Allen L. Meier

Flameless atomic-absorption determination of gold in geological materials

Abstract 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.

Natural or fertilizer-derived uranium in irrigation drainage: a case study in southeastern Colorado, U.S.A.

Abstract Drainage from heavily cultivated soils may be contaminated with U that is leached from the soil or added as a trace constituent of PO 4 -based commercial fertilizer. The effect of decades-long application of U-rich fertilizer on the U concentration of irrigation drainage was investigated in a small (14.2 km 2 ) drainage basin in southeastern Colorado. The basin was chosen because previous reports indicated locally anomalous concentrations of dissolved NO 3 (6–36 mg 1 −1 ) and dissolved U (61 pg 1 −1 ) at the mouth of the only stream. Results of this study indicated minimal impact of fertilizer-U compared to natural U leached from the local soils. Detailed sampling of the stream along a 6 mile (9.7 km) reach through heavily cultivated lands indicated marked decoupling of the buildup of dissolved NO 3 and U. Dissolved U increased markedly in the upstream half of the reach and correlated positively with increases in Na, Mg, SO 4 , B and Li derived from leaching of surrounding shaley soils. In contrast, major increases in dissolved NO 3 occurred farther downstream where stream water was heavily impacted by ground water return from extensively fertilized fields. Nitrogen isotopic measurements confirmed that dissolved NO 3 originated from fertilizer and soil organic N (crop waste). Uranium isotopic measurements of variably uraniferous waters showed little evidence of contamination with fertilizer-derived U of isotopically distinct 234 U/ 238 U alpha activity ratio (A.R. = 1.0). Leaching experiments using local alkaline soil, irrigation water and U-rich fertilizer confirmed the ready leachability of soil-bound U and the comparative immobility of U added with liquid fertilizer. Relatively insoluble precipitates containing Ca P U were formed by mixing liquid fertilizer with water containing abundant dissolved Ca. In the local soils soluble Ca is provided by dissolution of abundant gypsum. Similar studies are needed elsewhere because the mobility of fertilizer-derived U is dependent on fertilizer type, porewater chemistry and soil properties (pH, moisture, mineralogy, texture).

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 Eh 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 Eh 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.

The association of uranium with organic matter in Holocene peat: An experimental leaching study

Abstract Uraniferous peat was sampled from surface layers of a Holocene U deposit in northeastern Washington State. Dried, sized, and homogenized peat that contained5980 ±307 ppm U was subjected to a variety of leaching conditions to determine the nature and strength of U-organic bonding in recently accumulated organic matter. The results complement previous experimental studies of U uptake on peat and suggest some natural or anthropogenic disturbances that are favorable for remobilizing U. The fraction of U leached in 24 h experiments at 25°C ranged from 0 to 95%. The most effective leach solutions contained anions capable of forming stable dissolved complexes with uranyl (UO 2 +2 ) cation. These included H 2 SO 4 ( pH = 1.5) and concentrated (0.01M) solutions of sodium bicarbonate-carbonate ( pH = 7.0–10.0), or sodium pyrophosphate ( pH = 10). Effective leaching by carbonate and pyrophosphate in the absence of added oxidant, and the insignificant effect of added oxidant (as pressurized O 2 ) strongly suggest that U is initially fixed on organic matter as an oxidized U(VI) species. Uranium is more strongly bound than some other polyvalent cations, based on its resistance to exchange in the presence of large excesses of dissolved Ca 2+ and Cu 2+ . Measurements of the rate of U leaching indicate faster rates in acid solution compared to carbonate solution, and are consisten with simultaneous attack of sites with different affinities for U. Sulfuric acid appears a good choice for commercial extraction of U from mined peat. In situ disturbances such as overliming of peat soils, addition of fertilizers containing pyrophosphate, or incursions of natural carbonate-rich waters could produce significant remobilization of U, and possibly compromise the quality of local domestic water supplies.

