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By B. S. Butler

AN understanding of mineralizing solutions and how they carry and deposit metals is of prime importance to students of ore deposits. Lindgren states: "The whole problem surely is very complicated. One difficulty is that we know so little about the stability field of ore minerals."1 Lindgren further states: It is believed that they [the solutions] were in small part oxidized to sulphates, for instance, but in large part they were composed of hydrogen sulphide, alkaline sulphides and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of the double sulphides as important constituents of the solutions probably holds good. In the fourth edition of Mineral Deposits2 Lindgren had changed his views somewhat: From the work of Day, Allen, Shepard, and others, it would seem probable that many of the volcanic gases are acid when given off but are in unstable equilibrium, and could not have preserved this acid character after having been long in contact with the surrounding rocks. It is believed that they were in small part oxidized to sulphates, for instance, but in larger part they were composed of hydrogen sulphides, alkaline sulphide, and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of double alkaline sulphides as important constituents of the solution probably holds good. The writer wonders if progress would not result from an attack on the problem in steps, the steps to contribute to the attack on the whole. The initial step would deal with the simpler bodies of supposed magmatic (hydrothermal) origin, that is, those composed essentially of silicates, oxides, sulfates, and sulfides. The following discussion attempts to develop one step of a method that was proposed on a more comprehensive scale in 1929 by the writer and W. S. Burbank.3 The accompanying partial table (Table I) of the electromotive series is from a table distributed by Merck & Co. Inc., manufacturing chemists, prepared in turn from Fundamental Chemistry.& The electromotive arrangement brings together elements that in hypogene ore deposits occur: 1) in oxygen combination only; 2) in combination with sulfur as well as with oxygen; and 3) as sulfides, arsenides etc., and as native metals, see Table 11. The writer clearly recognizes that he is not qualified to discuss the formation of ore deposits as a chemical problem, but he feel that some of the relations that are met by the geologist can well be stated with the hope that the chemical explanation will be forthcoming. By consideration of a group including mainly the elements oxygen, hydrogen, sulfur and iron, complications are avoided, especially with elements of the lower electromotive group. The results can only contribute to the solution of the problem, not to the completion of it. The pH and Eh of the solutions and also temperature probably determine what minerals form. The mineral groups that contain elements high in the electromotive series are alumino-silicates, titanites, simple silicates, spinels, oxides, carbonates and sulfates, in all of which the elements are combined with oxygen. These groups are also recognized as the general order of temperature at which the minerals start to form, see Table 11. At low temperature are sulfides, arsenides, antimonides, sulfo-salts, and native metals, in all of which the elements are characteristically not combined with oxygen. The intermediate temperature group contains elements that form both oxygen compounds and sulfur compounds.

Jan 1, 1957

By B. S. Butler

Apropos of metals low in the series illustrated by Dr. Butler's Table 11, it is interesting to note that Cress and Feldman29 reported traces of platinum metals in several samples of alunite. They found, chemically and spectrographically, several traces of platinum, palladium, and rhodium in alunite from Sugar Loaf Peak, near Quartzite, Ariz.; silver, platinum, and rhodium in alunite from Rio Grande County, Colorado; and traces of rubidium and gallium in various samples of alunite. These authors stated that the platinum metals appear to be present as Oxides and suggested deposition by hydrothermal solutions under near-surface conditions. AS described by Heineman,30 the wall rock of the Sugar Loaf alunite veins shows considerable alunitic alteration. Pyrite and hematite are relatively abundant in the wall rock but decrease progressively near the veins. Assays of samples of the Sugar Loaf alunite, run by J. B. Cunningham of the University of Arizona College of Mines, showed traces of silver and 0.002 to 0.004 oz of gold per ton, but the chemical form of the gold and silver in this occurrence remains undetermined.

Jan 1, 1957

By Thomas A. Simpson

THE Birmingham red iron ore district in Jeffer-son County, north central Alabama, Fig. 1, is bounded on the northwest by the Warrior and Plateau coal fields and on the southeast by the Cahaba and Coosa coal fields. The area of study includes the ridge and valley between Red Mountain and Shades Mountain, Fig. 2, approximately 70 square miles extending from Homewood in the northeast to Greenwood in the southwest. The district is one of the most important producers of hematite in the United States, with an annual production of about 7 million tons.' The amount of hematite mined between 1870 and 1950 ranged from 6 to 16 pct of the nation's total annual production,' and the iron and steel products from blast furnaces in the Birmingham district supply the entire southeastern section of the country. Most of the mining in the Birmingham district is from slope mines along the outcrop of the ore on Red Mountain, such as Red Ore, Muscoda, Spaul- ding, and Sloss. The Pyne and the Shannon are the shaft mines of the area. The Shannon mine of Republic Steel Corp., in the central part of the area under study, is in Shades Valley at the foot of Shades Mountain. The Pyne mine of Woodward Iron Co. is 2 miles east of Readers Gap in Shades Valley. The hydrology problem has become more prevalent as mining in the area has progressed downdip. An extensive exploratory diamond drilling program is necessary to determine areas where water pressures and abnormal flows are excessive. This operation, added to higher pumpage rates, has greatly increased the costs of ore extraction. In November 1952 the U. S. Geological Survey began a detailed study of occurrence and movement of ground water in the iron mining areas of the Birmingham district. The study is a part of a small-scale but nationwide program to develop data that will be of help to the mining industry in solving mine water problems. The area of the study, in the Ridge and Valley province of the Appalachian system, Fig. 1, is a series of alternate ridges and valleys trending northeast. The principal ridges are Red Mountain, altitude about 1000 ft, and Shades Mountain, about 1100 ft. Shades Valley is between these two ridges, and its lowest point is about 480 ft. Shades Moun-

