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Flameless atomic-absorption determination of gold in geological materials

Gold in geologic material is dissolved using a solution of hydrobromic acid and bromine, extracted with methyl isobutyl ketone, and determined using an atomic-absorption spectrophotometer equipped with a graphite furnace atomizer. A comparison of results obtained by this flameless atomic-absorption method on U.S. Geological Survey reference rocks and geochemical samples with reported values and with results obtained by flame atomic-absorption shows that reasonable accuracy is achieved with improved precision. The sensitivity, accuracy, and precision of the method allows acquisition of data on the distribution of gold at or below its crustal abundance.

Journal of Geochemical Exploration↗

Geochemical evidence for a Brooks Range mineral belt, Alaska

Geochemical studies in the central Brooks Range, Alaska, delineate a regional, structurally controlled mineral belt in east—west-trending metamorphic rocks and adjacent metasedimentary rocks. The mineral belt extends eastward from the Ambler River quadrangle to the Chandalar and Philip Smith quadrangles, Alaska, from 147° to 156°W. longitude, a distance of more than 375 km, and spans a width from 67° to 69°N. latitude, a distance of more than 222 km. Within this belt are several occurrences of copper and molybdenum mineralization associated with meta-igneous, metasedimentary, and metavolcanic rocks; the geochemical study delineates target areas for additional occurrences. A total of 4677 stream-sediment and 2286 panned-concentrate samples were collected in the central Brooks Range, Alaska, from 1975 to 1979. The −80 mesh (< 177 μm) stream sediment and the heavy (specific gravity > 2.86) nonmagnetic fraction of the panned concentrates from stream sediment were analyzed by semiquantitative spectrographic methods. Two geochemical suites were recognized in this investigation; a base-metal suite of copper-lead-zinc and a molybdenum suite of molybdenum-tin-tungsten. These suites suggest several types of mineralization within the metamorphic belt. Anomalies in molybdenum with associated Cu and W suggest a potential porphyry molybdenum system associated with meta-igneous rocks. This regional study indicates that areas of metaigneous rocks in the central metamorphic belt are target areas for potential mineralized porphyry systems and that areas of metavolcanic rocks are target areas for potential massive sulfide mineralization.

Alaska↗

Manganese dioxide causes spurious gold values in flame atomic-absorption readings from HBr-Br2 digestions

False readings, apparently caused by the presence of high concentrations of manganese dioxide, have been observed in our current flame atomic-absorption procedure for the determination of gold. After a hydrobromic acid (HBr)-bromine (Br 2 ) leach, simply heating the sample to boiling to remove excess Br 2 prior to extraction with methyl-isobutyl-ketone (MIBK) eliminates these false readings.

Journal of Geochemical Exploration↗

Heavy metals and manganese oxides in the genesee watershed, New York state: Effects of geology and land use

Manganese oxide coatings on gravels from 255 sites on tributary streams in the Genesee River Watershed were analyzed for Mn, Fe, Zn, Cd, Co, Ni, Pb, and Cu. The results were compared with data on bedrock geology, surficial geology and land use, using factor analysis and stepwise multiple regression. All metals except Pb show strong positive correlation with Mn. This association results from the well-known tendency of Mn oxide precipitates to adsorb and incorporate dissolved trace metals. Pb may be present in a separate phase on the gravel surfaces; alternatively Pb abundance may be so strongly influenced by environmental factors that the effect of varying abundance of the carrier phase becomes relatively unimportant. When the effects of varying Mn abundance are allowed for, Pb and to a lesser extent Zn and Cu abundances are seen to be related to commercial, industrial and residential land use. In addition to this pollution effect, all the trace metals, Cd and Ni most strongly, tend to be more abundant in oxide coatings from streams in the forested uplands in the southern part of the area. This probably reflects increased geochemical mobility of the metals in the more acid soils and groundwater of the southern region. A strong Zn anomaly is present in streams draining areas underlain by the Lockport Formation. Oxide coatings in these streams contain up to 5% Zn, originating from disseminated sphalerite in the Lockport and secondary Zn concentrations in the overlying muck soils. The same group of metals, plus calcium and loss on ignition, were determined in the silt and clay (minus 230 mesh) fraction of stream sediments from 129 of the same sites, using a hot nitric acid leach. The amounts of manganese in the sediments are low (average 1020 ppm) and manganese oxides are, at most, of relatively minor significance in the trace-metal geochemistry of these sediments. The bulk of the trace metals in sediment appears to be associated with iron oxides, clays and organic matter.

