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Robert A. Zielinski

Publications and source records attributed to Robert A. Zielinski.

At least 19 recordsLinked to original sources

Reduction of red bed sedimentary rocks in connection with energy metal ore formation: A case study from the Sinbad seep, Mesa County, Colorado

The Paradox Basin’s Sinbad seep is a modern analog for ancient bleaching of red bed sediments by introduced alkaline, reducing brines. This bleaching, involving reductive alteration of former red beds, is essential ground preparation that enables the altered rocks to trap Cu, U, and V from later oxidized fluids, forming ore deposits. Study of Sinbad thus offers insights into these metallic mineralization processes in the Paradox and other sedimentary basins. The Sinbad seep occurs where shallow groundwater interacts with organic-rich petroleum source rocks, flows up a fault, and discharges into Salt Creek. Ratios of Na/Cl, Na/Br, and Cl/Br, plus high sulfate concentrations, indicate that the salinity of the seep water originated from dissolution of halite and gypsum during topographically driven flow of meteoric water across a diapir of the Pennsylvanian Paradox Formation, rather than from deep basinal brines. In contact with the organic-rich shales of the Paradox, these SO 4 -rich waters become reduced through bacterial reduction, producing H 2 S. The waters react with red beds of the Permian Cutler Formation, causing pervasive bleaching. The bleaching at Sinbad is characterized by iron-conservative reduction of ferric iron in diagenetic hematite and detrital ilmenite and magnetite to Fe sulfides. The ferrous iron is retained in these sulfides likely as sorbed Fe. Associated alteration includes precipitation of quartz and feldspar overgrowths, partial dissolution of detrital quartz and feldspar caused by pressure solution, formation of clay and authigenic rutile, and precipitation of carbonate and gypsum. The Fe sulfides rapidly degenerate to a mixture of jarosite and iron oxides on weathering at the surface. Among the major-oxide elements and most trace elements, there is no statistical difference between unbleached and bleached samples. The exceptions are uranium and sulfur, which are somewhat greater in bleached samples. Fission track radiography illuminates that uranium is preferentially concentrated in iron oxide cements, iron sorbed into detrital clasts, and finely disseminated iron oxide in illite cement in bleached samples. A leaching experiment suggests that uranium may be more easily available for mobilization from rocks that have undergone bleaching alteration, making them potential U sources. In addition, bleached rocks form effective traps for U, V, and some Cu mineralization.

Colorado↗

Sandstone-hosted uranium deposits of the Colorado Plateau, USA

More than 4,000 sandstone-hosted uranium occurrences host over 1.2 billion pounds of mined and in situ U 3 O 8 throughout the Colorado Plateau. Most of the resources are in two distinct mineral systems with deposits hosted in the Triassic Chinle and Jurassic Morrison Formations. In the Chinle mineral system, base metal sulfides typically accompany mineralization. The Morrison mineral system is characterized by V/U ratios up to 20. The uranium source was likely volcanic ash preserved as bentonitic mudstones in the Brushy Basin Member of the Morrison Formation, and lithic volcanic clasts, ash shards, and bentonitic clay in the lower part of the Chinle Formation. Vanadium originated from two possible sources: iron–titanium oxides that are extensively altered in bleached rock near deposits or from similar minerals in variably bleached red beds interbedded with and beneath the Morrison. In Chinle-hosted deposits, in addition to volcanic ash, a contributing source of both vanadium and uranium is proposed here for the first time to be underlying red beds in the Moenkopi and Cutler Formations that have undergone a cycle of reddening-bleaching-reoxidation. Transport in both systems was likely in groundwater through the more permeable sandstones and conglomerate units. The association of uranium minerals with carbonate and more rarely apatite, suggests that transport of uranium was as a carbonate or phosphate complex. The first comprehensive examination of paleoclimate, paleotopography, and subsurface structure of aquifers coupled with analysis of the geochronology of deposits suggests that that there were distinct pulses of uranium mineralization/redistribution during the period from about 259 Ma to 12 Ma when oxidized mineralizing fluids were intermittently rejuvenated in the Plateau in response to changes in tectonic regime and climate. Multiple lines of evidence indicate that deposits formed at ambient temperatures of about 25 °C to no greater than about 140 °C. In both systems, deposits formed where groundwater flow slowed and was subject to evaporative concentration. Stagnant conditions allowed for prolonged interaction of U- and V-enriched groundwater with ferrous iron-bearing reductants, such as illite and iron–titanium oxides, and more rarely organic material such as plant debris. Paragenetically late in the sequence, reducing fluids introduced additional organic matter to some deposits. Reducing fluids and introduced organic matter (now amorphous and altered by radiolysis) may originate from regional petroleum systems where peak oil and gas generation was from ∼ 82 to ∼ 5 Ma. Our novel analysis indicates that these reducing fluids bleached rock and protected affected deposits from remobilization during exposure and weathering that followed uplift of the Plateau (∼80 to 40 Ma).