Jan 1, 1956

By T. Cantwell, N. C. Rasmussen, H. E. Hawkes

Beryl is a mineral that may be difficult to distinguish from quartz by casual field inspection. The easily recognized green color and hexagonal crystal form of coarse-grained beryl are by no means universal, even in beryl from pegmatitic deposits. If it occurred as a fine-grained accessory mineral in an igneous rock, it would almost certainly escape detection unless samples were submitted for petrographic or chemical analysis. There may be substantial deposits of some beryllium mineral, other than beryl, that has been overlooked because that mineral also closely resembles the common rock-forming minerals. A reliable and simple method of identifying beryllium minerals and determining the beryllium content of a rock would be helpful in exploration. This article describes preliminary experiments in applying nuclear reaction to the qualitative identification of beryl and to the semiquantitative determination of the beryllium content of rock samples. Gaudin,1,2 the first to apply a nuclear reaction in detecting beryllium minerals, developed a method that irradiates the sample with gamma rays, which react with beryllium nuclei to produce neutrons. The neutrons are then measured with standard equipment. The cross section for this reaction is about 1 millibarn. The cross section is a measure of the probability that a reaction will take place, for example, between a beryllium nucleus and an incident gamma ray or alpha particles.3-5 At 1-millibarn cross section for the reaction, satisfactory performance required a source strength of the order of 1 curie (3.7 x 10"' disintegrations per sec, where each disintegration releases one or more gamma rays). The reactions will not take place if the gamma radiation is below a minimum energy, in this case 1.63 mev. The size of the source and the energy of the radiation made heavy shielding necessary for these experiments, both to reduce the background count of the neutron counter and to safeguard personnel. The original discovery of the neutron by Chad-wick in 1932 resulted from experiments with another nuclear reaction, induced by bombarding beryllium with alpha particles in which the products are carbon-12 and neutrons. The equation for this reaction is as follows:' " ,Be" + ,He'? 6C12 + 8,n' [1] re-particle neutron In the above nuclear equation (Eq. 1), the sub- script number indicates the number of protons in the nucleus (the atomic number) and the superscript the total number of neutrons and protons (approximately the atomic mass). For the alpha-neutron reaction the cross section is about 250 milli-barns, or 250 times that of the gamma-neutron reaction used by Gaudin. The positively charged alpha particle is repelled by the positive charge of the beryllium nucleus; it must, therefore, have a certain minimum energy in order to approach close enough to the beryllium nucleus to react. For reaction with the beryllium nucleus, the lower limit of the alpha-particle energy is 3.7 mev. The alpha-neutron reaction, with polonium-210 as an alpha source, was selected for the present experiments. Alpha particles are emitted by polonium-210 at 5.30 mev, which is adequate for the reaction with beryllium. Furthermore, this isotope of polonium emits alpha particles with negligible associated gamma radiation, thus eliminating the necessity of shielding. The half-life of polonium-210 is 138 days. Inasmuch as alpha particles carry a possible charge and are large compared with most nuclear particles, their energy is rapidly dissipated in passing through matter. Their range in standard air is 3.66 cm,3 and they penetrate only a few tens of microns into a mineral sample. The short range in air can be minimized by preparation of a flat sample surface that can be brought very close to the alpha source during analysis. On the other hand, short range of alpha particles in air lessens the radiological health hazard and makes it possible to use this method without shielding. It must be emphasized, however, that the alpha emitters are potentially very dangerous if they enter the human body. Polonium must be handled with extreme caution. The literature has reported experiments on the yield of neutrons from reaction of alpha particles with beryllium nuclei. Feld" reports that in intimate mixtures of polonium and beryllium, 3 x 106 eutrons per sec are produced per curie of polonium. Elsewhere in the same reference it is stated that a sandwich-type source yields about one third as many neutrons as an intimate mixture. A table of neutron yields for full energy polonium alpha-particles on thick targets as reported by Anderson7 is the basis of Table I. From Table I it can be deduced that the elements most likely to interfere, i.e., those that also produce neutrons when bombarded by alpha particles, are boron and fluorine. These data also show that it will probably not be possible to determine very small quantities of beryllium in rocks because of the masking effects of the major elements, sodium, magnesium, and aluminum. The neutrons emitted in the alpha reaction are detected by another nuclear reaction. Either of the

Jan 1, 1960

By Eugene N. Cameron

Pegmatites of these areas have become important sources of beryl and lepidolite and have yielded cassiterite, columbite-tantalite, and other minerals. Examination of about 60 of these pegmatites leads the author to question the opinion of earlier investigators that the concentrations of beryl, lepidolite, and columbite-tantalite found have mostly formed by hydrothermal or pneumatolytic replacement of previously formed quartz-feldspar pegmatites. The author concludes, on the contrary, that present knowledge of the occurrence of minerals in zoned pegmatites can be applied to prospecting and mining of pegmatite deposits in these two areas of South West Africa. PEGMATITES occur in abundance in certain areas of South West Africa and in adjacent parts of northern Cape Province in the Union of South Africa. Some of the pegmatite deposits were prospected before World War I, and intermittent mining was done during the period between the two World Wars. The deposits of the Jooste lithium mines became an important source of lepidolite, and beryl, columbite-tantalite, wolframite, and other minerals were produced. Since World War II prospecting and mining have been carried on vigorously, with the result that South West Africa produced nearly 3000 tons of beryl during 1949 through 1953, together with more than 40,000 tons of lithium minerals, chiefly lepidolite and petalite. Small amounts of tantalite, columbite, and other minerals have also been produced during the postwar period. Most of this mineral production has come from two pegmatite areas roughly outlined in Fig. 1. One is the Karibib-Omaruru area of north central South West Africa. The second is the northeastern part of the Orange River pegmatite area, which extends into adjacent parts of Namaqualand, in northern Cape Province of the Union of South Africa. The writer visited the two pegmatite areas in July 1951. The visit was brief. but it gave an opportunity to compare some of the' pegmatites of these areas with those studied and described in detail by many investigators in the U. S., Brazil, and Canada during and since World War 11.'-l' The writer has attempted to determine, in a preliminary way, whether the concepts of internal structure and distribution of minerals in pegmatite bodies developed out of these studies are applicable to prospecting and exploration of pegmatites in South West Africa. Previous Work In an important series of papers (1929 to 1942) T. W. Gevers, H. I?. Frommurze, S. H. Haughton, G. K. Joubert, and other geologists of the Geological Survey of South Africa described and discussed the pegmatites of the two areas.*-" These works are the principal sources of information on the pegmatite mineral deposits of South West Africa. The investigations showed that in the two areas pegmatites are profusely distributed in pre-Cambrian rocks. These rocks are meta-igneous and metasedimentary units that have been folded and subsequently invaded by younger pre-Cambrian granites and by other igneous rocks. The pegmatites are considered to be genetically related to the pre-Cambrian granites. Pegmatites occur in the granite bodies themselves but are most abundant in the surrounding metamor-phic rocks, a pattern repeated in many pegmatite districts of the world. The origin of the pegmatites and the factors controlling the occurrence of mineral deposits in them were discussed at length by Gevers and Frommurze (1929)" and later by Gevers 14, 15 pp. 41-51, Ref.