New York↗

Regional geochemical studies in the Patagonia Mountains, Santa Cruz County, Arizona

The Patagonia Mountains in southern Arizona contain the deeply buried porphyry copper system at Red Mountain as well as a number of other base- and precious-metal mines and prospects. The range contains complex Basin and Range geology with units ranging in age from Precambrian to Holocene. Rock types present include igneous intrusive and extrusive units as well as sedimentary and metamorphic units, most of which have been tectonically disturbed. A total of 264 stream-sediment samples were collected and analyzed for 32 elements. Geochemical maps for Sb, Ag, Pb, Te, B, Mn, Au, Zn, Cu (total), Cu (cold-extractable), and Mo, as well as for Cu (cold-extractable)/Cu (total) and Fe/Mn, are presented. Anomaly patterns for these elements generally occur over the Red Mountain deposit and (or) along a north-northwest trend parallel to the major Harshaw Creek Fault. Much of the entire area sampled contains widespread anomalies for Pb, Te, and Cu; the other elements are only locally anomalous. Various plots of ratios of Cu (cold-extractable) to Cu (total) did not produce any new information not readily apparent on either one of the two copper maps. A plot of ratios of Fe to Mn delineated many areas of pyrite mineralization. Several of these areas may represent the pyritic halos around deeply buried porphyry copper systems. The best ore guide for the Red Mountain porphyry system is the coincidence of positive anomalies of Mo, Pb, and Te and a negative anomaly of Mn. Other areas with anomalies of the same suite of elements are present within the Patagonia Mountains. It is concluded that geochemical sampling, even in a highly contaminated area, can be useful in delineating major geologic features, such as porphyry copper belts and major faults. Multielement geochemical surveys on a regional scale can effectively locate large, deeply buried, zoned mineral systems such as that at Red Mountain. Plots of element ratios, where adequately understood, can provide geochemical information not readily discernible from plots of single elements alone.

Arizona↗

Sequential extraction techniques applied to a porphyry copper deposit in the basin and range province

Samples of minus-80-mesh (<180 μm) stream sediment, rock containing exposed fracture coatings, and jarosite and chrysocolla were collected from an area surrounding the North Silver Bell porphyry Cu deposit near Tucson, Arizona. The samples were subjected to a series of extractions in a scheme originally designed for use on samples from humid or sub-humid environments, in which the following fractions can effectively be separated: (1) carbonates and exchangeable metals; (2) Mn oxides; (3) organic compounds and sulfides; (4) hydrous Fe oxides; and (5) residual crystalline minerals. Jarosite and chrysocolla, two major minerals of the North Silver Bell area, were found to dissolve over two or more steps of the extraction scheme. The results represent only a limited number of samples from one copper deposit. Nevertheless, they do suggest that in a semiarid to arid environment, where mechanical dispersion of such minerals predominates, uncritical assignment of unique phases, such as Mn oxides or organics to a given extraction would lead to false interpretations of weathering processes. However, the relative proportions of elements dissolved in each step of the jarosite and chrysocolla extractions could be used as a “fingerprint” for recognition of the presence of these two minerals in the stream-sediment and rock samples. The relative abundance of hydrous Fe oxide and jarosite and the alteration zoning could be mapped using data from jarosite and chrysocolla extractions. Manganese oxides were also found to have a greater influence on Zn than on Cu or Pb during supergene alteration. The rapid change in relative importance of the first (1 M -acetic acid) extraction for Cu, Zn, and Pb near the mineralized zone suggested the occurrence of minor hydromorphic processes within the stream sediments. Thus, the acetic acid extraction proved the most effective for pinpointing mineralization in sediments. In contrast, the residual fraction had the longest dispersion train, suggesting that total metal concentrations are most effective in arid environments for reconnaissance surveys.

Journal of Geochemical Exploration↗

Geochemical prospecting for hydrocarbons in the outer continental shelf, Southern Bering Sea, Alaska

This geochemical survey is based on 20 stations located on the outer continental shelf of the southern Bering Sea in an area of 30,000 km 2 that includes St. George basin. Hydrocarbon gases from sediment samples recovered by gravity coring at each of the stations were analyzed by gas chromatography. Data are summarized for a subbottom depth of 0.5 m, because core penetration, although variable, reached at least this depth at all of these stations. Two parameters were used to distinguish the possible presence of thermogenic hydrocarbons: (1) ratios less than 50 of methane to ethane plus propane; and (2) ratios greater than 1 of ethane to ethene. No major hydrocarbon anomalies were discovered; however, at two stations at the northern end of St. George basin, our data indicate that thermogenic hydrocarbons may be present at depth. Major faulting in the vicinity of these stations could provide the pathways for the gas.