Arizona, Colorado, Nevada, New Mexico, Utah↗

The Coles Hill uranium deposit, Virginia, USA: Geology, geochemistry, geochronology, and genetic model

The Coles Hill uranium deposit with an indicated resource of about 130 million lbs. of U 3 O 8 is the largest unmined uranium deposit in the United States. The deposit is hosted in the Taconian (approximately 480 – 450 Ma) Martinsville igneous complex, which consists of the Ordovician Leatherwood Granite (granodiorite) and Silurian Rich Acres Formation (diorite). The host rock was metamorphosed to orthogneiss during the Alleghanian orogeny (approximately 325 – 260 Ma) when it also underwent dextral strike-slip movement along the Brookneal shear zone. During the Triassic, extensional tectonics led to the development of the Dan River Basin that lies east of Coles Hill. The mineralized zone is hosted in brittle structures in the footwall of the Triassic Chatham fault that forms the western edge of the basin. Within brittle fracture zones, uranium silicate and uranium-bearing fluorapatite with traces of brannerite form veins and breccia fill with chlorite, quartz, calcite, titanium oxide, pyrite, and calcite. Uranium silicates also coat and replace primary titanite, zircon, ilmenite, and sulfides. Sodium metasomatism preceded and accompanied uranium mineralization, pervasively altering host rock, and forming albite from primary feldspar, depositing limpid albite rims on feldspar, altering titanite to titanium oxide and calcite and forming riebeckite. Various geothermometers suggest temperatures of less than approximately ~200°C during mineralization. In situ U-Pb analyses of titanite, Ti-oxide, and apatite, and Rb/Sr and U/Pb isotope-systematics of whole rock samples resolve the timing of geologic processes affecting Coles Hill. The host Leatherwood granite containing primary euhedral titanite is dated at 450 – 445 Ma, in agreement with previously obtained ages from zircon in the Martinsville igneous complex. A regional metamorphic event at 330 – 310 Ma formed anhedral titanite and some apatite, re-equilibrated whole rock Rb/Sr and U-Pb isotopes and is interpreted to have coincided with movement along the Brookneal shear zone. During shearing and metamorphism primary refractory uranium-bearing minerals including titanite, zircon, and uranothorite were recrystallized and uranium was liberated and incorporated locally into hematite, clay, and other fine-grained minerals. Uranium mineralization was accompanied by a metasomatic episode between 250 and 200 Ma that reset the Rb-Sr and U-Pb isotope systems, forming titanite and apatite that are associated and in places intimately intergrown with uranium silicate dating mineralization. This event coincides with rifting that formed the Dan River Basin and was a precursor to the breakup of Pangea. Based on the close spatial and temporal association of uranium with apatite, we conclude that uranium was carried as a uranyl-phosphate complex. The release of calcium during sodium metasomatic alteration of primary calcic feldspar and titanite in the host rock initiated successive reactions in which uranium and phosphate in mineralizing fluids combined with calcium to form U-enriched fluorapatite. Excess uranium was locally reduced by coupled redox reactions involving ferrous iron and sulfide minerals in the host rock, forming uranium silicates. Based on the deposit mineralogy, oxygen isotope geochemistry and trace element characteristics of uranium silicate and gangue minerals the primary mineralizing fluids likely included connate and/or meteoric water sourced from the local Dan River Basin. High heat flow related to Mesozoic rifting may have driven these (P-Na-F-rich) brines through local aquifers and into basin margin faults, transporting uranium from the basin or mobilizing uranium from previously formed U-minerals in the Brookneal shear zone, or from U-enriched older basement rock.