Jan 1, 1956

By D. L. Everhart

The search for new deposits raises two important questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? A review of the wide geological variety of recent uranium discoveries tells how these questions are being answered. SOONER or later intelligent exploration for uranium leads to these questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? These matters, of course, make a big difference in how best to look for orebodies. Before these questions are discussed it might be well to point out other factors bearing on the subject. The whole business of uranium exploration is only a little over ten years old, participation by the public is only about six years old, and real interest and activity by more than a few large mining companies has arisen only in the past two or three years. Throughout this short period, uranium exploration has been affected by the unique influences of necessary security measures and by division of the overall job into individual projects by a large number of specialists in diverse fields. This has meant that a normal interchange of information on the nature of uranium deposits has really only just begun. Compared to the vast amount of published studies on iron, copper, lead, zinc, and gold deposits over the past 50 to 75 years, current knowledge of uranium deposits is in its infancy and much of the pertinent information is still scattered about in a number of unpublished sources. The volume of reports on all phases of uranium exploration is now beginning to mount at a remarkable rate, and geologists with widely varying specialized backgrounds in uranium geology are engaging in spirited debates over the origin of uranium and the relative importance of geologic controls of various deposits. One of the most interesting features of known uranium deposits of the world is the wide variation, see Table I, in character and geologic environment. It should be noted that many types became prominent during 1953. The davidite-bearing veins of Radium Hill, South Australia, are almost unique, although the same mineral occurs in a different kind of deposit in Mozambique. Recent studies indicate that brannerite disseminated in the granite near Cracker's Well, South Australia, may soon constitute uranium ore. Basalt has been added to the list of favorable host rocks in the Northern Territory of Australia. Basalt is also the host of the pitchblende veins of the Martin Lake deposit, Beaverlodge district, Saskatchewan. The truly remarkable rich and extensive Steen deposit near Moab, Utah, is of the uraninite-vanadium oxide type. Secondary hydrous uranium arsenates and phosphates constitute the uranium minerals in the disseminated deposits of the Wind River Basin, Wyo., a new district discovered in the summer of 1953. Uranium minerals in shales adjacent to fractures were newly reported in New Mexico and several other parts of the world during the year. The well-known important uraninite dissemination in the Rand conglomerates of South Africa has a counterpart, as discovered in the summer of 1953, in the Mississagi quartzite and conglomerate of the Blind River district, Ontario. Gunnar deposit of the Lake Athabaska district, Saskatchewan, consists of uraninite in both granite and sedimentary gneiss beneath a granite cap, and large new orebody of the Eldorado Co. in the same general area follows a preferred stratigraphic horizon in schists. Uranium is, generally speaking, a very soluble and ubiquitous element. It occurs in at least two valency states and for this reason is not easily tied down in natural solutions. As Gruner' has pointed out, it is probable that uranium starts in the hexava-lent state in nearly all solutions instrumental in its transfer. It is believed that under oxidizing conditions the uranium moves in solution as the uranyl ion, UO. In solutions ranging in pH from 1 to 5, the uranyl ion is most commonly in association with

Jan 1, 1955

By P. L. Allsman

Butte mining district contains extensive manganese vein deposits forming a peripheral zone. Oxidation in the veins studied usually extends to a depth of about 75 ft. Secondary minerals formed by oxidation were found to be ramsdellite—always accompanied by intermixed pyrolusite—and cryptomelane. Enrichment of the gossan is accomplished by reduction of weight upon oxidation; theoretical enrichment is 32.2 pct. Additional enrichment is caused by leaching of soluble minerals, particularly calcium and magnesium carbonates. BUTTE mining district contains extensive manganese vein deposits in the outer zone, surrounding the copper and zinc deposits and corresponding to the well known silver zone. This article describes the mineralogy of the manganese veins, the oxidation and enrichment processes, and the use of this information in prospecting. Information was derived from a study of the Emma, Star West, Tzarena, and Norwich mines, selected as representative of the district. Vein exposures at these mines were mapped, studied, and sampled on the outcrops and throughout the oxidized zone. Specimens were cut and polished for minera-graphic examination, identification, and textural studies. Knowledge of the manganese oxide minerals is scanty, previous information having been rendered obsolete by publication of the first correctly identified list of manganese oxide minerals by Fleischer and Richmond in 1943. Positive identification of the manganese oxides is possible only by X-ray analysis. Identifications for this study were made by the author with a Phillip's Diffractometer at the Montana School of Mines and confirmed by Lester Zeihen of The Anaconda Co., using a Norelco X-ray camera. It was necessiary to re-evaluate some X-ray data, as published patterns of several manganese oxides proved to be of mixtures, mostly showing pyrolusite as a contaminant. Perhaps the most useful information on oxidation and enrichment of manganese is presented in recent books by Goldschmidt1 and Rankama and Sahama.2 While their hypotheses are not conclusively proved, all laboratory and field evidence has served to substantiate them. This information was very useful in this study. Mineralogy: The primary minerals of the manganese veins are chiefly rhodochrosite and quartz. Rhodonite is abundant in the northern part of the district and in places has been found to comprise over a third of the vein matter. A variable but generally small amount of sulfides may be present, principally pyrite and silver minerals. Sphalerite is progressively more abundant near the zinc zone. Rhodochrosite is believed to form complete iso-morphous series with siderite, ankerite, and calcite. Some variation into these compositions is common, and the intermediate forms are termed manganosid-erite, manganankerite, and rnanganocalcite. Much of the rhodochrosite is remarkably pure. Other manganese minerals in the district include huebner-ite, alabandite, and helvite. Ramsdellite (MnO2, orthorhnmbic) is the principal manganese oxide mineral, comprising perhaps two-thirds of the total oxides. It is dull to iron black, and generally massive or platy in structure. A prominent platy cleavage is the only distinguishing megascopic characteristic. Pyrolusite (MnO2, tetragonal) is next most abundant to ramsdellite, with which it is usually intimately mixed. The luster is often brighter or more metallic than in ramsdellite, and needle-like crystals are diagnostic. Pyrolusite is common in small cavities formed by oxidation of pyrite grains. It is relatively abundant in zones of high limonite content. Cryptomelane (KMnO16 tetragonal ?) is rare in the outcrop, but becomes more abundant with depth. At depths of several hundred feet it is the principal oxide. Although its appearance varies, a blue-black flinty luster and blocky to conchoidal fracture are most common. A potassium flame test will identify this mineral. Hardness of all three oxides varies from 2 to 6. The three are quite commonly intermixed, and their textures can vary greatly. The commonest textures are massive or colloform, representative of colloidal deposition, or vuggy and boxwork textures, formed by partial leaching and oxidation in place. A box-work of either ramsdellite or chalcedony is formed after rhodochrosite rhombs and is indicative of ore shoots in this district. Some replacement of both quartz and the granitic wallrock by ramsdellite has been noted, but most of the oxide was deposited as a fissure filling by fine particles. No trace of manganite, hausmannite, braunite, or manganosite was found. No minerals of the psilome-lane group were detected besides cryptomelane. Amorphous MnO, was found at several spots. A specimen of oxide coated with yellow barite crystals was amorphous and not psilomelane (BaMn9O18. 2H2O). Voids formed by the leaching of sphalerite were coated with cryptomelane, not hetaerolite (ZnMn2O4) as might be expected. No manganese sulfate minerals were found in the gossans; however manganese alum (apjohnite ?) has been re-

