Robert A. Zielinski

The mobility of uranium and other elements during alteration of rhyolite ash to montmorillonite: A case study in the Troublesome Formation, Colorado, U.S.A.

Abstract An unusual occurrence of juxtaposed glassy and clay-altered ash was sampled to estimate the degree and type of element mobility during alteration of glass to montmorillonite. The results are particularly interesting in that major mobilization of uranium is indicated. Closely spaced samples of glassy and montmorillonitic ash were collected from the same 20–50 cm thick stratigraphic horizon in the Troublesome Formation (Miocene) of northwestern Colorado. Sharp contacts exist between glassy ash and underlying pink montmorillonite and indicate that water-saturated conditions were restricted to basal ash layers. Formation of montmorillonite instead of zeolites suggests that the water was not highly saline or alkaline. Isotopic and chemical analyses of glassy and clay-altered samples indicate the following: 1. (1) Montmorillonite has U concentrations which are only 10–15% of the concentrations in coexisting glass. Similarly depleted elements include Cs, Rb, Na and K. Much smaller depletions of these elements in some glassy samples serve as sensitive indicators of incipient alteration of glass to montmorillonite. 2. (2) Abundances of relatively insoluble elements such as Th, Ta, Hf and Al are slightly higher (5–50%) in clay-altered ash and serve as indicators of the maximum levels of enrichment in residual material. Greater enrichment of elements such as Ca, Mg, Sr, Sc, P, Cr and Co indicate structural incorporation, adsorption, or ion-exchange uptake by clay or secondary hydrous oxides of Fe and Mn. 3. (3) The rare-earth-element patterns and abundances in glass are sufficiently mimicked by detritus-free montmorillonite to document the compositional equivalency of the two. 4. (4) Radioactive equilibrium exists between 238 U and its decay products 234 U and 230 Th. This documents minimal open-system mobility of U within the last ∼ 0.3 Ma.

Trace element evaluation of a suite of rocks from Reunion Island, Indian Ocean

Abstract Reunion Island consists of an olivine-basalt shield capped by a series of flows and intrusives ranging from hawaiite through trachyte. Eleven rocks representing the total compositional sequence have been analyzed for U, Th and REE. Eight of the rocks (group 1) have positive-slope, parallel, chondrite-normalized REE fractionation patterns. Using a computer model, the major element compositions of group 1 whole rocks and observed phenocrysts were used to predict the crystallization histories of increasingly residual liquids, and allowed semi-quantitative verification of origin by fractional crystallization of the olivine-basalt parent magma. Results were combined with mineral-liquid distribution coefficient data to predict trace element abundances, and existing data on Cr, Ni, Sr and Ba were also successfully incorporated in the model. The remaining three rocks (group 2) have nonuniform positive-slope REE fractionation patterns not parallel to group 1 patterns. Rare earth fractionation in a syenite is explained by partial melting of a source rich in clinopyroxene and/or hornblende. The other two rocks of group 2 are explained as hybrids resulting from mixing of syenite and magmas of group 1.

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).

Trace-element variations at Summer Coon volcano, San Juan Mountains, Colorado, and the origin of continental-interior andesite

The Oligocene Summer Coon center, an eroded continental-interior volcano of the eastern San Juan Mountains, Colorado, was the source of magmas ranging in composition from basaltic andesite to rhyolite. Previous Pb and Sr isotope studies indicate derivation of the magmas from an isotopically homogeneous source. This study presents new data for rare-earth elements (REE), U, Th, Ba, Sr, Rb, and Ni from 10 samples of the Summer Coon sequence. Alkali elements are high in all rocks; as SiO 2 increases, Ba increases from 900 to 2,000 ppm, Rb increases from 35 to 90 ppm, Sr decreases from 900 to 350 ppm, K/Rb decreases slightly, Ba/Sr increases, U increases from 0.5 to 2.5 ppm, and Th increases from 2 to 7 ppm. Chondrite-normalized REE patterns are strongly fractionated in comparison with oceanic-arc andesite-dacite sequences. La is 80 to 120 times chondritic abundance, but Yb and Lu are less than 10 times chondritic abundance. Small negative Eu anomalies characterize the rhyolites. Nickel in the andesites is 40 to 70 ppm. The origin of the andesite is interpreted in terms of nonmodal partial melting of a trace-element—enriched garnet-bearing source, possibly subducted crust that has converted to eclogite. Rhyodacite and rhyolite are interpreted as low-pressure crystal-fractionation products of silicic andesite, in which crystallizing phases are hornblende rich in REE and plagioclase.

