Analytical results and sample locality map of soil samples from the Rio Vivi porphyry copper district, municipios of Utuado and Adjuntas, Puerto Rico
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Geology topics
Publications and source records attributed to R. E. Learned.
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To test the relative effectiveness of stream water and sediment as geochemical exploration media in the Rio Tanama porphyry copper district of Puerto Rico, we collected and subsequently analyzed samples of water and sediment from 29 sites in the rivers and tributaries of the district. Copper, Mo, Pb, Zn, SO 4 2− , and pH were determined in the waters; Cu, Mo, Pb, and Zn were determined in the sediments. In addition, copper in five partial extractions from the sediments was determined. Geochemical contrast (anomaly-to-background quotient) was the principal criterion by which the effectiveness of the two media and the five extractions were judged. Among the distribution patterns of metals in stream water, that of copper most clearly delineates the known porphyry copper deposits and yields the longest discernable dispersion train. The distribution patterns of Mo, Pb, and Zn in water show little relationship to the known mineralization. The distribution of SO 4 2− in water delineates the copper deposits and also the more extensive pyrite alteration in the district; its recognizable downstream dispersion train is substantially longer than those of the metals, either in water or sediment. Low pH values in small tributaries delineate areas of known sulfide mineralization. The distribution patterns of copper in sediments clearly delineate the known deposits, and the dispersion trains are longer than those of copper in water. The partial determinations of copper related to secondary iron and manganese oxides yield the strongest geochemical contrasts and longest recognizable dispersion trains. Significantly high concentrations of molybdenum in sediments were found at only three sites, all within one-half km downstream of the known copper deposits. The distribution patterns of lead and zinc in sediments are clearly related to the known primary lead-zinc haloes around the copper deposits. The recognizable downstream dispersion trains of lead and zinc are shorter than those of copper.
A hydrogeochemical survey utilizing waters from streams and springs was conducted in the area of two known porphyry copper deposits in the tropical-marine climate of westcentral Puerto Rico. The most important pathfinder for regional hydrogeochemical surveys is sulfate which reflects the associated pyrite mineralization. Because of increased mobility due to intense chemical weathering and the low pH environment, dissolved copper can also be used as a pathfinder for regional surveys and has the advantage of distinguishing barren pyrite from pyrite associated with copper mineralization. For follow-up surveys, the most important pathfinders are copper, sulfate, pH, zinc, and fluoride. High concentrations of dissolved copper and moderate concentrations of sulfate is a diagnostic indication of nearby sources of copper minerals. An understanding of the geochemical processes taking place in the streambeds and the weathering environment, such as the precipitation of secondary copper minerals, contributes to the interpretation of the geochemical data and the selection of the most favorable areas for further exploration.
In experiments designed to determine the manner in which copper is partitioned among selected phases that constitute geologic media, we have applied the five-step sequential extraction procedure of Chao and Theobald to the analysis of drill core, soils, and stream sediments of the Rio Vivi and Rio Tanama porphyry copper districts of Puerto Rico. The extraction procedure affords a convenient means of determining the trace-metal content of the following fractions: (1) Mn oxides and “reactive” Fe oxides; (2) “amorphous” Fe oxides; (3) “crystalline” Fe oxides; (4) sulfides and magnetite; and (5) silicates. An additional extraction between steps (1) and (2) was performed to determine organic-related copper in stream sediments. The experimental results indicate that apportionment of copper among phases constituting geologic media is a function of geochemical environment. Distinctive partitioning patterns were derived from the analysis of drill core from each of three geochemical zones: (a) the supergene zone of oxidation; (b) the supergene zone of enrichment; and (c) the hypogene zone; and similarly, from the analysis of; (d) soils on a weakly leached capping; (e) soils on a strongly leached capping; and (f) active stream sediment. The experimental results also show that geochemical contrasts (anomaly-to-background ratios) vary widely among the five fractions of each sampling medium investigated, and that at least one fraction of each medium provides substantially stronger contrast than does the bulk medium. Fraction (1) provides optimal contrast for stream sediments of the district; fraction (2) provides optimal contrast for soils on a weakly leached capping; fraction (3) provides optimal contrast for soils on a strongly leached capping. Selective extraction procedures appear to have important applications to the orientation and interpretive stages of geochemical exploration. Further investigation and testing of a similar nature are recommended.