Jan 1, 1957

By R. D. Hagni

The following is a case study illustrating the use of thin sections and polished sections of crude ore to predict metallurgical response. By examining polished sections of the metallurgical products, the textural and mineralogical reasons for unsatisfactory separation can be explained. An area of oxidized Negaunee Iron-Formation located south of Negaunee, Michigan, in the Marquette Iron Range, has been considered for roast reduction-magnetic separation. Preliminary metallurgical studies and subsequent pilot plant testing produced varied results. These results prompted this microscopic study which began with an examination of 126 thin sections and 82 polished sections prepared from 126

Jan 1, 1967

By W. C. Lacy

THE Cuajone porphyry copper deposit is the northernmost of a group of three deposits in southern Peru controlled by the Southern Peru Copper Corp.-Toquepala, Quelleveco, and Cuajone— all within a 20-mile belt. Although small pockets of high-grade copper oxide ores were worked in the Cuajone area in the 19th century, it was not until 1939 that its potentialities as a disseminated deposit were recognized by 0. C. Schmedeman. An exploratory drilling pro- gram was begun in December 1942 and continued until early 1945. The program was revived in November 1952 and completed early in 1954. Early exploration was by diamond drilling. Later exploration was predominantly churn drilling, with diamond drilling used only for wildcat holes. Along this northwest-trending belt of deposits. which follows the western slopes of the Andean Range, quartz-monzonite has invaded earlier dio-rite intrusives and a series of warped and tilted Cretaceous volcanic flows. Little faulting of consequence has been recognized within the mineralized areas. Sulfide minerals were introduced into all these diverse rocks, and mineralization was followed by erosion, oxidation, and enrichment. In Late Tertiary and/or Quaternary time the entire

Jan 1, 1959

By W. M. Tuddenham, R. J. P. Lyon

In many areas surrounding the orebodies in mining districts rocks have been bleached and altered by the ore-forming solutions and have been oxidized during later weathering processes. A number of the rock-forming silic-ates have been broken down to clay, sericitic micas and chlorites have been developed, and pyrite may be found hundreds of feet outside the economic limits of the orebody. These halos of altered ground are prime targets used by geologists in many districts to delineate promising sites for drilling. Both in the field and in the laboratory it is often difficult to map these mineralogical changes in the halos in detail without numerous petrologic examinations. The secondary minerals are generally fine-grained, and since conversion of one mineral to another is often progressive, many alteration processes have not proceeded to completion (feldspars to clay to sericite mica). Qualitative detection of these minerals is difficult; quantitative determination is frequently impossible.

Jan 1, 1960

By W. C. Lacy

This article is a progress report of a program designed to quantitatively evaluate geological parameters to predict stable slope angles. The author feels that, although there does not appear to be any one technique or characteristics that will suffice as an index to the determination of stable slope angles, a combination of seismic methods as outlined here, detailed geological mapping and logging of core, and a better understanding of the angle of internal friction in rock types will permit accurate estimation. A mining engineer friend once remarked, "If we don't have pit slope failures, the slopes are too flat." Since economic justification of an open pit project is based upon ultimate pit slopes, we cannot wait until the pit is developed and slopes established by trial and error. Some combination of geological and/or geophysical techniques must be developed to permit accurate prediction of stable slope angles and to suggest modification of pit outlines to result in slopes enabling maximum economic yield. This presentation is a progress report of a program designed to quantitatively evaluate geological parameters to predict stable slope angles. The principle of the weakest link applies to any slope stability evaluation and necessitates detailed geological examination and recording of observations. Physical failure will occur along any surface where shearing stress exceeds shearing resistance. Rock conditions are seldom uniform even within a single cut or pit face, so stability conditions will vary. Consequently, both plan outline and ultimate slope limits must be tailored to the specific situation. Economic advantages to be gained by slight increases in slope angles in deep pits are well recognized and stimulate efforts to obtain maximum permissible slope angles. MECHANICS OF SLOPE FAILURE Excellent reviews on the nature of slope failure have been presented+2,6,8,11 For the purpose of this study, the writer considers failure to take place by one or more of three processes: 1) ravelling, 2) translation or slope failure, and 3) rotation or base failure (Fig. 1). The effects of increased pore water pressure in soils were recognized in 1923 by Terzaghi in his development of the concept of effective stress, and he has applied the same principle to jointed rocks designating water pressure as cleft-water pressure.8 Cleft-water pressure in a rock slope reduces normal pressure on the plane of failure, thus reducing shearing resistance and resulting in slope failure. In the following discussion it is assumed that adequate drainage is supplied to prevent any build-up of water pressure. This is the first step in any program to establish maximum slopes. Ravelling: Ravelling occurs in rocks with low cohesion and entails the free movement of individual fragments ranging from single rock falls to running ground. Removal of lateral support wherever slope angle exceeds the angle of repose of the rock parti-

