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Use of partial dissolution techniques in geochemical exploration

Application of partial dissolution techniques to geochemical exploration has advanced from an early empirical approach to an approach based on sound geochemical principles. This advance assures a prominent future position for the use of these techniques in geochemical exploration for concealed mineral deposits. Partial dissolution techniques are classified as single dissolution or sequential multiple dissolution depending on the number of steps taken in the procedure, or as “nonselective” extraction and as “selective” extraction in terms of the relative specificity of the extraction. The choice of dissolution techniques for use in geochemical exploration is dictated by the geology of the area, the type and degree of weathering, and the expected chemical forms of the ore and of the pathfinding elements. Case histories have illustrated many instances where partial dissolution techniques exhibit advantages over conventional methods of chemical analysis used in geochemical exploration.

Journal of Geochemical Exploration↗

Response of douglas fir (Pseudotsuga menziesii) to uraniferous groundwater in a small glaciated drainage, Northeastern Washington State

Douglas fir trees and associated soils were sampled from the slopes of a small (∼4 km 2 ) drainage basin in northeastern Washington to investigate the biogeochemical response to locally uraniferous groundwater. Uranium is preferentially incorporated in needles and twigs compared to larger branches or the trunk. The U concentration in needle ash ranges from 0.2 to 5.8μg g −1 (ppm) and shows no correlation with the U concentration in associated soils. Rather, the distribution of anomalously uraniferous douglas fir (> 1.0 μ g g −1 U in needle ash) appears to be controlled by observed or readily inferred pathways of near-surface groundwater movement in the drainage. These pathways include: (1) general downslope movement of subsurface runoff; (2) increased flux of near-surface groundwater near the toe of an alluvial fan; and (3) emergence of uraniferous (100–150 ng ml −1 [ppb] groundwater in the vicinity of a slope spring. The data also indicate the presence of near-surface uraniferous groundwater along a structurally controlled zone that parallels the north-south strike of the valley, and that includes the slope spring. The results suggest that biogeochemical sampling may be used to supplement more direct, but more limited, measurements of groundwater quality and flow regime in areas of near-surface contaminated groundwater.

Journal of Geochemical Exploration↗

The role of atomic absorption spectrometry in geochemical exploration

In this paper we briefly describe the principles of atomic absorption spectrometry (AAS) and the basic hardware components necessary to make measurements of analyte concentrations. Then we discuss a variety of methods that have been developed for the introduction of analyte atoms into the light path of the spectrophotometer. This section deals with sample digestion, elimination of interferences, and optimum production of ground-state atoms, all critical considerations when choosing an AAS method. Other critical considerations are cost, speed, simplicity, precision, and applicability of the method to the wide range of materials sampled in geochemical exploration. We cannot attempt to review all of the AAS methods developed for geological materials but instead will restrict our discussion to some of those appropriate for geochemical exploration. Our background and familiarity are reflected in the methods we discuss, and we have no doubt overlooked many good methods. Our discussion should therefore be considered a starting point in finding the right method for the problem, rather than the end of the search. Finally, we discuss the future of AAS relative to other instrumental techniques and the promising new directions for AAS in geochemical exploration.

Journal of Geochemical Exploration↗

Movement of elements into the atmosphere from coniferous trees in subalpine forests of Colorado and Idaho

Exudates from conifer trees, presumably consisting largely of volatile materials, were sampled at 19 subalpine localitites in Colorado and Idaho where anomalous amounts of several metals were determined in vegetation and mull during previous geochemical testing. The trees sampled were lodgepole pine ( Pinus contorta ), Engelmann spruce ( Picea engelmannii ) and Douglas fir ( Pseudotsuga menziesii ). The condensed exudates were passed through No. 40 Whatman filters, and through 5-micron, 0.45-micron, and 0.05-micron average-pore-diameter membrane filters, evaporated to dryness, and each residue was ashed and analyzed by a semiquantitative spectrographic method. The ashed residues of the exudates contain lithium, beryllium, boron, sodium, magnesium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, arsenic, strontium, yttrium, zirconium, molybdenum, silver, lead, bismuth, cadmium, tin, antimony, barium, and lanthanum. The presence of these elements suggests that volatile exudates from vegetation are a medium for the transport of elements in the biogeochemical cycle in subalpine environments. Thus, air sampling and analysis of aerosols derived from volatile exudates may be a useful tool in geochemical exploration.

