GEOL 471/671 - Ore Deposits Supergene Alteration Goals: At the conclusion of this lab, you should have a better

understanding of the transformations that accompany near-surface weathering of ore deposits, both in terms of mineralogical as well as geochemical changes. You should be able to predict underlying hypogene mineralogy based on supergene mineralogy. Introduction Supergene alteration (weathering) of sulfide systems yields many products which, if exposed at the earth's surface, allow some interpretation of original minerals present which, in turn, provide insights into the ore deposit at depth. These supergene products include secondary ore minerals, boxworks and other textures, and various common oxides, hydroxides, carbonates, and sulfates of Fe, Mn, and Ca. In some districts, other secondary oxide minerals may be present, depending on the original mineralogy of the hypogene ore and the conditions under which oxidation takes place. Secondary Ore Minerals Secondary ore minerals were frequently mined first in many of the old mining districts. For example, cerrusite and smithsonite constituted the early ores at Leadville, CO, along with precious metals. Many old silver districts started out in supergene silver mineralization. In some places the ores were only economic because of these secondary minerals and their relative ease of processing. This was particularly true for porphyry copper deposits, the secondary processes for which are described below. Recognition of these secondary minerals is, therefore, necessary for understanding the overall history of an ore deposit. This lab exercise includes hand samples of various secondary minerals with which you should become familiar. Boxworks and the Interpretation of Leached Outcrops Because most ore deposits have abundant pyrite, oxidation of sulfides (as well as silicates) yields cellular structures consisting of limonite or limonitic jasper. However, iron may be relatively mobile under the proper conditions (Figure 1), thus the presence of limonite in one location may not necessarily be indicative of the original rock in the immediate vicinity. Therefore, one of the first tasks in interpreting iron oxide mineralogy is determination of whether the limonite is indigenous, fringing, or exotic (Blanchard, 1966). Indigenous limonite has been formed in place from the original sulfide mineral, and its origin is usually fairly clearly demonstrable, as it forms pseudomorphs of the original sulfide (usually pyrite) or fills cavities where the parent mineral was originally. These may be used to determine which primary minerals were present as well as making some estimate of original sulfide percentages. The estimate of original sulfide percentages is important to the interpretation of porphyry copper systems, in terms of whether there is likely to be sufficient secondary Cu minerals to make a mineral deposit into an ore deposit. The essential chemical reactions take place only if sufficient quantities of S and Fe are present. The S is required for the generation of sulfuric acid and complete oxidation and dissolution of the sulfide minerals. Low S:metal ratios in primary sulfides prevent complete oxidation. Limonite formation will not occur unless sufficient Fe is in solution and can be precipitated, therefore, significant amounts of soluble iron-bearing minerals are required (generally silicate Fe does not fit this requirement). As a rule, then, an abundance of pyrite (FeS2) is necessary to satisfy these two requirements. A high ratio of pyrite:other sulfides results in strongly acidic solutions with consequent complete oxidation and leaching. The leaching removes the metals, and frequently, a limonite substitute is deposited which may inherit some of the physical characteristics of the primary minerals.
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Figure 1a. Stability relations of iron oxides and sulfides in water at 25C and 1 atm total pressure. From Garrels & Christ, 1965.

Figure 1b. Stability relations in the Cu-waterCO2-S system at 25C and 1 atm total pressure. PCO2 = 10-3.5. From Garrels & Christ, 1965.

"Limonite" includes a number of hydrous ferric oxides, sulfates, and carbonates. The most common of these include goethite, hematite, jarosite, and siderite. Additional impurities frequently present include silica, manganese, minor metals and late carbonate. Recognition of the limonite assemblage is required in order to estimate total sulfides originally present. The three major limonite minerals impart distinct colors to the limonite. In general, powdered jarosite is yellow (crystalline jarosite is brownish), goethite is brown, and hematite is red (crystalline hematite may be submetallic). Mixtures of these colors will yield intermediate shades. It is important to interpreting the original mineralogy and geochemical weathering history of rocks to understand the formation conditions of each of these limonite minerals. Figure 1 is an Eh-pH diagram for the Fe-O-H system and illustrates that goethite minerals (represented by Fe(OH)2 and Fe(OH)3) are stable under mildly acidic to very alkaline conditions (note that in most weathering environments the oxidized form Fe(OH)3 will predominate). Under acidic conditions, Fe3+ is the stable species. However, as noted above, oxidation of pyrite also releases S which oxidizes to sulfate and forms sulfuric acid. If sufficient Fe also is present (usually the case), jarosite may be a stable mineral phase. The standard reference on secondary minerals is Blanchard (1968). This is available in the lab for your review. Of particular interest to this lab are the introduction (Chapter 1), and sections on limonite definition (Chapter 2), spatial zoning of limonites (Chapter 3), and color (Chapter 15). The chemistry of limonite formation is reviewed in detail in Chapters 8 and 9. The color plates will give you some excellent examples beyond what is available in the lab materials.
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Figure 2. Correlation diagram for limonite and copper mineralogy with former pyrite and chalcopyrite in various copper deposits. Estimation of original sulfide percentage based on limonite mineralogy is possible from this chart. Curves represent the percentage of goethite in limonite. Fields for different known deposits include the following abbreviations: GALL = Gallagher; CERR = Cerrillos; HILL = Hillsboro; MB = Mineral Buttes; McA = McArthur; YER = Yerington. From Anderson, 1982, Figure 12.9.