Jan 1, 1963

By G. Carman Ridland

Front Range, Colorado: The majority of the rocks comprising the Front Range of Colorado are pre-Cambrian schists, gneisses, and intrusives which have been elevated to form part of the Southern Rocky Mountain physiographic province. The region is noted mainly for its production of gold and silver, but ores of tungsten, fluorspar, uranium, copper, and iron have been worked. Geological literature1-' describes pitchblende and other radioactive minerals occurring at Jamestown, Boulder County; Central City, Gilpin County; and Lawson, Clear Creek County (fig. 1). These three adjoining G. CARMAN RIDLAND, Member AIME, is a Consulting Geological Engineer, New York, N. Y. San Francisco Meeting, February 1949. TP 2738 IL. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received March 30, 1949. counties cover most of the highly mineralized section of the Front Range which extends from Jamestown to Breckenridge. As far as the writer is aware, uranium has been found only in the portion northeast of Lawson. Silver Deposits at Caribou Hill: The historic silver deposits of Caribou Hill, located approximately half way between Jamestown and Central City, and 35 miles in a straight line northwest of Denver, appeared particularly intriguing as an area to prospect for uranium for the following reasons: here exists an isolated group of high-grade silver veins in the center of a mining district containing occurrences of uranium, and, in two of the well-known uranium deposits of the world, those at Great Bear Lake, Canada, and Joachimsthal, Czechoslovakia, uranium is associated with silver in similar fissure veins. An exploration program, conducted in the spring of 1945, directed special attention to Caribou Hill and was rewarded with the discovery of heavy, canary-yellow stained specimens of'pitchblende. The veins are confined to shear zones cutting a north-south, elongated quartz-monzonite stock of Tertiary (?) age lying in the axis of a major anticline of the Idaho Springs biotite schist, the oldest pre-Cambrian formation in the district. The stock is one and three-quarter miles long by more than a mile wide, and Caribou Hill is approximately at its center. The ore zones vary in width from a few inches to 15 ft, and one structure has been traced for a length of over 4000 ft. The ore minerals are galena, sphalerite, ruby silver, native silver, chalcopyrite, pyrite, and pitchblende. They occur most common-

Jan 1, 1951

By G. Carman Ridland

Front Range, Colorado: The majority of the rocks comprising the Front Range of Colorado are pre-Cambrian schists, gneisses, and intrusives which have been elevated to form part of the Southern Rocky Mountain physiographic province. The region is noted mainly for its production of gold and silver, but ores of tungsten, fluorspar, uranium, copper, and iron have been worked. Geological literature1-' describes pitchblende and other radioactive minerals occurring at Jamestown, Boulder County; Central City, Gilpin County; and Lawson, Clear Creek County (fig. 1). These three adjoining G. CARMAN RIDLAND, Member AIME, is a Consulting Geological Engineer, New York, N. Y. San Francisco Meeting, February 1949. TP 2738 IL. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received March 30, 1949. counties cover most of the highly mineralized section of the Front Range which extends from Jamestown to Breckenridge. As far as the writer is aware, uranium has been found only in the portion northeast of Lawson. Silver Deposits at Caribou Hill: The historic silver deposits of Caribou Hill, located approximately half way between Jamestown and Central City, and 35 miles in a straight line northwest of Denver, appeared particularly intriguing as an area to prospect for uranium for the following reasons: here exists an isolated group of high-grade silver veins in the center of a mining district containing occurrences of uranium, and, in two of the well-known uranium deposits of the world, those at Great Bear Lake, Canada, and Joachimsthal, Czechoslovakia, uranium is associated with silver in similar fissure veins. An exploration program, conducted in the spring of 1945, directed special attention to Caribou Hill and was rewarded with the discovery of heavy, canary-yellow stained specimens of'pitchblende. The veins are confined to shear zones cutting a north-south, elongated quartz-monzonite stock of Tertiary (?) age lying in the axis of a major anticline of the Idaho Springs biotite schist, the oldest pre-Cambrian formation in the district. The stock is one and three-quarter miles long by more than a mile wide, and Caribou Hill is approximately at its center. The ore zones vary in width from a few inches to 15 ft, and one structure has been traced for a length of over 4000 ft. The ore minerals are galena, sphalerite, ruby silver, native silver, chalcopyrite, pyrite, and pitchblende. They occur most common-

Jan 1, 1951

By S. V. Krusiewski, J. W. Gabelman

Regional metallogenic zones and areas of equal paragenetic range have been interpreted from a compiled metallogenic map. of Mexico. Mineralization gradients of the pattern subsequently identified extend inland from coastal zones of high-temperature mineralization, and join in a central longitudinal zone of relatively low-temperature mineralization, apparently leaving no zonal room for lowest temperature deposits. The striking regional zoning pattern can be correlated with regional deformation gradients of similar position and orientation. The gradients represent at least three major orogenic cycles in two structural belts. Paleozoic structural belts existed along each coast with deformation gradients diminishing inland toward a narrow, central peninsular craton. The Mesozoic-Tertiary Mexican (Cordilleran) belt covered the entire country with a gradient oriented toward the Gulf of Mexico. Most ore deposits in this belt are of Tertiary age, although Tertiary mineralization gradients seem to have "inherited" the pattern left by Paleozoic tectonic gradients. Mineralization gradients can be used to identify the regions most favorable for the occurrence of selected metals. A metallogenic province is characterized by particular proportions of various metals, and the relative proportions can vary from province to province; but within any province the same intensity of mineralization would produce similar deposits in different places. Declining intensity of minetalization produces different kinds and sizes of deposits in zones that are concentrically arranged around sites of strongest rock alteration. On a regional basis, districts of similar average intensity of mineralization occur in zones that generally parallel some tectonic grain with the result that tectonic deformation has been designated a principal cause of mineralization. Variations in the type and intensity of deformation would determine the type as well as size of metal deposits. Mexico is especially favorable for such a study be- cause of its great abundance and variety of epi-genetic mineral deposits in various lithologic, structural and tectonic environments. The concept is also useful in recognizing portions of Mexico favorable for the occurrence of specific metals. METALLOTECTONIC ZONING IN MEXICO Theory: In studies of individual districts and groups of districts throughout North and South America, areal zoning of metal deposits generally seemed to respond to the paragenetic sequence of iron, gold, copper, zinc, lead, silver, antimony and arsenic, gold and fluorite. However, the definition of district zones is greatly obscured by contemporaneous or rhythmic deposition of metals, especially in the middle of the paragenetic range, and by the common superimposi-tions of different generations of metals. Zones could usually be distinguished only for groups of metals, such as early precious metals, base-metal sulfides, sulfosalts and late precious metals. The best defined zoning in a district is normally the spatial separation of the greatest volumes of altered and metallized rocks.' Exceptions are districts representing the high- and low-temperature extremes of the mineralization range where the former creates a matrix for the latter. In most districts the total quantity of alteration products is greatly in excess of, and appears to be roughly proportional to, the total quantity of metallization products. Subsequent to the bicomponent nature of each district, the most important mineralogical feature is the great excess of one to several metals or minerals which results in a district identifiable as one of predominantly gold, copper, lead-zinc, fluorite, etc., although a great variety of other elements may be present. The para-genetic range for the abundant elements in any district is only a portion of the entire possible range for all the elements representing the complete process throughout the region. Early during investigations of this type, it became apparent that the consistent bicomponent character of districts allows two methods for studying epi-genetic mineralization patterns. One is to identify and plot altered rock "pipes,"* which are easily recognizable in the landscape by their anomalous