Journal of Geochemical Exploration↗

Estimation of the geochemical threshold and its statistical significance

A statistic is proposed for estimating the geochemical threshold and its statistical significance, or it may be used to identify a group of extreme values that can be tested for significance by other means. The statistic is the maximum gap between adjacent values in an ordered array after each gap has been adjusted for the expected frequency. The values in the ordered array are geochemical values transformed by either ln( χ - α ) or ln( α - χ ) and then standardized so that the mean is zero and the variance is unity. The expected frequency is taken from a fitted normal curve with unit area. The midpoint of an adjusted gap that exceeds the corresponding critical value may be taken as an estimate of the geochemical threshold, and the associated probability indicates the likelihood that the threshold separates two geochemical populations. The adjusted gap test may fail to identify threshold values if the variation tends to be continuous from background values to the higher values that reflect mineralized ground. However, the test will serve to identify other anomalies that may be too subtle to have been noted by other means.

Journal of Geochemical Exploration↗

Uranium in spring water and bryophytes at basin creek in central idaho

Arkosic sandstones and conglomerates of Tertiary age beneath the Challis Volcanics of Eocene age at Basin Creek, 10 km northeast of Stanley, Idaho, contain uranium-bearing vitrainized carbon fragments. The economic potential of these sandstones and conglomerates is currently being assessed. Springs abound at the contacts of rock units, and water from these springs supports abundant growths of bryophytes (mosses and liverworts). Water from 22 springs and associated bryophytes were sampled; two springs were found to contain apparently anomalous concentrations (normalized) of uranium — as much as 6.5 μg/L (ppb) in water and 1800 μg/g (ppm) in ash of mosses. Moss samples from both springs also contained anomalous concentrations of arsenic, and one contained highly anomalous amounts of beryllium. Water from a third spring contained slightly anomalous amounts of uranium, and two species of mosses at the spring contained anomalous uranium (400 and 700 μg/g) and high levels of both cadmium and lead. Water from a fourth spring was normal for uranium (0.18 μg/L), but the moss from the water contained a moderate uranium level and highly anomalous concentrations of lead, germanium, and thallium. These results suggest that, in the Basin Creek area, moss sampling at springs may give a more reliable indication of uranium occurrence than would water sampling. The reason for this may be the ability of mosses to concentrate uranium and its associated pathfinder elements and to integrate uranium fluctuations that occur in the spring water over any period of time.

Idaho↗

Guidelines for finding concretionary Mn-Fe oxides in streams

Concretionary Mn-Fe oxides in streams form at interfaces between oxidizing and reducing environments. A reducing environment produces waters high in dissolved Mn and Fe, and an oxidizing environment causes precipitation. Mineralogical, microprobe, and optical studies of concretionary Mn-Fe oxides may further our understanding of the role of Mn-Fe oxides in determining the trace-element geochemistry of stream sediments.

Journal of Geochemical Exploration↗

Scoresum - A technique for displaying and evaluating multi-element geochemical information, with examples of its use in regional mineral assessment programs

A technique called SCORESUM was developed to display a maximum of multi-element geochemical information on a minimum number of maps for mineral assessment purposes. The technique can be done manually for a small analytical data set or can be done with a computer for a large data set. SCORESUM can be used with highly censored data and can also weight samples so as to minimize the chemical differences of diverse lithologies in different parts of a given study area. The full range of reported analyses for each element of interest in a data set is divided into four categories. Anomaly scores — values of O (background), 1 (weakly anomalous), 2 (moderately anomalous), and 3 (strongly anomalous) — are substituted for all of the analyses falling into each of the four categories. A group of elements based on known or suspected association in altered or mineralized areas is selected for study and the anomaly scores for these elements are summed for each sample site and then plotted on a map. Some of the results of geochemical studies conducted for mineral assessments in two areas are briefly described. The first area, the Mokelumne Wilderness and vicinity, is a relatively small and geologically simple one. The second, the Walker Lake 1° × 2° quadrangle, is a large area that has extremely complex geology and that contains a number of different mineral deposit environments. These two studies provide examples of how the SCORESUM technique has been used (1) to enhance relatively small but anomalous areas and (2) to delineate and rank areas containing geochemical signatures for specific suites of elements related to certain types of alteration or mineralization.