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.

Leaching characteristics of ash from the May 18, 1980, eruption of Mount St. Helens Volcano, Washington

Leaching of freshly erupted air-fall ash, unaffected by rain, from the May 18, 1980, eruption of Mount St. Helens volcano, Washington, shows that Ca2+, Na+, Mg2+, SO42−, and Cl− are the predominant chemical species released on first exposure of the ash to water. Extremely high correlation of Ca with SO4 and Na with Cl in water leachates suggests the presence of CaSO4 and NaCl salts on the ash. The amount of water soluble material on ash increases with distance from source and with the weight fraction of small (less than 63 micrometers) ash particles of high-surface area. This suggests that surface reactions such as adsorption are responsible for concentrating the soluble material. CaSO4, NaCl, and other salts are probably formed as microscopic crystals in the high-temperature core of the eruption column and are then adsorbed by silicate ash particles.The environmentally important elements Zn, Cu, Cd, F. Pb, and Ba are released by a water leach in concentrations which could pose short-term hazards to some forms of aquatic life. However, calculated concentrations are based on a water-to-ash ratio of 4:1 or less, which is probably an underestimation of the regionally operative ratio. A subsequent leach of ash by warm alkaline solution shows dramatic increases, in the amount of dissolved SiO2, U, and V, which are probably caused by increased dissolution of the glassy component of ash. Glass dissolution by alkaline ground water is a mechanism for providing these three elements to sedimentary traps where they may coaccumulate as uraniferous silica or U-V minerals.Leaching characteristics of ash from Mount St. Helens are comparable to characteristics of ash of similar composition from volcanoes in Guatemala. Ashes from each locality show similar ions predominating for a given leachate and similar fractions of a particular element in the ash removed on contact with the leach solution.

Uraniferous opal, Virgin Valley, Nevada: conditions of formation and implications for uranium exploration

Abstract Uraniferous, fluorescent opal, which occurs in tuffaceous sedimentary rocks at Virgin Valley, Nevada, records the temperature and composition of uranium-rich solutions as well as the time of uranium-silica coprecipitation. Results are integrated with previous geologic and geochronologic data for the area to produce a model for uranium mobility that may be used to explore for uranium deposits in similar geologic settings. Uraniferous opal occurs as replacements of diatomite, or silicic air-fall ash layers in tuffaceous lakebeds of the Virgin Valley Formation (Miocene) of Merriam (1907). Fission-track radiography shows uranium to be homogeneously dispersed throughout the opal structure, suggesting coprecipitation of dissolved uranium and silica gel. Fluid inclusions preserved within opal replacements of diatomite have homogenization temperatures in the epithermal range and are of low salinity. Four samples of opal from one locality all have U-Pb apparent ages which suggest uraniferous opal precipitation in late Pliocene time. These ages correspond to a period of local, normal faulting, and highangle faults may have served as vertical conduits for transport of deep, thermalized ground water to shallower levels. Lateral migration of rising solutions occurred at intersections of faults with permeable strata. Silica and some uranium were dissolved from silica-rich host strata of 5–20 ppm original uranium content and reprecipitated as the solutions cooled. The model predicts that in similar geologic settings, ore-grade concentrations of uranium will occur in permeable strata that intersect high-angle faults and that contain uranium source rocks as well as efficient reductant traps for uranium. In the absence of sufficient quantities of reductant materials, uranium will be flushed from the system or will accumulate in low-grade disseminated hosts such as uraniferous opal.

The geochemistry of water near a surficial organic-rich uranium deposit, Northeastern Washington state, U.S.A.