Virginia↗

Calcrete uranium deposits in the Southern High Plains, USA

The Southern High Plains (SHP) is a new and emerging U.S. uranium province. Here, uranyl vanadates form deposits in Pliocene to Pleistocene sandstone, dolomite, and limestone. Fifteen calcrete uranium occurrences are identified; two of these, the Buzzard Draw and Sulfur Springs Draw deposits, have combined in-place resources estimated at about 4 million pounds of U 3 O 8 . Ore minerals carnotite and finchite are hosted in dolomite at the Sulfur Springs Draw deposit, with accessory fluorite, celestine, smectite/illite, autunite, and strontium carbonate. Host carbonate at the Sulfur Springs Draw deposit is ∼190 ka and mineralization mobilized as recently as 3.8 ka. Ash collected near the deposit is 631 ka and erupted from the Yellowstone caldera complex. The Triassic Dockum Group that contains sandstone-hosted uranium deposits throughout the region and underlies the SHP is a potential source for uranium and vanadium. Regional uplift and dissection reintroduced oxygenated groundwater into the Dockum Group, mobilizing uranium. Additional uranium may have been contributed to groundwater by weathering of volcanic ash in Pliocene and Pleistocene host rocks. The locations of the uranium occurrences are mostly in modern drainage systems in the southeast portion of the SHP. Modelling of modern groundwater in the SHP carried out in a parallel study shows that a single fluid could form carnotite through evaporation, and that fluids of the requisite composition are more prevalent in the southern portion of the SHP. The southeastern portion of the SHP hosts more uranium occurrences due to a variety of factors including (1) upward transport of groundwater and connectivity between source and host rock, (2) higher uranium and vanadium content of groundwater, (3) higher rates of groundwater recharge in this region to drive the mineralizing system, and (4) shallower groundwater facilitating surface evaporation. Ongoing erosion of host rocks challenges preservation of deposits and may limit their size.

Southern High Plains↗

Uranium delivery and uptake in a montane wetland, north-central Colorado, USA

Comprehensive sampling of peat, underlying lakebed sediments, and coexisting waters of a naturally uraniferous montane wetland are combined with hydrologic measurements to define the important controls on uranium (U) supply and uptake. The major source of U to the wetland is groundwater flowing through locally fractured and faulted granite gneiss of Proterozoic age. Dissolved U concentrations in four springs and one seep ranged from 20 to 83 ppb (μg/l). Maximum U concentrations are ∼300 ppm (mg/kg) in lakebed sediments and >3000 ppm in peat. Uranium in lakebed sediments is primarily stratabound in the more organic-rich layers, but samples of similar organic content display variable U concentrations. Post-depositional modifications include variable additions of U delivered by groundwater. Uranium distribution in peat is heterogeneous and primarily controlled by proximity to groundwater-fed springs and seeps that act as local point sources of U, and by proximity to groundwater directed along the peat/lakebeds contact. Uranium is initially sorbed on various organic components of peat as oxidized U(VI) present in groundwater. Selective extractions indicate that the majority of sorbed U remains as the oxidized species despite reducing conditions that should favor formation of U(IV). Possible explanations are kinetic hindrances related to strong complex formation between uranyl and humic substances, inhibition of anaerobic bacterial activity by low supply of dissolved iron and sulfate, and by cold temperatures.

Colorado↗

Persistent U(IV) and U(VI) following in-situ recovery (ISR) mining of a sandstone uranium deposit, Wyoming, USA

Drill-core samples from a sandstone-hosted uranium (U) deposit in Wyoming were characterized to determine the abundance and distribution of uranium following in-situ recovery (ISR) mining with oxygen- and carbon dioxide-enriched water. Concentrations of uranium, collected from ten depth intervals, ranged from 5 to 1920 ppm. A composite sample contained 750 ppm uranium with an average oxidation state of 54% U(VI) and 46% U(IV). Scanning electron microscopy (SEM) indicated rare high uranium (&sim;1000 ppm U) in spatial association with P/Ca and Si/O attributed to relict uranium minerals, possibly coffinite, uraninite, and autunite, trapped within low permeability layers bypassed during ISR mining. Fission track analysis revealed lower but still elevated concentrations of U in the clay/silica matrix and organic matter (several 10 s ppm) and yet higher concentrations associated with Fe-rich/S-poor sites, likely iron oxides, on altered chlorite or euhedral pyrite surfaces (but not on framboidal pyrite). Organic C (<1.62%), total S (<0.31%), and P (<0.03%) were in low abundance relative to the overall bulk composition. Microbial community analysis showed a diverse group of bacteria present with a wide range of putative metabolisms, and provides evidence for a variety of redox microenvironments co-existing in core samples. Although the uranium minerals persisting in low permeability areas in association with organic carbon were less affected by oxidizing solutions during mining, the likely sequestration of uranium within labile iron oxides following mining and sensitivity to changes in redox conditions requires careful attention during groundwater restoration.