NEOCHIM: An electrochemical method for environmental application

Abstract Ion migration and electroosmosis are the principal processes underlying electrokinetic remediation of hazardous wastes from soils. These processes are a response of charged species to an applied electrical current and they are accompanied by electrolysis of water at the electrodes through which the current is applied. Electrolysis results in the formation of OH − at the cathode and H + at the anode. The current drives the OH − and H + thus formed from the electrodes, through the soil and to the electrode of opposite charge. Introduction of OH − and H + into the soil being treated modifies soil chemistry and can interfere with either the collection or immobilization of hazardous waste ions. The introduction of either OH − or H + to the soil can be problematic to electrokinetic remediation but the problem caused by OH − has been the focus of most researchers. The problem has been addressed by flushing the OH − from the soil near the cathode or treating the soil with buffers. These treatments would apply as well to soils affected by H + . With the NEOCHIM technology, developed by the U.S. Geological Survey (USGS) for use as a sampling technique in exploration for buried ore deposits, OH − and H + are retained in the inner compartment of two-compartment electrodes and are thus prevented from reaching the soil. This enables the extraction of cations and anions, including anionic forms of toxic metals such as HAsO 2− 4 . One of the principal attributes of NEOCHIM is the large volume of soil from which ions can be extracted. It is mathematically demonstrable that NEOCHIM extraction volumes can be orders of magnitude greater than volumes typically sampled in more conventional geochemical exploration methods or for environmental sampling. The technology may also be used to introduce selected ions into the soil that affect the solubility of ceratin ions present in the soil. Although field tests for mineral exploration have shown NEOCHIM extraction efficiencies of about 25–35%, laboratory experiments suggest that significantly higher efficiencies are possible. The attributes of NEOCHIM combined with relatively low cost of electrical power, indicate that the technology may be useful for remediation and monitoring of hazardous waste sites. Of particular importance is that NEOCHIM extractions affect only dissolved and electrically charged species, hence those prone to move in groundwater.

Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization

Abstract Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206 Pb/ 204 Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206 Pb/ 204 Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb-rich base-metal veins, and sedimentary country rocks. Stream-sediment anomalies detected using oxalic acid leaches can be evaluated using Pb isotope analysesof selected geochemical anomalies. Such an evaluation procedure, given regional target Pb isotope signatures for concealed mineralization, can greatly reduce the cost of exploration for undiscovered ore deposits concealed beneath barren overburden. Lead isotope measurements on aliquots of the same solutions showed that ICP-MS determinations are of low precision and vary non-systematically when compared with the Pb isotope values of the higher precision thermal ionization method. These variations and lower precision of the ICP-MS measurements are attributed to matrix effects.

Uraniferous waters of the Arkansas River valley, Colorado, U.S.A.: a function of geology and land use

Abstract The effect of local geology and land-use practices on dissolved U was investigated by analysis of surface water and some springs in the Arkansas River valley of southeastern Colorado. Water samples were collected during a 2 week period in April, 1991. The rate of increase of U concentration with distance downriver increased markedly as the river flowed from predominantly undeveloped lands underlain by igneous and metamorphic rocks to agriculturally developed lands underlain by marine shale and limestone. An additional abrupt increase in dissolved U was observed along the section of river where discharge is often greatly reduced because of extensive diversions for irrigation and where remaining flow is largely composed of irrigation return water. Dissolved U in this last section of river and in most of its tributaries exceeded the proposed U.S. drinking water standard of 20 μ/L In water samples collected from agricultural areas dissolved U showed strong positive correlation with major dissolved constituents Na, Ca, Mg, and SO4 that increase as a result of sulfate mineral dissolution and clay mineral ion-exchange reactions in weathered shale bedrock and shaley soils. Highly soluble minor and trace elements Cl, Li, B, Sr, and Se that are not subject to strong sorptive uptake or precipitation in this setting also correlated positively with U. These combined observations indicate that natural leaching of U-bearing shale bedrock and derivative soils, additional leaching of rock and soil by irrigation water, and evaporative concentration in a semi-arid climate can produce concentrations of dissolved U in surface water and shallow ground water that may threaten nearby drinking water supplies. Other agriculturally developed areas of the semi-arid Western U.S. with similar geology are likely to contain high concentrations of U in irrigation drain water.

A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

Abstract Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS.

Hydrogeochemical investigations in the Osgood mountains, north-central Nevada. Chapter B.

Field investigations performed in the Osgood Mountains during the summers of 1999 and 2000 were designed to test methods of combining geologic, hydrologic, and geochemical investigations. The goals were to develop a more thorough understanding of the movement of water through the study area and to understand the water-rock reactions that may occur along flow paths. The Osgood Mountains were chosen for study because they represent a well-defined geologic system, based on existing and new field data. New work in the area focused on gathering more data about fractures, faults, and joints and on collecting water samples to evaluate the role of geologic structures on hydrologic and geochemical properties of the ground-water/surface-water system. Chemical methods employed in the study included measuring traditional field parameters (e.g., pH, temperature, conductivity, dissolved oxygen) as well as Fe2+ and collecting a variety of samples that were preserved for later laboratory analysis. Hydrologic methods included closely spaced evaluations of substream hydraulic head to define ground-water discharge and recharge zones as well as some measurements of stream discharge. Geologic investigations focused on the locations and orientations of fractures and kinematic indicators of slip observable in outcrops.