Abstract The chemistry of three stream, three spring and six near-surface waters in the vicinity of a Holocene organic-rich uranium deposit is described, with particular emphasis on the chemistry of U. Results characterize the solution behavior of uranium as U-bearing water interacts with relatively undecomposed, surficial organic matter. Of the measured major and trace chemical species, only U is consistently highly enriched (17–318 ppb) relative to reported values for regional waters, or to literature values for waters in largely granitic terrains. R-mode factor analysis of the chemical data suggests that most U is present in a soluble form, but that some U is also associated with fine suspended particulates of clay, organic matter, or hydrous oxides. Calculations that apply thermodynamic data to predict U speciation in solution indicate the relative importance of uranyl carbonate and uranyl phosphate complexes. Analysis of more finely filtered samples (0.05 μm vs. 0.45 μm), and direct radiographic observations using fission-track detectors suspended in the waters indicate the presence of some uraniferous particulate matter. Application of existing thermodynamic data for uranous- and uranyl-bearing minerals indicates that all waters are undersaturated with U minerals as long as ambient Eh ≳ +0.1 v. If coexisting surface and near-surface waters are sufficiently oxidizing, initial fixation of U in the deposit should be by a mechanism of adsorption. Alternatively, more reducing conditions may prevail in deeper pore waters of the organic-rich host sediments, perhaps leading to direct precipitation or diagenetic formation of U4+ minerals. A 234 U 238 U alpha activity ratio of 1.08 ± 0.02 in a spring issuing from a hillslope above the deposit suggests a relatively soluble source of U. In contrast, higher activity ratios of 234 U 238 U (∼ 1.3) in waters in contact with the uraniferous valley-fill sediments suggest differences in the nature of interaction between groundwater and the local, U-rich source rocks.

Uranium mobility during interaction of rhyolitic obsidian, perlite and felsite with alkaline carbonate solution: T = 120° C, P = 210 kg/cm2

Abstract Well-characterized samples of rhyolitic obsidian, perlite and felsite from a single lava flow are leached of U by alkaline oxidizing solutions under open-system conditions. Pressure, temperature, flow rate and solution composition are held constant in order to evaluate the relative importance of differences in surface area and crystallinity. Under the experimental conditions U removal from crushed glassy samples proceeds by a mechanism of glass dissolution in which U and silica are dissolved in approximately equal weight fractions. The rate of U removal from crushed glassy samples increases with decreasing average grain size (surface area). Initial rapid loss of a small component (≈ 2.5%) of the total U from crushed felsite. followed by much slower U loss, reflects variable rates of attack of numerous uranium sites. The fractions of U removed during the experiment ranged from 3.2% (felsite) to 27% (perlite). An empirical method for evaluating the relative rate of U loss from contemporaneous volcanic rocks is presented which incorporates leaching results and rock permeability data.

The distribution and mobility of uranium in glassy and zeolitized tuff, Keg Mountain area, Utah, U.S.A.

Abstract The distribution and mobility of uranium in a diagenetically altered, 8 Ma old tuff in the Keg Mountain area, Utah, are modelled in this study. The modelling represents an improvement over similar earlier studies in that it: (1) considers a large number of samples (76) collected with good geologic control and exhibiting a wide range of alteration; (2) includes radiometric data for Th, K and RaeU (radium equivalent uranium) as well as U; (3) considers mineralogic and trace-element data for the same samples; and (4) analyzes the mineral and chemical covariation by multivariate statistical methods. The variation of U in the tuff is controlled mainly by its primary abundance in glass and by the relative abundance of non-uraniferous detritus and uraniferous accessory minerals. Alteration of glass to zeolite, even though extensive, caused no large or systematic change in the bulk concentration of U in the tuff. Some redistribution of U during diagenesis is indicated by association of U with minor alteration products such as opal and hydrous Fe−Mn oxide minerals. Isotopic studies indicate that the zeolitized tuff has been open to migration of U decay products during the last 0.8 Ma. The tuff of Keg Mountain has not lost a statistically detectable fraction of its original U, even though it has a high (≈ 9 ppm) trace U content and has been extensively altered to zeolite. Similar studies in a variety of geological environments are required in order to identify the particular combination of conditions most favorable for liberation and migration of U from tuffs.