Wyoming↗

Geology, geochemistry, and geophysics of the Fry Canyon uranium/copper project site, southeastern Utah: Indications of contaminant migration

The Fry Canyon uranium/copper project site in San Juan County, southeastern Utah, was affected by the historical (1957–68) processing of uranium and copper-uranium ores. Relict uranium tailings and related ponds, and a large copper heap-leach pile at the site represent point sources of uranium and copper to local soils, surface water, and groundwater. This study was designed to establish the nature, extent, and pathways of contaminant dispersion. The methods used in this study are applicable at other sites of uranium mining, milling, or processing. The uranium tailings and associated ponds sit on a bench that is as much as 4.25 meters above the level of the adjacent modern channel of Fry Creek. The copper heap leach pile sits on bedrock just south of this bench. Contaminated groundwater from the ponds and other nearby sites moves downvalley and enters the modern alluvium of adjacent Fry Creek, its surface water, and also a broader, deeper paleochannel that underlies the modern creek channel and adjacent benches and stream terraces. The northern extent of contaminated groundwater is uncertain from geochemical data beyond an area of monitoring wells about 300 meters north of the site. Contaminated surface water extends to the State highway bridge. Some uranium-contaminated groundwater may also enter underlying bedrock of the Permian Cedar Mesa Sandstone along fracture zones. Four dc-resistivity surveys perpendicular to the valley trend were run across the channel and its adjacent stream terraces north of the heap-leach pile and ponds. Two surveys were done in a small field of monitoring wells and two in areas untested by borings to the north of the well field. Bedrock intercepts, salt distribution, and lithologic information from the wells and surface observations in the well field aided interpretation of the geophysical profiles there and allowed interpretation of the two profiles not tested by wells. The geophysical data for the two profiles to the north of the well field suggest that the paleochannel persists at least 900 m to the north of the heap leach and pond sites. Contamination of groundwater beneath the stream terraces may extend at least that far. Fry Creek surface water (six samples), seeps and springs (six samples), and wells (eight samples) were collected during a dry period of April 16–19, 2007. The most uranium-rich (18.7 milligrams per liter) well water on the site displays distinctive Ca-Mg-SO 4 -dominant chemistry indicating the legacy of heap leaching copper-uranium ores with sulfuric acid. This same water has strongly negative δ 34 S of sulfate (–13.3 per mil) compared to most local waters of –2.4 to –5.4 per mil. Dissolved uranium species in all sampled waters are dominantly U(VI)-carbonate complexes. All waters are undersaturated with respect to U(VI) minerals. The average 234 U/ 238 U activity ratio (AR) in four well waters from the site (0.939±0.011) is different from that of seven upstream waters (1.235±0.069). This isotopic contrast permits quantitative estimates of mixing of site-derived uranium with natural uranium in waters collected downstream. At the time of sampling, uranium in downstream surface water was mostly (about 67 percent) site-derived and subject to further concentration by evaporation. Three monitoring wells located approximately 0.4 kilometer downstream contained dominantly (78–87 percent) site-derived uranium. Distinctive particles of chalcopyrite (CuFeS) and variably weathered pyrite (FeS 2 ) are present in tailings at the stream edge on the site and are identified in stream sediments 1.3 kilometers downstream, based on inspection of polished grain mounts of magnetic mineral separates.

Utah↗

Uranium in surface waters and sediments affected by historical mining in the Denver West 1:100,000 Quadrangle, Colorado

Geochemical sampling of 82 stream waters and 87 stream sediments within mountainous areas immediately west of Denver, Colorado, was conducted by the U.S. Geological Survey in October 1994. The primary purpose was to evaluate regionally the effects of geology and past mining on the concentration and distribution of uranium. The study area contains uranium- and thorium-rich bedrock, numerous noneconomic occurrences of uranium minerals, and several uranium deposits of variable size and production history. During the sampling period, local streams had low discharge and were more susceptible to uranium-bearing acid drainage originating from historical mines of base- and precious-metal sulfides. Results indicated that the spatial distribution of Precambrian granites and metamorphic rocks strongly influences the concentration of uranium in stream sediments. Within-stream transport increases the dispersion of uranium- and thorium rich mineral grains derived primarily from granitic source rocks. Dissolved uranium occurs predominantly as uranyl carbonate complexes, and concentrations ranged from less than 1 to 65 micrograms per liter. Most values were less than 5 micrograms per liter, which is less than the current drinking water standard of 30 micrograms per liter and much less than locally applied aquatic-life toxicity standards of several hundred micrograms per liter. In local streams that are affected by uranium-bearing acid mine drainage, dissolved uranium is moderated by dilution and sorptive uptake by stream sediments. Sorbents include mineral alteration products and chemical precipitates of iron- and aluminum-oxyhydroxides, which form where acid drainage enters streams and is neutralized. Suspended uranium is relatively abundant in some stream segments affected by nearby acid drainage, which likely represents mobilization of these chemical precipitates. The 234U/238U activity ratio of acid drainage (0.95-1.0) is distinct from that of local surface waters (more than 1.05), and this distinctive isotopic composition may be preserved in iron-oxyhydroxide precipitates of acid drainage origin. The study area includes a particularly large vein-type uranium deposit (Schwartzwalder mine) with past uranium production. Stream water and sediment collected downstream from the mine's surface operations have locally anomalous concentrations of uranium. Fine-grained sediments downstream from the mine contain rare minute particles (10-20 micrometers) of uraninite, which is unstable in a stream environment and thus probably of recent origin related to mining. Additional rare particles of very fine grained (less than 5 micrometer) barite likely entered the stream as discharge from settling ponds in which barite precipitation was formerly used to scavenge dissolved radium from mine effluent.