Colorado, Idaho↗

Multiple gas analyses using a mobile mass spectrometer

A truck-mounted mass-spectrometer gas analyzer is described and field examples of its use are given. This unit provides a gas analyzer that can be used in the field to rapidly analyze a large number of gases. It has enabled us to establish that gas anomalies occur over a variety of deposit types and in different environments. Gases may prove to be useful geochemical indicators in exploration for concealed mineral deposits.

Journal of Geochemical Exploration↗

Geochemical exploration for copper-nickel deposits in the cool-humid climate of northeastern Minnesota

Water was used as a medium for geochemical exploration to detect copper-nickel mineralization along the basal zone of the Duluth Complex. Ni 2+ is the most important pathfinder for the detection of the mineralized rocks, followed by Cu 2+ and SO 4 2− and to a lesser extent Mg 2+ and SiO 2 . A normalized sum plot using these species defines the mineralization more consistently than a single-element plot, mainly because the absence of one variable does not significantly influence the normalized sum value. A hydrogeochemical survey was conducted in an area of known copper-nickel mineralization in the cool-humid climate of northeastern Minnesota. The area is covered with glacial drift, and wetlands are abundant. Modeling of the chemistry of waters indicates that the waters are oxidizing and have a pH of 7 or less. The most important pathfinder species in the waters, Cu 2+ , Ni 2+ , and SO 4 2− , are derived from the simple weathering of sulfide minerals and are mobile in the waters in this environment. Plots of Cu and Ni concentrations in soils show that Cu followed by Ni are the most useful indicator elements for delineating copper-nickel mineralization. The ability of soils and water to delineate the mineralization supports the use of both media for geochemical exploration in this cool-humid environment. In the wetlands, abundant water is available and soils are scarce or absent; where soils are abundant, waters are generally scarce or absent. The use of both media is recommended for geochemical exploration in this environment.

Journal of Geochemical Exploration↗

Hydrogeochemical prospecting for porphyry copper deposits in the tropical-marine climate of Puerto Rico

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.

Puerto Rico↗

Copper and cobalt in aquatic mosses and stream sediments from the Idaho Cobalt Belt

Samples of stream sediments and aquatic mosses were collected from nine sites across several mineralized zones at the southeasternmost extension of the Idaho Cobalt Belt. Because the steepness of the terrain and the attendant high flow rate of the streams made it difficult to obtain adequate sediment samples, mosses were considered as an alternative sampling medium. The results not only showed that the Cu and Co content of the mosses correlated almost perfectly with that of the sediments, but that the contrast between samples taken from mineralized and background areas was greater in mosses, especially for Co. Maximum concentrations of 35,000 μg/g Cu and 2000 μg/g Co were observed in the ash of mosses, compared to maximum concentrations of 1700 μg/g and 320 μg/g, respectively, in the associated sediments. Species identification was considered unimportant, which should dispel some reluctance to use mosses in mineral exploration.

Journal of Geochemical Exploration↗

Using stream-side groundwater discharge for geochemical exploration in mountainous terrain

Groundwater chemistry has been predominantly used in geochemical exploration studies to identify mineralized targets concealed under transported cover in areas with gentle topography. Another potentially valuable ap-plication that has received little attention is using groundwater chemistry to identify deposits concealed within mountain ridges. A number of geochemical exploration studies have employed surface water chemistry in hilly and mountainous terrain and have demonstrated mixed success. However, groundwater chemistry is potentially a more refined and powerful tool because groundwater sample locations can be selected to target a specific hillslope zone, whereas surface water integrates the geochemical signature of the entire watershed area above the sample site. In this study, we propose an approach that utilizes shallow groundwater samples collected from near-stream, hand-installed sampling points. We tested this approach in Handcart Gulch, an unmined catchment in the Montezuma Mining District, Colorado, USA, where previous studies suggested the possible presence of a concealed mineral occurrence. Seventeen near-stream mini-boreholes were drilled in a stream-parallel 3.3-km-long transect to depths of ~2 m in ferricrete (iron-oxide cemented colluvium and alluvium) using a handheld rock-coring drill. Groundwater in the mini-boreholes was sampled for major and trace element chemistry, as well as environmental tracers including stable water isotopes, dissolved noble gases, helium isotopes, and tritium, to identify possible variations in groundwater age and recharge conditions/sources. Chemistry data delineate a well-defined 900-m-wide zone of elevated SO4, Cu, and other metal concentrations on the east side of the stream. In this zone, Cu concentrations up to 2670 μg/L are 1–3 orders of magnitude greater than concentrations in upstream and downstream areas. Environmental tracer data show no corresponding anomalies in groundwater age or recharge conditions/sources within the zone, suggesting that the source of the elevated metals is a change in bedrock mineralogy as opposed to other hydrologic factors. The groundwater samples therefore successfully identify and refine the location of a potential concealed high-Cu mineral occurrence in the watershed, de-monstrating that near-stream groundwater discharge may be a valuable medium for geochemical exploration in mountainous areas.

