ates, because the carbonates neutralize most of the sulfuric acid generated by sulfide oxidation. Chaleanthite is common in the mixed oxide-sulfide zone cof 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 fish the zone of oxidation, The hydrated ferric sulfates shown by solid triangle in Figure 12.7 are rarely found in eappings 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, €g,, 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 deseribed in the literature have been dscred- ited by X-ray studies by Posnjak and Merwin (1922). Alunite is common in certain types of cappings. It is included with the imonite minerals because ofthe solid solu- tion series it forms with jarosite. Jarosite may also form a solid solution series withthe mineral borgstromite (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 coppet 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 ‘The empirical relationships illustrated in Figure 12.8, and, in more detail in the sections in Figures 12.9 and 12.10 demonstrate that the limonite and copper mineralogy of a capping are sensitive indicators of the total sulfide content and sulfide mineralogy of the former sulfide zone. The per- cent of goethite in limonite, ic, 100X 6/6 + H+ J, (G soethite, H = roste), is diagnostic ofthe total sulfide content of the former sulfide 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 chaleocite 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 eapping when the mole ratios of chalcopyritespyrite and chaleocite:pyrite are greater than 0.5 in the sulfide zone (see Figs. 12.8, 12.9, and 12.10).282 JAMES A. ANDERSON IRON MINERALS HEMATITE =F GOETHIT BORGSTROMITE 30) Fes(S0q)e(0Hg SAROSITE (KI Fes(504)2(0%e ALUNITE-(H).A5(S0,)0H)e HOHMANNITE SERIES F405 2509 94,0 COPIRPITE (WS -2Fe05°580317H0 COQUIMBITE SERIES Fez05'380s:aH20 RHOMBOCLASE SERIES —Fez03-4505 9Hz0 MaRTITE~Fe,03 Leproocnocire-Feoton) (W3.)woter sie discredited minerals 1203- YeeO (2) AyarogoetbiteFez0y-V/sHg0 (3) moniteF9e03 2 Heo (a) xenthosiaerita=Feg0y 210 (8) fimnite-F2e0y: Fed (6) esmorideite-4z05 44:0 AMORPHOUS COPPER AND IRON COMPOUNDS PITCH LIMONITE ~WiFe.cul0p NEOTOCITE ~comnre sig CHRYSOCOLLA-cu5i 05-10 TURQUOISE~Cu0 381965 28,05:9H,0 COPPER MINERALS H,0 io) Sas) er STROMITE \yi3) 7 2) i GOETHITE, Fa JAROSITE— LEPIDOCROCITE ALUNITE ARTITI HEMATITE (MARTITE) Feros LEGEND © Common Minerals CUPRITE-cu,0 NATIVE COPPER-cw" 2 ANTLERITE~CulorgS0e ' BROCHANTITE-ceqiOHe50y CHALCANTHITE~cuS04 31.0 MALACHITE~cu,om,60, AZURITE~CusiOhtgl€Oaly TenoRire=cx0 . Projected from K-AL Compositions { H30* substitution for K+ x discredited limonite minerals Rare sulfates Figure 12.7. Compositions of supergene foc on and copper minerals shown as functions of H,0-S0s-Fes0, 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 sullide-iron content of the former sulfide zone, because significant leaching of iron from a capping does not occur until solutions have sufcient acidity to form jarosite or hematite. The empirical correlations summarized in Figures 12.8, 129, 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 eappings 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 limonite 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 {gocthite in limonite. This correlation of the percent of gocth- itein limonite with the residual copper content ofthe capping is valid for all degrees of rock reactivity, because the pH Of the capillary solutions influences the ratios of limoniteMINERAL ABBREVIATIONS A ~ANTLERITE EOUPRITE,NaTIVE coPPER 8 -BrocnantiTe. ECUPRITE,NATIVE COPPER G-coernire ANTLERITE- BROCHANTITE GOETHITE JAROSITE HEMATITE CAPPING CLASSIFICATION Figure 12.8. Correlation of imonita and copper mineralogy with former sulde mineralization.284 JAMES A. ANDERSON (CHALCOPYRITE 100: Mole percent chalcopyrite in sult PYRITE 0. 