Colorado↗

Composition of pore water in lake sediments, research site "B", Osage County, Oklahoma: Implications for lake water quality and benthic organisms

Shallow ground water at US Geological Survey research site B in northeastern Oklahoma is contaminated with NaCl-rich brine from past and present oil production operations. Contaminated ground water provides a potential source of salts, metals, and hydrocarbons to sediment and water of adjacent Skiatook Lake. A former brine storage pit 10 m in diameter that is now submerged just offshore from site B provides an additional source of contamination. Cores of the upper 16–40 cm of lake sediment were taken at the submerged brine pit, near an offshore saline seep, and at a location containing relatively uncontaminated lake sediment. Pore waters from each 2-cm interval were separated by centrifugation and analyzed for dissolved anions, cations, and trace elements. High concentrations of dissolved Cl − in pore waters (200–5000 mg/L) provide the most direct evidence of contamination, and contrast sharply with an average value of only about 37 mg/L in Skiatook Lake. Chloride/Br − mass ratios of 220–240 in contaminated pore waters are comparable to values in contaminated well waters collected onshore. Dissolved concentrations of Se, Pb, Cu and Ni in Cl − -rich pore waters exceed current US Environmental Protection Agency criteria for probable toxicity to aquatic life. At the submerged brine storage pit, the increase of Cl − concentration with depth is consistent with diffusion-dominant transport from deeper contaminated sediments. Near the offshore saline seep, pore water Cl − concentrations are consistently high and vary irregularly with depth, indicating probable Cl − transport by layer-directed advective flow. Estimated annual contributions of Cl − to the lake from the brine storage pit (∼20 kg) and the offshore seep (∼9 kg) can be applied to any number of similar sources. Generous estimates of the number of such sources at site B indicate minimal impact on water quality in the local inlet of Skiatook Lake. Similar methodologies can be applied at other sites of NaCl contamination surrounding Skiatook Lake and elsewhere.

Oklahoma↗

Mode of occurrence and environmental mobility of oil-field radioactive material at US Geological Survey research site B, Osage-Skiatook Project, northeastern Oklahoma

Two samples of produced-water collected from a storage tank at US Geological Survey research site B, near Skiatook Lake in northeastern Oklahoma, have activity concentrations of dissolved 226 Ra and 228 Ra that are about 1500 disintegrations/min/L (dpm/L). Produced-water also contains minor amounts of small (5–50 μm) suspended grains of Ra-bearing BaSO 4 (barite). Precipitation of radioactive barite scale in the storage tank is probably hindered by low concentrations of dissolved SO 4 (2.5 mg/L) in the produced-water. Sediments in a storage pit used to temporarily collect releases of produced-water have marginally elevated concentrations of “excess” Ra (several dpm/g), that are 15–65% above natural background values. Tank and pit waters are chemically oversaturated with barite, and some small (2–20 μm) barite grains observed in the pit sediments could be transferred from the tank or formed in place. Measurements of the concentrations of Ba and excess Ra isotopes in the pit sediments show variations with depth that are consistent with relatively uniform deposition and progressive burial of an insoluble Ra-bearing host (barite?). The short-lived 228 Ra isotope (half-life = 5.76 a) shows greater reductions with depth than 226 Ra (half-life = 1600 a), that are likely explained by radioactive decay. The 228 Ra/ 226 Ra activity ratio of excess Ra in uppermost pit sediments (1.13–1.17) is close to the ratio measured in the samples of produced-water (0.97, 1.14). Declines in Ra activity ratio (excess) with sediment depth can be used to estimate an average rate of burial of 4 cm/a for the Ra-bearing contaminant. Local shallow ground waters contaminated with NaCl from produced-water have low dissolved Ra (<20 dpm/L) and also are oversaturated with barite. Barite is a highly insoluble Ra host that probably limits the environmental mobility of Ra at site B.