Jan 1, 1969

By George M. Schwartz, Ian L. Reid

THE Soudan mine in the Vermilion district of northeastern Minnesota is the oldest iron mine in the state. It has shipped ore every year since 1884 and still contributes a yearly quota of high grade lump ore. No comprehensive report on the Vermilion iron-bearing district has appeared since Clements' monograph,' but Gruner2 discussed the possible origin of the ores in 1926, 1930, and 1932, and recently Reid and Hustad have added data on mining and geology .3, 4 For many years geologists of the Oliver Iron Mining Div., U. S. Steel Corp., have kept up to date a series of plans and vertical sections of the Soudan mine. In connection with mine operation considerable diamond drilling has been done, and this, together with the mine openings, has permitted a reasonably accurate picture of the structure of the orebodies and wall rocks. It has long been evident to geologists familiar with the mine that the ores were not a result of weathering, a point emphasized by Gruner in 1926 and 1930. As the deeper orebodies were developed it also became clear that replacement had played an important part in their development. In recent years it has been recognized that other iron ores were formed by replacement, as Roberts and Bartly5 have argued strongly for the deposits at Steep Rock Lake. On the basis of these facts G. M. Schwartz suggested to members of the Oliver staff that it would be desirable to study the evidence of replacement, particularly the possible alteration of the wall rock which would be expected if the replacement was a result of hypogene solutions. Rock Formations: The formations directly involved in the iron orebodies of the Soudan mine are few though far from simple. The country rock is largely the Ely greenstone of Keewatin age consisting of a mass of metamorphosed lava flows, tuffs, and intrusives which have been more or less altered by hydrothermal solutions. The predominant rock is chlorite schist. Interbedded with the original flows and tuffs are a series of beds and lenses of jasper to which the name Soudan formation has been applied. In the Vermilion district the term jaspilite has been used for interbanded jasper and hematite. According to modern usage these jasper or jaspilite beds do not comprise a formation separate from the Ely greenstone, inasmuch as the beds of jasper are interbedded with the flows and tuffs of the upper part of the greenstone. It would more nearly accord with modern usage to consider the Soudan beds a member of the upper part of the Ely formation. Because of incomplete rock exposure and exploration the number of interbedded jaspilite beds is unknown. In the mine, however, as many as nine major beds of jasper are known on a cross-section of one limb of the syncline, with an equal number on the other limb. In addition diamond drill cores show beds of greenstone down to half an inch in thickness. The thin beds are probably always tuffs. Structure: Rock structure in the Soudan area is complex, and because there are no recognizable horizons within the greenstone it is extremely difficult to work out the details. Generally speaking, the major regional structure is an anticlinorium, the axis trending east-west, with a westerly pitch. The Soudan mine is related to a synclinal structure on the north limb of the anticline about a mile from the west nose of the folded iron formation. The general structure at the mine is that of a closely folded minor syncline on the major regional anticline. A cross fault has dropped the east side so that the bottom of the syncline has not been reached, whereas to the west it is well shown by the mine openings and diamond drill exploration. Throughout the mine the beds of jasper, and ore-bodies that have replaced the jasper, normally dip northward at angles of 80" or steeper. In detail the jasper beds are extremely folded, probably as a result of deformation while they were still relatively unconsolidated. Orebodies: Ore in the Soudan mine is mainly a hard, dense, bluish hematite. Locally ore has been brecciated and cemented by quartz. The vugs commonly occurring near the borders of orebodies are lined with quartz crystals. They seem to have formed as part of the ore-forming process and are evidence that no folding or compression of the ore has taken place. The orebodies are numerous, varying greatly in size. Many lenses of high grade hematite are too small to be mined. Some of the larger orebodies have been followed vertically for as much as 2500 ft and horizontally up to 1500 ft. The large ore-bodies are extremely irregular in outline in the plane of the beds of jaspilite. In width they are more regular, as they are strictly governed by the width of the jaspilite beds and the greenstone wall rock, which seems to have resisted replacement by hematite. At many places the orebodies replace the jaspilite completely and have a footwall and hanging wall of greenstone. At other places either one or both walls may be jaspilite. Geologists who have studied the orebodies in recent years agree that evidence for the replacement origin of the hematite bodies seems conclusive. AS noted above, many of the orebodies replace jaspilite beds from wall to wall with no evidence whatever of compaction. The replacement origin is also supported by details of the banding which is characteristic of the

