Geology topics
Publications and source records attributed to R. F. Sanzolone.
Samples of massive sulfide layers show an enrichment in many minor and trace elements in the central part of layers. Comparison of trace element contents of massive sulfides, magnetite, and disseminated sulfides suggests differences in origin. Trace element contents of samples from various mines suggest regional variations.
We evaluated the trace element content of gossans at four mines in the West Shasta Cu-Zn mining district in California. We found little difference in trace element content between the chipped rock rind and whole-rock gossan samples. Gossans derived from disseminated sulfides were found to have a lower trace element content as well as a narrower range of values than did gossans derived from massive sulfides. Extreme differences in trace element concentrations in field duplicates of both chip and whole-rock gossan samples due to variations within the gossan bodies prevented use of the data at individual sampling sites for areal pattern studies. A computer program (REM), which uses a cell concept and groups the analysis of gossan at each mine, was used to characterize the trace element content. The gossan at the Mammoth mine had the highest anomaly magnitude and the highest element magnitudes for the most elements. Gossan at the Spread Eagle mine had a much different assemblage of elements relative to the other mines studied and had the lowest anomaly magnitude.
Iron is a common interferent in the determination of many elements in geochemical samples. Two approaches for its removal have been taken. The first involves removal of iron by extraction with methyl isobutyl ketone (MIBK) from hydrochloric acid medium, leaving the analytes in the aqueous phase. The second consists of reduction of iron(III) to iron(II) by ascorbic acid to minimize its extraction into MIBK, so that the analytes may be isolated by extraction. Elements of interest can then be determined using the aqueous solution or the organic extract, as appropriate. Operating factors such as the concentration of hydrochloric acid, amounts of iron present, number of extractions, the presence or absence of a salting-out agent, and the optimum ratio of ascorbic acid to iron have been determined. These factors have general applications in geochemical analysis by atomic-absorption spectrophotometry.
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.
We evaluated the effectiveness of iron oxide-rich fracture coatings as a geochemical sampling medium for disseminated gold deposits, as compared with conventional lithogeochemical methods, for samples from the Pinson mine and Preble prospect in southeastern Humboldt County, Nevada. That disseminated gold mineralization is associated with Hg, As, and Sb is clearly demonstrated in these deposits for both fracture coatings and rock chip samples. However, the relationship is more pronounced for fracture coatings. Fracture coatings at Pinson contain an average of 3.61, 5.13, 14.37, and 3.42 times more Au, As, Sb and Hg, respectively, than adjacent rock samples. At Preble, fracture coatings contain 3.13, 9.72, 9.18, and 1.85 times more Au, As, Sb and Hg, respectively, than do adjacent rock samples. Geochemical anomalies determined from fracture coatings are thus typically more intense than those determined from rock samples for these elements. The sizes of anomalies indicated by fracture coatings are also somewhat larger, but this is less obvious. In both areas, Sb anomalies are more extensive in fracture coatings. At Preble, some Hg and Au anomalies are also more extensive in fracture coatings. In addition to halos formed by the Hg, As and Sb, high values for Au/Ag and Zn/(Fe + Mn) are closely associated with gold mineralization at the Pinson mine. The large enhancement in geochemical response afforded by fracture coatings indicates a definite potential in the search for buried disseminated gold deposits.
Based on modifications and expansion of the original Tindall's solvent extraction flame atomic-absorption procedure, an atomic-absorption spectrophotometric method has been developed for the determination of mercury in geological materials. The sample is digested with nitric and hydrochloric acids in a boiling water-bath. The solution is made ammoniacal and potassium iodide and silver nitrate are added. The mercury is extracted into isobutyl methyl ketone as the tetraiodomercurate(ll). Added silver is co-extracted with mercury and serves as a matrix modifier in the carbon-rod atomiser. The mercury in the isobutyl methyl ketone extract may be determined by either the flame- or the carbon-rod atomisation method, depending on the concentration level. The limits of determination are 0.05-10 p.p.m. of mercury for the carbon-rod atomisation and 1 -200 p.p.m. of mercury for the flame atomisation. Mercury values for reference samples obtained by replicate analyses are in good agreement with those reported by other workers, with relative standard deviations ranging from 2.3 to 0.9%. Recoveries of mercury spiked at two levels were 93-106%. Major and trace elements commonly found in geological materials do not interfere.
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.
Silver as a matrix modifier is shown to improve the carbon-rod atomization of both arsenic and selenium for atomic absorption spectrometry. Compared to nickel, the efficiency of silver is greater for arsenic and about the same for selenium. Silver fulfils two functions in its reaction, namely stabilization during the ashing stage and enhancement of absorbance in the final atomization.
An atomic-absorption spectrophotometric method with electrothermal atomisation has been developed for the determination of selenium in geological materials. The sample is decomposed with a mixture of nitric, perchloric and hydrofluoric acids and heated with hydrochloric acid to reduce selenium to selenium(IV). Selenium is then extracted into toluene from a hydrochloric acid-hydrobromic acid medium containing iron. A few micro-litres of the toluene extract are injected into a carbon rod atomiser, using a nickel solution as a matrix modifier. The limits of determination are 0.2–200 p.p.m. of selenium in a geological sample. For concentrations between 0.05 and 0.2 p.p.m., back-extraction of the selenium into dilute hydrochloric acid is employed before atomisation. Selenium values for reference samples obtained by replicate analysis are in general agreement with those reported by other workers, with relative standard deviations ranging from 4.1 to 8.8%. Recoveries of selenium spiked at two levels were 98–108%. Major and trace elements commonly encountered in geological materials do not interfere. Arsenic has a suppressing effect on the selenium signals, but only when its concentration is greater than 1 000 p.p.m. Nitric acid interferes seriously with the extraction of selenium and must be removed by evaporation in the sample-digestion step.