Oklahoma↗

Geologic controls on movement of produced-water releases at US geological survey research Site A, Skiatook lake, Osage county, Oklahoma

Highly saline produced water was released from multiple sources during oil field operations from 1913 to 1973 at the USGS research Site A on Skiatook Lake in northeastern Oklahoma. Two pits, designed to hold produced water and oil, were major sources for release of these fluids at the site. Produced water spills from these and other features moved downslope following topography and downdip by percolating through permeable eolian sand and colluvium, underlying permeable sandstone, and, to a lesser extent, through shales and mudstones. Saline water penetrated progressively deeper units as it moved through the gently dipping bedrock to the north and NW. A large eroded salt scar north of the pits coincides with underlying fine-grained rocks that have retained substantial concentrations of salt, causing slow revegetation. Where not eroded, thick eolian sand or permeable sandstone bedrock is near the surface, and vegetation has been little affected or has reestablished itself after the introduced salt was flushed by precipitation. The extent of salt-contaminated bedrock extends well beyond existing surface salt scars. These results indicate that one of the legacies of surface salt spills can be a volume of subsurface salinization larger than the visible surface disturbance.

Oklahoma↗

Characterization and modes of occurrence of elements in feed coal and coal combustion products from a power plant utilizing low-sulfur coal from the Powder River Basin, Wyoming

The U.S. Geological Survey and the University of Kentucky Center for Applied Energy Research are collaborating with an Indiana utility company to determine the physical and chemical properties of feed coal and coal combustion products from a coal-fired power plant. The Indiana power plant utilizes a low-sulfur (0.23 to 0.47 weight percent S) and lowash (4.9 to 6.3 weight percent ash) subbituminous coal from the Wyodak-Anderson coal zone in the Tongue River Member of the Paleocene Fort Union Formation, Powder River Basin, Wyoming. Based on scanning electron microscope and X-ray diffraction analyses of feed coal samples, two mineral suites were identified: (1) a primary or detrital suite consisting of quartz (including beta-form grains), biotite, feldspar, and minor zircon; and (2) a secondary authigenic mineral suite containing alumino-phosphates (crandallite and gorceixite), kaolinite, carbonates (calcite and dolomite), quartz, anatase, barite, and pyrite. The primary mineral suite is interpreted, in part, to be of volcanic origin, whereas the authigenic mineral suite is interpreted, in part, to be the result of the alteration of the volcanic minerals. The mineral suites have contributed to the higher amounts of barium, calcium, magnesium, phosphorus, sodium, strontium, and titanium in the Powder River Basin feed coals in comparison to eastern coals. X-ray diffraction analysis indicates that (1) fly ash is mostly aluminate glass, perovskite, lime, gehlenite, quartz, and phosphates with minor amounts of periclase, anhydrite, hematite, and spinel group minerals; and (2) bottom ash is predominantly quartz, plagioclase (albite and anorthite), pyroxene (augite and fassaite), rhodonite, and akermanite, and spinel group minerals. Microprobe and scanning electron microscope analyses of fly ash samples revealed quartz, zircon, and monazite, euhedral laths of corundum with merrillite, hematite, dendritic spinels/ferrites, wollastonite, and periclase. The abundant calcium and magnesium mineral phases in the fly ash are attributed to the presence of carbonate, clay, and phosphate minerals in the feed coal and their alteration to new phases during combustion. The amorphous diffraction-scattering maxima or glass 'hump' appears to reflect differences in chemical composition of fly ash and bottom ash glasses. In Wyodak-Anderson fly and bottom ashes, the center point of scattering maxima is due to calcium and magnesium content, whereas the glass 'hump' of eastern fly ash reflects variation in aluminum content. The calcium- and magnesium-rich and alumino-phosphate mineral phases in the coal combustion products can be attributed to volcanic minerals deposited in peat-forming mires. Dissolution and alteration of these detrital volcanic minerals occurred either in the peat-forming stage or during coalification and diagenesis, resulting in the authigenic mineral suite. The presence of free lime (CaO) in fly ash produced from Wyodak-Anderson coal acts as a self-contained 'scrubber' for SO3, where CaO + SO3 form anhydrite either during combustion or in the upper parts of the boiler. Considering the high lime content in the fly ash and the resulting hydration reactions after its contact with water, there is little evidence that major amounts of leachable metals are mobilized in the disposal or utilization of this fly ash.