75— dantite in Line (0° 2/y 4444) Volume % Sulfides (decreasing pH) —> LEGEND Fae 129, Comeation diagram of eit and copverminclogy wih former py and chacopyitin various copper deposi precipitates (see 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 chaleocite (see white area in Fig. 12.10) are not capable of leaching significant copper or iron. The oxide zone is, therefore, characterized by moderate to strong iron staining, predominantly goethite Conversely, highly acid solutions derived from the oxidation of sulfide deposits with a high total sulfide content or low Proportion of chalcocite (area with dark shading in Fig. 12.10) are capable of leaching most of the copper and iron from the oxide zone. These cappings are characterized by ‘weak iron oxide staining, predominantly jarosite or hematite. In both examples, most of the copper in the capping is ‘camouflaged in the limonite minerals when the chalenmrite: pyrite ratio (see Fig. 12.9) or the chalcocite;pyrite ratio (see Fig. 12.10) is less than 0.5 (.c., 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 chalcopyrite:pyrite or chal- cocite:pyrite ratios greater than 0.5 (ve., 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, cither antlerite, brochantite, cuprite, native copper, or resid val chalcocite 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 limonite composition and rock copper geochemistry with theis explained by the marked reduction in acidity, and, thus, in copper leaching produced by oxidation of chaleocite;pyite or chaleocitechaleopyrit 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 chalcocite in the former sullide zone. Addi- ‘tional empirical correlations demonstrate that the percent of hematite in limonite and the residual copper content of the ‘capping are related to the amount of copper enrichment at ‘depth; the relationship between these parameters is shown on CHALCoCITE 100. Mole percent cholcocite in sulfides ——> PYRITE 01 H] Tenorite ~ cur Native Copper Brochantite ~ tcupite Motive conser [7] Anttovite~ scuprive native copser Leached Capping and Techniques of Appraisal 285 the chalcocite-enrichment prediction chart in Figure 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 chalcocite 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 cone yielding satisfactory results. The values obtained (’)cor- respond to the equation V (in ft. % Cu) = (EG - PG)T. where £G is the average grade of the enrichment zone, PO is the average grade of the primary zone (the average grade of the upper part of the 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 ee ee ae 5 6 7 a Volume % Sulfides (decreasing px) ——> LEsenD, Figure 12:10. Crelation of imoite and copper minoraogy with former pyrite chaleocita, and chalcopyrie mineralization.286 JaMes A. ANDERSON FORMER MOLE PERCENT CHALCOCITE FORMER MOLE PERCENT CHALCOPYRITE TN SULFIDES TN SULFIDES we o ~ » “ 6 70 %° 100 EXAMPLE OF NOMOGRAPH USE Given ‘nd copper mineralogy of capping indicate that the former sulfide zone ‘contained: 1 10 Mole percent Cholcopyrite in Sulfides (point A) 2-30Mole percent Chalcocite in Sulfides (point 8) ‘3-3 Volume percent Total Sulfides (point D) Procedure: Proje ne A-B to determine pit ¢ I= Projet line 6-0 to point € ond read the percent opper inthe former sutide‘tone'"™ "* Pe® PERCENT COPPER IN FORMER SULFIDE ZONE ° 0 02 os os os os Figure 12.11, Nomograph for converting volume percent sulde to weight percent copper in rock. zone can be predicted from calculations using the primary sgrade and feet-percent copper enrichment predictions if the thickness ofthe 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 degrees 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. Chalcocite 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) LEGEND 909 200} 00] +100 INTERPRETATIVE oara reat copper lerChatcoce rope 00] ete [ Envehes Zone 400] Pon eroge cred of Primary Zone Figure 12.18. Chalcosite-onrichment prediction chi ‘rochantit, cuprte nae copper. or residual chal ‘enrichment blanket orally pvacent at th nant % HEMATITE WW LiMoNiTe m0 art based upon hematite and copper contants of capping. H anterit, te 8 present in the samplo, the chat gives the orade ofthe siete‘most of the copper is retained in this type of capping and is, not 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 coppet leach- ing, produced by oxidation of chalcocite:pyrite or chal- cocite: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 chalcocite, 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 enrichment indications of local isolated “pods” of hema- tite formed by second-cycle oxidation of local zones of prior chalcocite enrichment—are the only techniques available. APPLICATION OF CONCEPTS OF CAPPING APPRAISAL ‘The data and interpretations concerning supergene min- eralization 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, and 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, () percent