Colorado↗

Conceptual models in exploration geochemistry-The Basin and Range Province of the Western United States and Northern Mexico

This summary of geochemical exploration in the Basin and Range Province is another in the series of reviews of geochemical-exploration applications covering a large region; this series began in 1975 with a summary for the Canadian Cordillera and Canadian Shield, and was followed in 1976 by a similar summary for Scandinavia (Norden). Rather than adhering strictly to the type of conceptual models applied in those papers, we have made use of generalized landscape geochemistry models related to the nature of concealment of ore deposits. This study is part of a continuing effort to examine and evaluate geochemical-exploration practices in different areas of the world. Twenty case histories of the application of geochemical exploration in both district and regional settings illustrate recent developments in techniques and approaches. Along with other published reports these case histories, exemplifying generalized models of concealed deposits, provide data used to evaluate geochemical-exploration programs and specific sample media. Because blind deposits are increasingly sought in the Basin and Range Province, the use of new sample media or anomaly-enhancement techniques is a necessity. Analysis of vapors or gases emanating from blind deposits is a promising new technique. Certain fractions of stream sediments show anomalies that are weak or not detected in conventional minus 80-mesh fractions. Multi-element analysis of mineralized bedrock may show zoning patterns that indicate depth or direction of ore. Examples of the application of these and other, more conventional methods are indicated in the case histories. The final section of this paper contains a brief evaluation of the applications of all types of sample media to geochemical exploration in the arid environment of the Basin and Range Province. ?? 1978.

Journal of Geochemical Exploration↗

The partitioning of copper among selected phases of geologic media of two porphyry copper districts, Puerto Rico

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.

Puerto Rico↗

Comparison of hot hydroxylamine hydrochloride and oxalic acid leaching of stream sediment and coated rock samples as anomaly enhancement techniques

A hot hydroxylamine hydrochloride (H-Hxl) extraction in 25% acetic acid is compared with the commonly used oxalic acid extraction as a method of anomaly enhancement for Cu and Zn in samples from two very different metal deposits and climatic environments. Results obtained on minus-80-mesh stream sediments from an area near the Magruder massive sulfide deposit in Lincoln County, Georgia, where the climate is humid subtropical, indicate that H-Hxl enhances the anomaly for Cu by a factor of 2 and for Zn by a factor of 1.5, compared to the oxalic method. Analyses of Fe oxide-coated rock samples from outcrops overlying the North Silver Bell porphyry copper deposit near Tucson, Arizona, where the climate is semi-arid to arid, indicate that both techniques effectively outline the zones of hydrothermal alteration. The H-Hxl extraction can also perform well in high-carbonate or high-clay environments, where other workers have suggested that oxalic acid is not very effective. Therefore, the H-Hxl method is recommended for general exploration use.

Journal of Geochemical Exploration↗

Uranium in big sagebrush from western U.S. and evidence of possible mineralization in the Owyhee mountains of Idaho

Two regional studies of big sagebrush ( Artemisia tridentata ), a widely distributed and dominant shrub in the western United States, have shown its responsiveness to known uranium mineralization in the Monument Hill and Pumpkin Buttes districts of the southern Powder River Basin, Wyoming, and the Uravan mineral belt area in southeastern Utah and southwestern Colorado. Uranium concentrations in the ash of 154 stem-and-leaf samples of sagebrush are plotted on two maps, one representing the sampling design for the Powder River Basin study, and the other representing the sampling design for the Colorado Plateaus, the Basin and Range, and the Columbia Plateaus physiographic provinces of the West. Sites having high concentrations in sagebrush correspond not only to the above uranium districts, but also reveal an area along the northeast flanks of the Owyhee Mountains in Idaho that should be further explored for its possible uranium potential.