Livingstonite is the principal ore mineral in the deposits of the Huitzuco District in the State of Guerrero, Mexico. The ore is found in the lower part of the Morelos Formation, which consists of a thick bed of sedimentary anhydrite containing lenses of dolomite and dolomite breccia. In the unweathered ore practically all the mercury is in the livingstonite, whereas the antimony occurs partly in the livingstonite and partly in stibnite. Native sulfur forms pockets as much as 30 centimeters in diameter in the ore and is also found in gypsum on the surface away from the ore. It appears that the deposition of livingstonite, rather than of the combination of cinnabar and stibnite that is more usual in other districts, was caused by the native sulfur present in considerable quantity scattered through the sedimentary dolomite and anhydrite above, below, and in the ore. Since the formula of livingstonite is actually HgSb 4 S 8 (not HgSb 4 S 7 as was previously supposed), it is not stable in solutions containing only HgS, Sb 2 S 3 , Na 2 S, and H 2 O. It has been proved by one of us, experimentally, that in order to form livingstonite, the solutions must contain elemental sulfur in addition to HgS, Sb 2 S 3 , Na 2 S, and H 2 O. In such solutions the solubility of mercuric sulfide is extremely low. However, the problem of transport is overcome if the elemental sulfur is already present in the wall rock. In that case, the reaction of the elemental sulfur with a solution containing mercuric sulfide and antimony sulfide, but not saturated with either, would precipitate livingstonite, as was proved by our experimental work.
The common occurrence of cinnabar and stibnite in well-defined districts in the same epithermal environments suggests that similar physiochemical processes are responsible for the genesis of the two minerals; however, cinnabar and stibnite tend to be segregated within these districts and also within individual deposits that contain both minerals. Where cinnabar and stibnite occur in contact, textural evidence indicates that cinnabar is generally younger, although some textures suggest overlap of deposition. To better understand the physicochemical processes involved in the formation of cinnabar and stibnite deposits, we investigated the solubilities of cinnabar and stibnite in aqueous Na 2 S solutions that were simultaneously saturated with both cinnabar and stibnite at concentrations from 0.384 percent (0.0492 mol/kg) to 1.772 percent(0.227 mol/kg)Na 2 S at temperatures from 150° to 250°C, at 100 bars pressure. The ratio of dissolved Sb 2 S 3 to HgS under most conditions is larger than 25:1 moles per mole. We conclude that alkaline sulfide solutions could not transport geologically appreciable amounts of HgS while they are saturated with stibnite; major amounts of HgS could only be transported in solutions that are undersaturated with stibnite. Solubility behavior of HgS and Sb 2 S 3 is thus a possible mechanism for the segregation of cinnabar and stibnite, especially when the conduit system is modified during the episode of mineralization. The deposition of stibnite before that of cinnabar in most places but with minor overlapping deposition in some places is in accord with deductions made from the solubility studies.
The mercury content in soil gas and in the atmosphere was measured in several mining districts to test the possibility that the mercury content in the atmosphere is higher over ore deposits than over barren ground. At Cortez, Nev., the distribution of anorhalous amounts of mercury in the air collected at ground level (soil gas) correlates well with the distribution of gold-bearing rocks that are covered by as much as 100 feet of gravel. The mercury content in the atmosphere collected at an altitude of 200 feet by an aircraft was 20 times background over a mercury posit and 10 times background over two porphyry copper deposits. Measurement of mercury in soil gas and air may prove to be a valuable exploration tool.
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