An inductively coupled plasma atomic fluorescence spectrometric (ICP-AFS) method was used for the determination of nine elements in natural water. Reference and acid mine water samples were analysed by this method to demonstrate its usefulness for hydrogeochemical exploration. The elements were determined in two groups based on the compatibility of operating conditions and consideration of element abundance levels in natural water. Ca, Mg and Na were determined as a group using one set of instrumental conditions and a 1 + 99 dilution of the sample, and Cd, Cu, Fe, K, Li and Zn were determined using another set of conditions and the undiluted sample. The detection limits for the elements are as follows: Ca, 1.4; Mg, 1.7; Na, 2.0; Cd, 1.8; Cu, 6.2; Fe, 15.8; K, 3.5; Li, 0.3; and Zn, 1.2 ng ml –1 . Each element has a linear range spanning about four orders of magnitude. The method has good precision and accuracy, as shown by statistics on replicate analyses and by the agreement between values obtained and those recommended for the reference water samples, and also those obtained by atomic absorption spectrometry for the acid mine water samples.

The Analyst↗

USGS1986

Inductively coupled plasma atomic fluorescence spectrometric determination of cadmium, copper, iron, lead, manganese and zinc

An inductively coupled plasma atomic fluorescence spectrometric method is described for the determination of six elements in a variety of geological materials. Sixteen reference materials are analysed by this technique to demonstrate its use in geochemical exploration. Samples are decomposed with nitric, hydrofluoric and hydrochloric acids, and the residue dissolved in hydrochloric acid and diluted to volume. The elements are determined in two groups based on compatibility of instrument operating conditions and consideration of crustal abundance levels. Cadmium, Cu, Pb and Zn are determined as a group in the 50-ml sample solution under one set of instrument conditions with the use of scatter correction. Limitations of the scatter correction technique used with the fluorescence instrument are discussed. Iron and Mn are determined together using another set of instrumental conditions on a 1-50 dilution of the sample solution without the use of scatter correction. The ranges of concentration (??g g-1) of these elements in the sample that can be determined are: Cd, 0.3-500; Cu, 0.4-500; Fe, 85-250 000; Mn, 45-100 000; Pb, 5-10 000; and Zn, 0.4-300. The precision of the method is usually less than 5% relative standard deviation (RSD) over a wide concentration range and acceptable accuracy is shown by the agreement between values obtained and those recommended for the reference materials.

Journal of Analytical Atomic Spectrometry↗

USGS1985

Trace elements in disseminated sulfides, magnetite, and massive sulfides, West Shasta district, California.

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.

Economic Geology↗

USGS1985

Trace element content of gossans at four mines in the West Shasta massive sulfide district

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.

Economic Geology↗

USGS1985

Removal of iron interferences by solvent extraction for geochemical analysis by atomic-absorption spectrophotometry

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.

Talanta↗

USGS1985

A comparative study of stream water and stream sediment as geochemical exploration media in the Rio Tanama porphyry copper district, Puerto Rico

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.

Journal of Geochemical Exploration↗

USGS1985

Analytical results and sample locality map of stream sediment, heavy-mineral-concentrate, and rock samples from the Lost Creek Wilderness Area, Jefferson and Park Counties, Colorado

No abstract available.

Colorado↗

USGS1984

A comparison of iron oxide-rich joint coatings and rock chips as geochemical sampling media in exploration for disseminated gold deposits

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.

Journal of Geochemical Exploration↗

USGS1983

Atomic-absorption determination of mercury in geological materials by flame and carbon-rod atomisation after solvent extraction and using co-extracted silver as a matrix modifier

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.

The Analyst↗

USGS1981

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↗

USGS1981

Matrix modification with silver for the electrothermal atomization of arsenic and selenium

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.

Analytica Chimica Acta↗

USGS1981

Determination of sub-microgram amounts of selenium in geological materials by atomic-absorption spectrophotometry with electrothermal atomisation after solvent extraction

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.

The Analyst↗

USGS1979

Atomic-absorption spectrometric determination of cobalt, nickel, and copper in geological materials with matrix masking and chelation-extraction

An atomic-absorption spectrometric method is reported for the determination of cobalt, nickel, and copper in a variety of geological materials including iron- and manganese-rich, and calcareous samples. The sample is decomposed with HP-HNO 3 and the residue is dissolved in hydrochloric acid. Ammonium fluoride is added to mask iron and 'aluminum. After adjustment to pH 6, cobalt, nickel, and copper are chelated with sodium diethyl-dithiocarbamate and extracted into methyl isobutyl ketone. The sample is set aside for 24 h before analysis to remove interferences from manganese. For a 0.200-g sample, the limits of determination are 5–1000 ppm for Co, Ni, and Cu. As much as 50% Fe, 25% Mn or Ca, 20% Al and 10% Na, K, or Mg in the sample either individually or in various combinations do not interfere. Results obtained on five U.S. Geological Survey rock standards are in general agreement with values reported in the literature.

Analytica Chimica Acta↗

USGS1979

Determination of arsenic in geological materials by electrothermal atomic-absorption spectrometry after hydride generation

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.

Analytica Chimica Acta↗