Journal of Geochemical Exploration↗

The use of sagebrush (Artemisia) as a biogeochemical indicator of base-metal deposits in Precambrian rocks of west-central Colorado

The efficacy of sagebrush ( Artemisia ) as a biogeochemical indicator of base-metal mineralization in stratabound Precambrian ore deposits in west-central Colorado was investigated by collecting new (mostly flowering) growth from several sagebrush shrubs over and near five such deposits in three different areas. These are the Sedalia mine and two mines in the Turret district near Salida, and two mines in the Cochetopa district southeast of Gunnison. Two species were used, A. tridentata and A. frigida , depending on the area. Sagebrush clippings were separated into two subsamples consisting of (1) stems, and (2) leaves and blossoms stripped from the stems. These subsamples were ashed separately and the ash analyzed with an emission spectrograph for 30 elements. There appear to be no appreciable differences in the analyses of the two subsamples, indicating that composite samples would provide adequate information for further investigations. Eight of these elements, Ag, Bi, Cu, Pb, Sn, Y, Zn, and Zr, are present in notably higher concentrations in the ash of samples growing over mineralized ground than in that of control samples growing over barren ground. Although the distribution pattern, and the number of these anomalous elements, differs at each of the five localities, three of them, silver, copper, and lead, show good contrast and close association with subjacent mineralization in all five study areas.

Journal of Geochemical Exploration↗

Gold in natural water: A method of determination by solvent extraction and electrothermal atomization

A method has been developed using electrothermal atomization to effectively determine the amount of gold in natural water within the nanogram range. The method has four basic steps: (1) evaporating a 1-L sample; (2) putting it in hydrobromic acid-bromine solution; (3) extracting the sample with methyl-isobutyl-ketone; and (4) determining the amount of gold using an atomic absorption spectrophotometer. The limit of detection is 0.001 μg gold per liter. Results from three studies indicate, respectively, that the method is precise, effective, and free of interference. Specifically, a precision study indicates that the method has a relative standard deviation of 16–18%; a recovery study indicates that the method recovers gold at an average of 93%; and an interference study indicates that the interference effects are eliminated with solvent extraction and background correction techniques. Application of the method to water samples collected from 41 sites throughout the Western United States and Alaska shows a gold concentration range of < 0.001 to 0.036 μ g gold per liter, with an average of 0.005 μg/L.

Journal of Geochemical Exploration↗

Gases and trace elements in soils at the North Silver Bell deposit, Pima County, Arizona

Soil samples were collected over the North Silver Bell porphyry copper deposit near Tucson, Arizona. Volatile elements and compounds in gases derived from the soils and metallic elements in the soils were analyzed in order: (1) to see which volatile constituents of the soils might be indicative of the ore body or the alteration zones; and (2) to distinguish the ore and alteration zones by comparison of trace elements in the soil. Plots of analytical data on trace elements in soils indicated a typical distribution pattern for metals around a porphyry copper deposit, with copper, molybdenum, and arsenic concentrations higher over the ore body, and zinc, lead, and silver concentrations higher over the alteration zones. Higher than average concentrations of helium, carbon disulfide, and sulfur dioxide adsorbed on soils were found over the ore body, whereas higher concentrations of carbon dioxide and carbonyl sulfide were found over the alteration zones.

Journal of Geochemical Exploration↗

A rapid, partial leach and organic separation for the sensitive determination of Ag, Bi, Cd, Cu, Mo, Pb, Sb, and Zn in surface geologic materials by flame atomic absorption

A solution of dilute hydrochloric acid, ascorbic acid, and potassium iodide has been found to dissolve weakly bound metals in soils, stream sediments, and oxidized rocks. Silver, Bi, Cd, Cu, Mo, Pb, Sb, and Zn are selectively extracted from this solution by a mixture of Aliquat 336 (tricaprylyl methyl ammonium chloride) and MIBK (methyl isobutyl ketone). Because potentially interfering major and minor elements do not extract, the organic separation allows interference-free determinations of Ag and Cd to the 0.05 ppm level, Mo, Cu, and Zn to 0.5 ppm, and Bi, Pb, and Sb to 1 ppm in the sample using flame atomic absorption spectroscopy. The analytical absorbance values of the organic solution used in the proposed method are generally enhanced more than threefold as compared to aqueous solutions, due to more efficient atomization and burning characteristics. The leaching and extraction procedures are extremely rapid; as many as 100 samples may be analyzed per day, yielding 800 determinations, and the technique is adaptable to field use. The proposed method was compared to total digestion methods for geochemical reference samples as well as soils and stream sediments from mineralized and unmineralized areas. The partial leach showed better anomaly contrasts than did total digestions. Because the proposed method is very rapid and is sensitive to pathfinder elements for several types of ore deposits, it should be useful for reconnaissance surveys for concealed deposits.

Journal of Geochemical Exploration↗