jarosite in limonite, (4) diagnostic copper min- eralogy, and () residual copper content of the capping. Recognition and Interpretation of Cappings First-cycle oxidation-leaching of the pyrite-chaleopyrite deposit in Figure 12.144 produces a chalcocite enrichment blanket overlain by an oxide capping containing goethite and Leached Capping and Techniques of Appraisal 289 jarosite (see Fig. 12.148). The capping formed over the py- Fitic halo containing 0.5 volume percent pyrite contains go- cthite and may, therefore, be classified as a goethitic capping (represented by classification type I in Fig. 12.14). No copper or iron is leached from this type of capping Limonite in the capping formed over the pyritic halo containing 4 volume percent pyrite consists of jaroste with minor goethite, while limonite in the capping over the ore zone containing 5 volume percent total sulfides consists of pure jarosite. Both of these cappings are classified as the jarositic type (See the upper jarosite capping at Toquepala shown in Fig. 12.15; represented by classification type 2 in Fig. 12.14). Most of the copper and iron has been leached from these cappings. The primary grade of the sulfide zone ‘beneath each of these eappings may be reconstructed by the use of the prediction chart in Fig. 12.12. The amount of chalcocite enrichment in the sulfide zone below these jarositic ccappings must be evaluated by qualitative indirect methods, such as applying a range of probable enrichment factors to the primary-grade prediction values. Enrichment factors ob- served in similar deposits range from 1.5x to >10x. The most common range is 2x to 6x. ‘Oxidation of sulfides in the limestone inclusion shown in Figure 12.14 A—D is not accompanied by leaching of copper cor iron, because the acid is consumed by the reactive carbon- ate minerals. A goethitic capping is formed in the limestone inclusion inthe pyritic halo. Trace amounts of malachite may be observed in the capping over a pyritic halo that contains 0.02 percent copper. A malachite capping (represented by classification type 3 in Fig. 12.14), which consists of malach- ite (local azurite) and goethite, is formed in the limestone 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 chalcocite ensichment blankets (compare Figs. 12.148 and 12.14C) that are overlain by one or more of the following cappings: 1. original jarostic eapping formed by oxidation ofa pyrite- chalcopyrite zone (see upper jafosite capping in Fi 12:15; represented by claefcation type 2m Fig. 12.14); 2. hematitie capping, containing hematite, jroste, and go- hit, formed by oxidation ofthe former chalcociteen- Fichment blanket (see hematite capping at Chino in Fig 12.16 and hemate layer in capplag’at Toquepala Fig. 12-15; represented by classdcation type 4 in Fig Inia), 3, lower jarositic capping, containing small zones of chalco- ‘ite enrichment or stbsequent stall zones of hematite capping, formed by oxidation of a pytite-chalcopyrite.” Zone oecupying a gap between two entichment zones (see lower jaroste capping at Toquepala in Fig. 2-15 and jarosite capping at Butte in Fig’ 1217, represented by Eassiteation pe 2A tn Pig. 14 4. antlertebrochantite capping, containing antlerte or bro- hantite with hematite, goethite, and occasionally cu prite, native copper, of residual chaleocte, formed. by the in stu oxidation of multi-eycle, high-grade, chalco- Cite enrichment blankets in which chalcocite;pyrite or shscottalepyts mele rato re greater than 8 represented by classication type 5 capping shown 33 the crosshatch pattem in Fig. 12.14C,D).290 JAMES A. ANDERSON Gaps are commonly present between successive chalco- 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 ofthese 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. Chalcocite enrich- ment grades for the sulfide zone below jarositic 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. 