Journal of Geochemical Exploration↗

Epithermal gold-siver deposits in the western United States: time-space products of evolving plutonic, volcanic and tectonic environments

The western United States has been the locus of considerable subaerial volcanic and plutonic igneous activity since the mid-Mesozoic. After the destruction of the Jurassic-Cretaceous magmatic arc-trench system, subduction was re-established in the Late Mesozoic with low-angle underthrusting of the oceanic plate beneath western North America. This resulted in crustal shortening during the Late Cretaceous to Early Tertiary and removal of the mantle lithosphere west of the Rocky Mountains. Commencing in the Eocene, flat subduction ceased, the volcanic arc began to re-establish itself along the continental margin, and the hingeline along the steepening subducting plate migrated from east to west. The crust east of the migrating hingeline was exposed to hot asthenosphere, and widespread tectonics and volcanic activity resulted. Hydrothermal activity accompanied the volcanism resulting in numerous epithermal gold-silver deposits. The temporal and spatial distributions of epithermal deposits in the region are therefore systematic and can be subdivided into discrete time intervals which are related to widespread changes in magmatic activity. Time intervals selected for discussion are Pre-Cenozoic, 66-55 Ma, 54-43 Ma, 42-34 Ma, 33-24 Ma, 23-17 Ma, and <17 Ma. Many of these intervals contain both sedimentary-rock and two varieties of volcanic-rock hosted deposits (adularia-sericite and alunite-kaolinite ± pyrophyllite). Continental rifting is important to the formation of deposits, and, within any given region, it is at the initiation of deep rifting that alunite-kaolinite ± pyrophyllite type epithermal deposits are formed. Adularia-sericite type deposits are most common, being related to all compositions and styles of volcanic activity. Therefore, the volcano-tectonic context of the western United States provides a unified framework in which to understand and explore for epithermal type deposits.

Journal of Geochemical Exploration↗

Anomalous gold, antimony, arsenic, and tungsten in ground water and alluvium around disseminated gold deposits along the Getchell Trend, Humboldt County, Nevada

Ground-water, alluvium, and bedrock samples were collected from drill holes near the Chimney Creek, Preble, Summer Camp, and Rabbit Creek disseminated gold deposits in northern Nevada to determine if Au and ore-related metals, such as As, Sb, and W, are being hydromorphically mobilized from buried mineralized rock, and, if they are, to determine whether the metal-enriched ground water is reacting with the alluvial material to produce a geochemical anomaly within the overburden. Results of chemical analyses of drill-hole water samples show the presence of hydromorphic dispersion anomalies of Au, As, Sb, and W in the local ground-water systems associated with these deposits. Background concentrations for Au in the ground water up-gradient from the buried deposits was less than 1 nanogram per liter (ng/L), near the deposits the Au values ranged from 1 to 140 ng/ L, and in drill holes penetrating mineralized rock, concentrations of Au in the ground water were as high as 4700 ng/L. Highest concentrations of Au were found in ground-water samples where the measured E h and the distribution of arsenic species, arsenite [As(III)] and arsenate [As(V)], indicated oxidizing redox potentials. Similarly, As, Sb, and W concentrations in the ground water near the deposits were significantly enriched relative to concentrations in the ground water up-gradient from the deposits. In general, however, the highest concentrations of As, Sb, and W occurred in ground-water samples where the measured E h and the distribution of arsenic species indicated reducing conditions. Arsenic concentrations ranged from 9 to 710 micrograms per liter (μg/L); Sb, from less than 0.1 to 250 μg/L; and W, from 1 to 260 μg/L. In addition, analysis of sequential dissolution and extraction solutions of drill cuttings of alluvium and bedrock indicate geochemical anomalies of gold and ore-related metals in the overburden at depths corresponding to the location of the present-day water table. This relationship suggests that water-rock reactions around these buried deposits are active and that this information could be very useful in exploration programs for concealed disseminated gold deposits.

Journal of Geochemical Exploration↗

Disequilibrium in the 238uranium series in samples from Yeelirrie, Western Australia

Uranium-series disequilibrium studies carried out on samples from the Yeelirrie uranium deposit, Western Australia, indicate that uranium and radium have been migrating within the deposit during recent times, and are actually being removed from the deposit. Samples collected for 230 Th/ 234 U age dating were found to be substantially out of equilibrium, with 230 Th/ 234 U activity ratios ranging from 0.750 to 1.345. This can be explained by a dynamic hydrologic system in which there has been, and continues to be, uranium migration caused by leaching in this arid, oxidizing environment, and a fluctuating water table. Recent, extensive 226 Ra migration ( 226 Ra/ 230 Th activity ratios range from 0.53 to 1.30), and a very low emanation factor ( E ) of 222 Rn limit the quantitative application of radon exploration techniques in this environment.

Journal of Geochemical Exploration↗