Jan 1, 1956

By J. B. Stubbins, R. A. Blais

Extensive geological work was initiated — and continues — when operations of the Iron Ore Co. of Canada commenced in the Labrador-New Quebec area. Such geological operations include: mapping, test pitting, drilling, underground workings, volume factor and structure tests, and the calculation of ore grades and tonnages. Details of such work are given. Development is carried sufficiently ahead of mining to provide reliable tonnage and grade estimates and allow final mine planning. In order to make full use of geology in mining operations, the pit engineer combines the duties of geologist and mining engineer. The iron deposits of the Knob Lake range are located in the central part of the Labrador peninsula, a territory nearly twice the size of Texas, which is bounded by Hudson Bay on the west, Hudson Strait on the north, the Atlantic Ocean on the east and the Gulf of St. Lawrence on the south. The mining district proper is about 1000 miles northeast of Toronto. A 360-mile railroad links this mining area to the port of Sept-Iles on the Gulf of St. Lawrence. Schef-ferville, which is only a few miles from the open-pit mines, is the center of operations of the Iron Ore Co. of Canada. It has a population of nearly 5000. The nearest settlement is Labrador City, some 120 miles to the south, where this company is erecting a large plant for beneficiating its huge reserves of local low-grade iron ores. HISTORY The mineral possibilities of the area were recognized as early as the end of the last century, when A.P. LOW' of the Geological Survey of Canada made his famous trek across the Labrador Peninsula. After mapping several belts of iron formation, Lovr recommended that the area be thoroughly prospected for iron. In 1929, two well known Canadian geologists, J.E. Gill and U'.F. James, led a private expedition in central Labrador and discovered the first deposit of high-grade iron ore near what is now the Ruth Lake Mine. In 1936 the Labrador Mining and Exploration Co. was formed to 11ake over a prospecting concession of over 20,000 sq miles in central Labrador. An adjoining concession of 3900 sq miles in New Quebec was obtained in 1942 by Hollinger Consolidated Gold Mines, which had just Purchased the Labrador Co. The same year the M.A. Hanna Co. Purchased an interest in both exploration companies. From 1942 to 1950 extensive exploration was conducted by the Hollinger-Hanna technical staff to systematically appraise these vast concessions. More than 40 deposits of high grade ore were found and, by the end of 1950, the total ore reserves reached 418 million tons. In 1949 five American steel companies joined the Hollinger-Hanna interests and formed the Iron Ore Co. of Canada. Financing and full-scale construction were decided upon in 1950. This included the construction of a 360-mile railroad through very difficult terrain, the erection of two hydroelectric plants, the installation of terminal port facilities at Sept-IIes, the building of a modern town-site at Schefferville, the construction of crushing and screening plants, and the preparation of deposits for mining. Ore was first shipped in July 1954. Total open-pit mine production to date is 66 million long tons of direct-shipping ore. GEOLOGICAL ENGINEERING The above achievements would not have been possible without irtegrated teamwork of people of diverse skills and extensive use of geology. In their paper on the role of geologists in the development of this iron ore field, (Gustafson and Moss1 rightly emphasized the difficulties facing the early workers in the area. In an uninhabited land with no roads or railroads and no navigable rivers leading to the interior, everything had to be flown in. It was not until 1948 that aerial photographs and adequate base maps became available. In spite of these and other difficulties, an impressive amount of field work has been done since 1942. Nearly all this work has been directed by geological engineers and geologists. About 15,000 :sq miles have been geologically

Jan 1, 1962

By H. E. Hawkes, D. A. Barr

Time variations in the copper content of the sediments of streams draining mineralized areas were studied in two areas of contrasting climatic environment, one in northern and one in southern British Columbia. In each area, samples were collected and observations made of rainfall, stream discharge and air and water temperature at intervals throughout the summer season. Samples were analyzed for total and cold-extractable copper. Results showed a weak inverse relation between cold-extractable copper and discharge in two out of the three test sites in the southern area, and a decrease in ratio of COld-extractable to total copper over the duration of the test period at a highly anomalous site in the northern area. In suspended rock flour resulting from glacial erosion of mineralized rock in the northern area, virtually all the copper was found to be soluble in cold, dilute hydrochloric acid. None of the variations observed is sufficient to cause serious problems in geochemical sediment surveys. Systematic collection and trace analysis of stream sediments has seen wide application in recent years as a method of primary prospecting in primitive areas. Common practice is to collect fine-grained samples of sediment either from the active channel or from the flood plain near the channel. Samples are dried, sieved and the -80-mesh fraction analyzed after breakdown of the sample by a relatively strong attack, such as by fusion or by treatment with hot perchloric acid. Drying, sieving and rigorous chemical attack requires established facilities, either in a well equipped central laboratory or in base camp. Thus analysis for total metal involves a substantial delay from the time the samples are collected until the analytical data can be reported. An alternative system uses a cold aqueous extrac-tant in place of the hot acid or flux.4 Advantages of the cold-extraction techniques are that kits can be prepared for use directly at the sample site and that, in some problems, the patterns in cold-extractable metal, usually abbreviated cxMe, are more useful as ore guides than the patterns in total metal.' In the course of operational geochemical sediment surveys, a problem that has come up repeatedly is failure to reproduce anomalous values or patterns by resampling the same areas. The mystery of the vanishing anomaly has led to speculation as to whether there is a significant variation in the metal content of sediment samples with the weather or with the time of year. Review of the published literature shows that a number of experiments have been carried out on time variations in the metal content of stream water.1,2,5,7-9 The only published report on time variations in stream sediments that has come to the authors' attention, however, is by Govett,3 working in Northern Rhodesia.

Jan 1, 1963

By J. Ruben Velasco, Roland B. Mulchay

CANANEA has long been recognized as a remarkable field for geologic study. The copper deposits and rocks of the district have been described by many geologists and engineers, but only the most general correlations have been made between Can-anea sedimentary rocks and other known sedimentary sections in the southwestern United States and northern Mexico. The present paper describes the Cananea sediments in greater detail than has been done before and attempts to fit the Cananea sedimentary section more closely into the geologic time table. The lack of well-preserved fossils has made it difficult to date the sediments accurately in geologic time, but it is possible to make tentative correlations between the Cananea sediments and the southeastern Arizona sections, based largely upon lithology and general position in the geologic column. It appears that sedimentation at Cananea and Bisbee may have been closely similar during Paleozoic time. Even such generalized correlations, however, may be subject to considerable modification in the future. The present study has led to the recognition of other problems of age and mineralization relationships in the Cananea district. Cananea is located in the north-central part of the state of Sonora, Mexico, at an elevation of 5270 ft. It is about 135 miles northeast of Hermosillo, the state capital, and 25 miles south of the international boundary. By road Cananea is 40 miles from the twin towns of Naco, Ariz., and Naco, Sonora, and about 50 miles from Bisbee, Ariz. It is served by the Nogales-Naco branch of the railroad, F.C. Pacifico, and is connected with Chihuahua and Mexico City by the Aeronaves airline. The headwaters of three rivers flowing to the Gulf of California are located in the Cananea Mountains: the San Pedro River, flowing to the north; the Sonora River, flowing south and west; and the Mag-dalena River, flowing west. Elenita Mountain, the highest point in the district, has an elevation of 8140 ft. The Cananea Mountains extend in a series of north-south to northwest-southeast spurs and ridges and are surrounded by gently sloping gravel plains. The mineralized area, lying across the southern and central parts of the range, is about 6 miles long and at most 2 miles wide. Elevations at the mines vary from 5300 ft at Cananea-Duluth mine at the southeast end of the district to between 6000 and 7000 ft at the west end of the mineralized area at Puertecitos-Elenita mines. Principal production has been from the intensely mineralized and altered area of Capote Basin in the central part of the district and the immediately surrounding area to the southeast. The district has produced over 2 billion lb of copper, substantial molybdenum, and minor amounts of lead, zinc, silver, and gold. Total production through 1949 is estimated at more than $300 million. In 1900 large-scale development was started at Cananea by W. C. Greene. Until World War II only high-grade ores were exploited; low-grade ores were extracted after the installation of a large concentrator in the early 1940's, and subsequent operations have been based upon mining and processing ores containing less than 1.0 pct copper from open-pit and underground workings. Mining and concentration of such low-grade ores, however, are made possible only by continued high copper prices, and active exploration for high-grade orebodies has been continued throughout the important mineralized areas. General Geology Study of the involved rock pattern at Cananea has indicated a complex geologic history for the district. Widespread alteration and mineralization have masked many of the salient features and have led to widely varying geologic interpretations over the years. Further work will probably disclose new information which will modify current beliefs. At Cananea a conformable series of sediments of probable Paleozoic age was deposited on an unknown basement. Following Paleozoic time there was an extended period of erosion common to many districts in the southwestern U. S., and there is no present evidence of marine sedimentation at Cananea after the Paleozoic. The eroded surface was eventually covered with a great thickness of extrusive volcanic rocks. The entire series of sediments and volcanic rocks was later intruded by a variety of deep-seated igneous rocks. These included the Cananea granite, the Cuitaca granodiorite, the El Torre syenite, the Tinaja diorite, the Campana diabase and gabbro and the Colorada rhyolite quartz porphyry. Faulting of early age, probably prior to the deposition of the volcanic rocks, may have been responsible for the present position of some of the intrusive rock masses. In the Capote mine on the third and fourth levels the northwest-striking Rick-etts fault zone, with apparent offset of about 800 ft, has been sealed by a dike-like mass of Cananea granite which gradually increases in size with depth. In lower levels of the mine the granite forms a large southeast-plunging mass generally following the course of the Ricketts zone. The granite is not known southeast of the Capote-Oversight mine areas and the Ricketts fault does not appear in the vol-canic~ southeast of Capote Basin, but several plugs of Colorada quartz porphyry cut the volcanics along the assumed general southeast trend of the Ricketts zone. These porphyritic intrusives may be the up-