Scientific Investigations Report↗

Chapter 8 Petrogenesis and mineralogic residence of selected elements in the meade peak phosphatic shale member of the permian phosphoria formation, Southeast Idaho

The Meade Peak Phosphatic Shale Member of the Permian Phosphoria Formation hosts the ore mined by the phosphate industry of southeast Idaho. It also hosts environmentally sensitive elements (ESE) such as Se, As, Hg, Ni, Cd, Zn, and Cr. Primary chemistry, elemental distribution patterns, and mineralogy within the Meade Peak were modified by element migration and possibly the introduction of elements. Fluids moved within the Meade Peak throughout its history, although the passage of fluids was highly variable in space and time, resulting in small domains of different rock chemistry and different mineralogy. Timing of major events affecting the Meade Peak and mineral habit are used to differentiate among detrital, diagenetic, epigenetic, and supergene mineral assemblages. Cross-cutting relationships among minerals are too rare to provide much paragenetic infor- mation. Carbonate fluorapatite (CFA) occurs in several forms, but dominantly as pelloids, some of which may have formed in situ during diagenesis. The other volumetrically signifi- cant form of CFA is interstitial cement that formed during diagenesis. Beginning during diagenesis and continuing intermittently, multiple generations of carbonate (dolomite and calcite) formed overgrowths and texturally complex carbonate cements. Movement and precipitation of silica followed a similar pattern. The ammonium feldspar buddingtonite, which generally rims orthoclase, also formed during diagenesis. Bacteria apparently played a significant role during diagenesis as well as during supergene processes, resulting in extreme fractionation of S isotopes and the possible bacterially mediated formation of minerals such as glauconite and sphalerite. Catagenesis, apparently culminating in oil generation, was the last significant diagenetic change. Thrusting accompanied by fluid (oil and brine) migration began during catagenesis in the Late Jurassic or Cretaceous and continued into the early Eocene. Fluorite ± carbonate ± barite± bitumen veins formed as a result of brittle deformation and accompanying fluid movement. This fracturing event may have been associated with a period of extension and normal faulting (Neogene to Holocene). Passage of the Yellowstone hot spot to the north of the area during the Neogene is marked by silicic domes and basaltic flows. The enrichment of Hg in fracture coatings might be the result of deposition from warm fluids associated with the emplacement of the silicic domes or a generally elevated, regional thermal gradient associated with the volcanism. Many of the fracture systems are still open and continue to provide fluid pathways that are the primary depositional sites for a wide variety of supergene minerals (such as Se, efflorescent salts) and element associations (such as Hg, Cd-S, Fe-Cr-O) in which many of the ESE are concentrated. Native Se is the most commonly identified host of Se in the studied samples. The largest concentration of Se occurs in open-fracture systems that cross-cut waste rock and ore units. The age(s) of native Se formation is not known; how- ever, the latest period of Se mobility is the present. Direct measurement of efflorescent “salts” forming on new mine faces indicate that several ESE, including both Se and Zn, are concentrated on the faces soon after they are exposed. Zinc is present as hydrous sulfates, but the residence of Se in these “salts” is unknown.

Idaho↗

Weathering of the meade peak phosphatic shale member, phosphoria formation: Observations based on uranium and its decay products

Variably weathered outcrop samples of the Meade Peak Phosphatic Shale Member of the Phosphoria Formation have 5-10% of the contained uranium (U) in a form readily extractable by 0.1 M sodium bicarbonate. Fission track radiography of outcrop samples and other less-weathered channel and core samples indicate that this mobile fraction of U is likely hosted by organic matter, secondary iron oxides and clay minerals, trace uraninite, and very fine-grained apatite cement. During weathering, this extractable U fraction is especially susceptible to redistribution, which produces small but measurable departures (1-15%) from radioactive (secular) equilibrium in the 238 U decay-series. The most weath- ered samples show the strongest isotopic evidence for redistribution of U during the last 350 ka, but sequestration of U by alteration products limits open-system losses of U at the whole-rock scale. In less-weathered samples, isotopic evidence for minor U loss (or gain) over longer time periods (1 Ma) is consistent with relatively non-aggressive attack of phosphatic rock during weathering. Comparative extractability of selenium (Se) suggests that a larger fraction of Se (19%) is readily available for mobilization during the earliest stages of weathering.