12.14CD and 12.17). Es- timates of chalcocite entichment indicated by hematitie cappings may be obtained from the prediction chart in Figure 12.13. Note that the irregular nature of the grade in the chalcocite enrichment zone in Figure 12.148 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 12.5, ‘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 ofthis capping 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 and 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. All transitions from primary pyrite-chalcopyrite miner- alization (see Fig. 12.144) to primary mineralization con- sisting only of chalcopyrite (see Fig. 12.14) are found in nature. A common occurrence of the chalcopyrite type is Aepicted in Figure 12.14, wherein the sulfide mineralization consists of approximately 1 volume percent chalcopyrite, First-eycle oxidation of this chalcopyrite deposit produces a pitch limonite-neotoeite capping (classification type 6 in Fig, 12.14-H) consisting of oxide ore containing pitch limonite, neotocite, chrysocolla, goethite, and occasionally residual chalcopyrite. No copper or iron is leached from this capping except in local areas of higher sulfide content. Successive ceyeles of oxidation produce similar cappings (see Fig. 12.14 G.H). Neotocite cappings form over deposits with chal- ‘copyrite;pyrite ratios ranging from 9.0 to 0.5 (Gee Figs. 12.8 and 12.9), 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 neotocite is present in each type of capping over the ore zone. Primary-grade and. chaleocite-grade prediction techniques outlined above for the cappings shown in Figure 12.14E-H also apply for these cappings. Field observations at Chuquicamata, Chile, and Cuajone, Peru, have confirmed that antlerite-brochantite, eotocite, and neotocite-antlerite-bronchantite cappings ‘overlie zones of enrichment 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 oo- 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 northern 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 “ted bed” sediments, hot spring deposits, iron formations, lateritic and desert soils, ‘tc. 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 8 capping provide sufficient evidence for capping classfica- 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 and detailed mapping of the limonite and copper mineralogy. ‘The empirical correlations summarized in Figures 12.8, 12.8, and 12.10 demonstrate that field estimates of the per. ent goethite in limonite (100 X G/G + H + J), of the Percent hematite in limonite, of the percent jatosite 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 outcrop examined. The limonite and copper mineralogy of areas deemed 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 goethite, 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 at a rapid rate (much faster than alteration zones, forsuing SUBSEQUENT OXIDATION -LEACHIN oF careIns TON W ENRICHMENT ZONE Figure 12.14. Idoalzed cross sections tough typical porphyry copper deposits showing oxidation cyces, capping classic: tion, and limonite characterises Intrprota tions shown for a system with 0.2 parcont ‘copper and 5 volume porcent total ‘sulides (4-0) and for @systom with 0.5 per- + ind 1 volume percent292 James A. ANDERSON oad Cau Figure 12.15. Layored jarosite and homatite capping overlying chalcocito ore at Toquepala, Pru. Upper fr formed by oxidation of pyrte-caleopyite. Hematite capping formed by oxation ofa chaleoito enrichment Blanket teeert Lower jaresite capping formod by oxcaton ofa pyite-chalcopyita zane between two chalcocite onachmaont blankets ne {8p batwoen tho former and prosentchalcocte enrichment blankets fs tho result ofa marked drop nthe grounawatr lable Produced by susden upland ting Cs Cel y) es e Figure 12.16. Hematite capping overying chalocito nico. The hematite capping formed By Qaialion ofa chaleocteenichmant blanket. Continuous lowering of he foundwate ake produced worteal Sorene ‘of chaleocte enrichment zones with subseavent ssLeached Capping and Techniques of Appraisal 293 Figure 12.17 Jaroste capping with loca zones of hematite capping over chaloocite ore at Butt, Montana Jarosite capping formed by oxidation of pyrte-chaleopytte, Hematite capping formed from destruction of local zones of chalcocite ench 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 sam- 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. Verifi 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 for all observers. The above-described procedure of capping appraisal pro- Vides a method of predicting primary and chalcocite enrich- ‘ment grades that is suitable for reconnaissance, examination, and project decisions. Identification of Limonite Mixtures and Copper Miner- The observed colors of limonite mineral mixtures ate luenced by grain size, surface weathering (“desert var- nish”), nature of illumination, impurities, and the color sen- al sitivity ofthe viewer. Most ofthese variables can be compen- sated for by seratching the limonite in the rock sample and comparing the color of the resulting powder (streak) with standard powders. A limonite color chart, containing stan- dard mixtures of actual mineral powders, is @ useful aid in the field identification of mixtures of goethite, jaroste, and hematite. Neotocite [(Cu.Mn,Fe)SiO,] and pitch limonite [H(Fe, ‘Cu)O,] ?) may sometimes be confused with manganese oxide and goethite, respectively. Neotocite is distinguished from ‘manganese oxide by its vitreous black to drab black appear- ance and by a black to dark olive, waxy streak when scratched; fine-grained mixtures of gocthite ina sample com- ‘monly impart a brownish tint to the streak. Neotocite, which may contain up to 21 percent copper, can also be distin- guished by a simple field test for copper. This test consists of applying 10 percent sulfuric acid to the mineral surface; rub- ‘bing the acid-wetted surface with metallic iron, such as a knife blade; and examining the blade for an obvious coating ‘of metallic copper. Pitch limonite may be distinguished from goethite in the field by its brown resinous appearance and shining black conchoidal fractures, which commonly show red internal reflection when viewed with a hand lens. It can also be identi- fied by the fcld test for copper described above; this testis particularly useful for fine-grained occurrences, since the olor of the powder (streak) is identical to that of goethite. This similarity to goethite is explained by X-ray studies,294 TaMES A. ANDERSON which indicate that pitch fimonite is a copper-bearing hy- drous iron oxide mineraloid that occasionally gives weak X-ray reflections similar to those of goethite. Limitations of Capping Interpretations The grade prediction techniques summarized in this chapter are by no means a panacea for porphyry copper ‘uterop evaluation. On the contrary, the validity ofthis ap- proach to capping appraisal (outcrops or sub-outcrops) relies heavily on correct 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 AD. Pre-ore or post-ore structures may control or produce offsets in sulfide mineralization. Rock types commonly have 4 marked influence on the distribution of primary sulfides. Highly reactive carbonate rocks below the outerop may ins 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 mi ‘ralogy, 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 eappings are recognized: (1) goethite, (2) Jarosite, (3) hematite, (4) pitch limonite-neotocite, (5) antler- itebronchantite, and (6) malachite. Grade predictions for each type of capping utilize empirical correlations of the primary grade and chalcocite enrichment grade ofthe sulfide Zone with (a) percent goethite in limonite, (b) percent hema. tite in limonite, (¢) percent jarosite in limonite, (4) 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 classifica. tions and for semi-quantitative 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 ofthe sulfide Zone below capping require geochemical analyses for copper jin rock and detailed mapping of limonite and copper ‘mineralogy. As a part of the study reported here, copper grade pre- dictions were completed at 9 properties prior to drilling and Post-mortem capping appraisals were made at 9 other prop- erties. Drilling results available demonstrate that over 15 Percent of the primary-grade predictions (in % Cu) agreed within 30 percent of the actual values encountered in drilling, Over 80 percent of the chaleocite enrichment predictions (in ft. % Cu) agreed within 20 percent of the values obtained by drilling ACKNOWLEDGMENTS The author wishes to acknowledge 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, ideas, 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 asis- tance in collection, interpretation, field application, and eval- uation of research data, SELECTED REFERENCES ‘Baas Becking, LG. M.; Kaplan, LR; and Moore, D., 1960, Limits ‘of the natural environments in terms of pH and oxidation. reduction potentials: Jour. Geol, v. 68, p. 243-284 Bladh, K. W., 1978, The weathering of sulfde-beating rocks ass0- ciated with porphyry-type copper deposits: Unpub. Ph.D. Diss, Univ. Ariz, 98 p. 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