Jan 1, 1955

By Robert E. Sorenson

EXPLORATION for deep-seated orebodies in the Silver Belt area of the Coeur d'Alene mining district is complicated by meager surface expressions of diagnostic criteria, lack of knowledge of the significance of specific alteration phenomena, and the great expense involved in the exploration for ore shoots, the tops of which often occur near sea level elevation or below and as much as 4000 ft or more below the surface. Except for the early studies of Ransome and Calkins in 1903 and 1904,' little geological work was done in the Coeur d'Alene district for many years, and it is only during the last 15 to 20 years that complete and careful geological mapping has been applied to most of the mines in the area. Much early information, which now would prove invaluable, is lost in hundreds of miles of caved and inaccessible mine openings not mapped by mining geologists. In more recent years mining geology has become a tool of greater use in the district, and some measurable progress is being made in the accumulation of observations that are adding gradually to the knowledge of ore deposits in the district. The recognition of alteration phenomena and related features by Hoyt S. Gale3 in 1935, followed by the work of Shenon and McConnel in 1936-37,4 changed many of the concepts formerly held and opened the way for more critical study and mapping of alteration effects. Mapping of these effects has been in progress for several years but no well-organized, careful, and complete laboratory study of the alteration has been made by mining companies or by government agencies. Recently, Thomas Mitcham of Columbia University has been occupied in the collection and study of specimens carefully selected from several producing mines in the Silver Belt as well as from several prospects exhibiting alteration effects. Mr. Mitcham and the writer have discussed some of the preliminary results of his investigations, which indicate that definite and interesting material is forthcoming from his studies. Work of this kind, aided by careful observation by district geologists, should advance the knowledge of the environment of Silver Belt ore shoots and establish additional criteria for recognizing meager shallow expressions of deep-lying orebodies. Structural details in the Silver Belt area are extremely difficult to decipher on the surface because the area is almost completely covered by a deep mantle of surface debris and soil. A dense growth of small trees and buck brush adds to a geologist's difficulties. Often large areas reveal only scattered small outcrops with great intervening areas where the underlying formations must be deduced from small altered rock fragments. Some considerable success in obtaining surface information has come from bulldozer roads and cuts in selected areas. As this type of work receives more attention, knowledge of the surface expressions of formations, alterations, faulting, and veining is expanding and giving more reliable information to guide deeper development. Lack of diagnostic marker beds in the district contributes to a geologist's difficulties in determining fault displacements. In the Silver Belt, known commercally important sulphide orebodies commonly are associated with siderite and quartz gangue. Some of the veins at shallow horizons above productive ore shoots are composed of quartz with light-colored carbonate minerals such as calcite, ferrocalcite, ferrodolomite, ankerite, and carbonates with variable amounts of manganese. The relation of these carbonates to commercial orebodies is a problem offering possibilities for research. Shallow exposures of veins composed of quartz and the light-colored carbonates, often with some associated barite, grade into quartz and siderite veins at deeper horizons. The vertical range of these carbonates has been partially established for some veins, but no reliable method has been devised for predicting where the change in a vein may take place. Careful observation and analysis of carbonates may make it possible to predict more closely where the change to siderite may be expected. In 1926 Shannon5 pointed out some of the characteristics of the carbonate veins of the district and included a few chemical analyses. Some of the Silver Belt ore shoots have small commercial outcrops, and very shallow development of some properties has led to the opening of small ore shoots." Several small ore shoots developed at shallow depths have not been explored at deep horizons, and some important ore shoots with no commercially significant exposures at shallow horizons have been developed. The greatest problem of the mining geologist working in the Silver Belt area is to find the all-important link between the very meager shallow expressions of mineralization and the rich ore shoots that may be found below. To develop criteria for use in the recognition of the weak upper expression of ore shoots, the experience of past development programs must be relied upon heavily. The investment of more than a million dollars in the exploration for such ore shoots requires some reliable criteria if these ore shoots are to be found. Management needs some assurance that the risk involved is justified by well-developed and acceptable geological inference. The richness of some of the ore shoots found thus far has contributed greatly to the justification for a bold approach, but many negative results of blind exploration programs would lead eventually to extreme caution on the part of management. Fortunately, recent experiences of development programs have been quite successful. It is hoped that added knowledge. of the environment of Silver Belt ore shoots will contribute greatly to the sureness of approach toward their development. The Coeur d'Alene mining district is located in the panhandle of Idaho in Shoshone County. The population of the county is either employed in the

Jan 1, 1952

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963