References: Anderson, J.A., 1982, Characteristics of leached capping and techniques of appraisal; in: Titley, S.R., 1982, Advances in Geology of the Porphyry Copper Deposits, Southwestern North America, University of Arizona Press, p. 275-295. Blanchard, R.L., 1968, Interpretation of leached outcrops; Nevada Bureau of Mines Bulletin 66, 196 pgs.

Examples of supergene minerals & environments: There are two trays of samples in the lab cabinet for you examine. Please return the samples to the tray and cabinet when you are done looking at them. The trays also include 6 samples that go with questions 1-6 of the assignment. Samples in lab trays with brief descriptions:
Sample 3 37 44 AS-1 Baghdad BD-1 BOW Carlin, NV CE-1 CH-10 Chino Chino pit CP-42 CP-51 DML-76-7 DML-76-8 DP4600 DP4780 Elijah Grand Hem Ithaca JG-1 Leach MACL Ohc (2 spls) Silver Peak SLMn SS-1 Taylor TC TC-81-8 Description Unknown: Fringing to exotic limonite Unknown: Exotic goethite Unknown: Indigenous goethite - note pseudomorphs after pyrite crystals Antelope Springs district, NV: Cervantite (Sb oxide) after stibnite in fractures. Baghdad, AZ: secondary Cu minerals as conglomeratic cement Black Diablo, NV: secondary Mn oxide minerals Unknown (on cabinet): boxwork goethite after sulfides Carlin, NV: goethite + jarosite Fringing limonite - note liesegang banding, indicative of deposition from solution Chino, NM: native Cu, chalcocite, malachite Chino, NM: native Cu, chalcocite, malachite Chino, NM: exotic stalactitic limonite Chino, NM: hematite-cemented breccia, exotic limonite Chino, NM: hematite in fractures, exotic limonite Sherman Mine, Leadville, CO: bladed barite + sulfides + oxidation products Sherman Mine, Leadville, CO: boxwork quartz+barite+limonite; most sulfides leached out Post pit, NV: primary realgar altering to orpiment Post pit, NV: hypogene stibnite + barite, supergene (pink) alunite Ely, NV (on cabinet): boxworks after sulfides, some primary sulfides (gn) still present White Pine County, NV: secondary Cu minerals, cuprite + malachite Hematite stain in sedimentary clays Kingman, AZ: chalcocite, turquoise, molybdenite in silicified monzonite Jasperoidal goethite Ruth, NV: leached cap of primarily goethite MacLaughlin, CA: mixed iron oxides - hematite, jarosite, goethite Carlin, NV: silica boxwork with limestone removed Silver Peak, OR: (2 samples) massive ore (unweathered) and gossan zone Sleeper, NV: Mnox coating on volcanic rock fragment Sunnyside, CO: rhodochrosite with Mnox coating Taylor, NV: stibnite starting to alter to stibiconite Tincup, CO: anglesite + hemimorphite with traces of remnant sulfides Tincup, CO: Cerussite, limonite, and pyrolusite

Tuscarora VW98-1 Tiko-1

Tuscarora, NV: jarosite + goethite Veteran West area, Ruth, NV: secondary Cu oxides Mali: Ferricrete laterite

Lab Assignment Examine the following specimens and answer the questions. Please provide your typewritten answers to Ingrid by 2 pm, Monday 11 December. Grading will be based on the following: 40 points for handing in on time, 5 points for each question, 5 points (overall) for neatness/grammar (total 100 points). Sample CP-54 CE-6 Pinson TC-81-8 PC Questions Identify the iron oxide(s) present, and indicate if significant acid was generated during weathering. If more than one limonite mineral is present, estimate relative proportions. Identify the supergene mineral(s) present, and name the probable precursor(s). Estimate the relative proportions of limonite minerals present. Identify the limonite mineral(s) present, and indicate if significant acid was generated during weathering. If more than one limonite mineral is present, estimate relative proportions. Estimate the original pyrite content based on limonite mineralogy. Identify the original (hypogene vein) mineral(s) and the secondary (supergene) mineral(s). Write the chemical reaction that is occurring in this rock as weathering proceeds. The surrounding wallrock is a rhyolitic breccia. Speculate on the origin of the chemical components for the supergene mineral(s). Identify the major limonite mineral(s) present, and estimate their relative proportions. Indicate whether they are indigenous, fringe, or exotic, based on the evidence you see in the rock. Speculate on the origin of this rock (i.e., what is it and how did it form?).

RK-1

Mal

List the minerals that might form as secondary (supergene) products from the assemblages in the following list. Be sure to consider what other parameters (like pH) and components are necessary to form those secondary minerals. 1. chalcopyrite-molybdenite-quartz vein stockwork in granite porphyry 2. galena-sphalerite-pyrite-scheelite-quartz vein in basalt 3. massive jamesonite-arsenopyrite-pyrite replacing limestone 4. galena-sphalerite-pyrite-quartz vein in dolostone