Rock and soil samples are decomposed with HClO 4 —HNO 3 ; after further treatment, arsine is generated and absorbed in a dilute silver nitrate solution. Aliquots of this solution are injected into a carbon rod atomizer. Down to 1 ppm As in samples can be determined and there are no significant interferences, even from chromium in soils. Good results were obtained for geochemical reference samples.
Suppression caused by five of the seven matrix elements studied (Si, Al, Fe, Ca and Mg) was observed in the atomic-absorption determination of manganese in geological materials, when synthetic solutions and the recommended oxidizing air—acetylene flame were used. The magnitude of the suppression effects depends on (1) the kind and concentration of the interfering elements, (2) the type of acid medium, and (3) the concentration of manganese to be determined. All interferences noted are removed or alleviated by using a reducing nitrous oxide—acetylene flame. The atomic-absorption method using this flame can be applied to the determination of total and extractable manganese in a wide range of geological materials without interferences. Analyses of six U.S. Geological Survey rock standards for manganese gave results in agreement with the reported values.
The sample is digested with a solution of hydrobromic acid and bromine and the excess of bromine is expelled. After dilution of the solution to approximately 3 M in hydrobromic acid, ascorbic acid is added to reduce iron(III) before extraction of tellurium into methyl isobutyl ketone (MIBK). An oxidizing air-acetylene flame is used to determine tellurium in the 0.1–20 ppm range. For samples containing 4–200 ppb of tellurium, a carbon-rod atomizer is used after the MIBK extract has been washed with 0.5 M hydrobromic acid to remove the residual iron. The flame procedure is useful for rapid preliminary monitoring, and the flameless procedure can determine tellurium at very low concentrations.
The geochemical investigation of the Superstition Wilderness, Maricopa, Pinal and Gila Counties, Arizona, consisted of the collection and analyses of 2269 samples. This included 1231 rocks and 1038 stream sediments. All samples were prepared and analyzed on location during two separate field seasons (fall of 1975 and 1976) by mobile laboratories of the U.S. Geological Survey. Sample localities and analytical results are listed in this report. Samples lie within the following U.S.G.S. topographic quadrangles: Goldfield, Mormon Flat Dam, Weavers Needle, Horse Mesa Dam, Iron Mountain, Pinyon Mountain, Haunted Canyon, and Two Bar Mountain. Locations for all samples are in Universal Transverse Mercator (UTM) coordinates, the X coordinate is the northing value, which ranges from 3,693,000 m to 3,720,000 m and the Y coordinate is the casting value, which ranges from 453,500 m to 500,000 m. Because of limitations of the computer program, the initial digit of the northing numbers has been dropped. Data of rocks are listed on Table 1 and stream sediments on Table 2. The analytical and geologic data were entered into a computer storage system (RASS II) by S. K. McDanal and retrievals were handled by T. M. Billings and George VanTrump. Geochemical sampling was carried out during geologic mapping by a U.S. Geological Survey field party consisting of D. W. Peterson, D. L. Gaskill, M. L. Sorenson, and W. E. Yeend, assisted by Kerwin Stark, N. H. Suneson, and G. D. Johnpeer. Analytical support was given by R. N. Babcock and D. G. Murrey.
Chemical dissolution treatments involving the use of aqua regia, 4 N HNO 3 , H 2 O 2 -ascorbic acid, oxalic acid, KClO 3 +HCl, and KClO 3 +HCl followed by 4 N HNO 3 were applied to specimens of nine common sulfide minerals (galena, chalcopyrite, cinnabar, molybdenite, orpiment, pyrite, stibnite, sphalerite, and tetrahedrite) mixed individually with a clay loam soil. The resultant decrease in the total sulfur content of the mixture, as determined by using the Leco induction furnace, was used to evaluate the effectiveness of each chemical treatment. A combination of KClO 3 +HCl followed by 4 N HNO 3 boiling gently for 20 min has been shown to be very effective in dissolving all the sulfide minerals. This treatment is recommended to dissolve metals residing in sulfide minerals admixed with secondary weathering products, as one step in a fractionation scheme whereby metals in soluble and adsorbed forms, and those associated with organic materials and secondary oxides, are first removed by other chemical extractants.
An atomic absorption spectrophotometric method has been developed for the determination of seven metal ions in the hydroxylamine extract of soils and sediments. Mn, Fe, and Zn are directly determined in the aqueous extract upon dilution. Co, Ni, Cu, and Pb in a separate aliquot of the extract are chelated with APDC (ammonium pyrrolidine dithiocarbamate) and extracted into MIBK (methyl isobutyl ketone) before determination. Data are presented to show the quantitative recovery of microgram levels of Co, Ni, Cu, and Pb by APDC-MIBK chelation-extraction from synthetic solutions containing as much as 2,000 ug/ml (micrograms per milliliter) Mn or 50 ug/ml Fe. Recovery of known amounts of the metal ions from sample solutions is equally satisfactory. Reproducible results are obtained by replicate analyses of two sediment samples for the seven metals.