Book chapter↗

Dinosaurs that did not die: Evidence for Paleocene dinosaurs in the Ojo Alamo Sandstone, San Juan Basin, New Mexico

Palynologic and paleomagnetic data confirm a Paleocene age for the Ojo Alamo Sandstone (and its contained dinosaurs) throughout the San Juan Basin of New Mexico. The recently reported discovery of 34 skeletal elements from a single hadrosaur in the Ojo Alamo provides unequivocal evidence that these bones were not reworked from underlying Cretaceous strata. Geochemical studies of samples from several single-dinosaur-bone specimens from the Paleocene Ojo Alamo Sandstone and the underlying Late Cretaceous (Campanian) Kirtland Formation show that mineralized bones from these two rock units contain distinctly different abundances of uranium and rare-earth elements and demonstrate that Cretaceous and Paleocene bones were mineralized at different times when mineralizing fluids had distinctly different chemical compositions. These findings indicate that the dinosaur bone from the Paleocene Ojo Alamo is indigenous and not reworked. These data show that a relatively diverse assemblage of dinosaurs survived the end-Cretaceous asteroid-impact extinction event of 65.5 Ma. The San Juan Basin’s Paleocene dinosaur fauna is herein named the Alamoan fauna. Magnetic-polarity chronology shows that these survivors lived for about one million years into the Paleocene and then became extinct around 64.5 Ma. We suggest that a plausible survival mechanism for this Lazarus fauna may have been the large numbers of buried dinosaur eggs, laid just before the asteroid impact occurred. These buried eggs would have provided a safe haven for developing dinosaur embryos for the first one to two years after the impact, thereby making it possible for them to survive the worst of the impact’s early devastation.

Colorado, New Mexico↗

Produced water and hydrocarbon releases at the Osage-Skiatook petroleum environmental research sites, Osage County, Oklahoma: Introduction and geologic setting

In February 2001, the USGS started studies of the impacts of produced water and hydrocarbon releases at 2 research sites adjacent to Skiatook Lake in southeastern Osage County near Tulsa, Oklahoma. Both sites are in a dissected area of modest relief underlain by interbedded shale, siltstone, and sandstone. Thicker resistant sandstone units typically form the hill crests. Hillslopes are underlain by shale, siltstone, and thin sandstone beds. Core drilling during February and March of 2002 indicates that the depth of weathering of the bedrock is about 10-25 m on the ridges and 5-6 m in small stream valleys. These sites are located in the Cross Timbers ecosystem area of northeastern Oklahoma. Oak forests cover the hillslopes. Grassslands occur on most ridge crests. Site "A" is an area where produced water and hydrocarbon releases occurred primarily 60-85 years ago. The site is located in section 13, T22N, R10E. The entire site is underlain by 1) a surface layer of eolian sand of varying thickness (maximum observed about 80 cm); 2) colluvium that ranges from large boulders of sandstone to thin, granule-pebble conglomerate; 3) weathered shale, siltstone, and sandstone; and 4) underlying unweathered bedrock. Much of the site appears to have been impacted by early salt-water releases that killed the oak forest, however a few oak trees persist as single trees or clumps of trees within the original kill area. The gently sloping upper part of the site is slightly eroded in places and has been mostly revegetated with grasses, forbs, sumac, and a few trees. The lower, steeper, more heavily salt-impacted portion has been eroded to depths of as much as 2 m. This area drains into the Cedar Creek arm of Skiatook Lake. Oil from two redwood tanks at the top of the site was transported via ditch to two roadside pits at mid-site. Oil spills from pipeline breaks and tank batteries (no longer present) are scattered around the site. Most of the oil is highly weathered however, one pit contains what appears to be relatively fresh asphaltic tank bottom material. Site "B" is located in sections 29 and 32, T22N, R10E. It includes an active production tank battery and adjacent large pit, two injection well sites, one with an adjacent small pit, and an old tank battery. All of these sites are within 45 m of the shoreline of the lake (at normal pool elevation). The pit associated with the active tank battery is within 15 m of the lake. Two small creeks cross the northern and southern parts of the site. The upper part of the site is characterized by a thin surface layer of eolian sand mixed with sandstone-clast colluvium underlain by weathered and unweathered shale whereas the lower part of the site is underlain by 1) a surface layer of eolian sand (20-70 cm thick); 2) colluvial apron and alluvial deposits of varying thickness comprised of sandstone pebbles, cobbles, and boulders with a fine sand matrix; 3) weathered shale; and 4) unweathered bedrock. Three salt scars extend downslope from the active tank battery, the injection well/pit, and the old tank battery to the lake edge. The area underlain by shallow saline ground water is substantially larger than the salt-scarred areas. Dissolved hydrocarbons can be detected in the shallow ground water below the active pit.

Oklahoma↗

Use of soil leachates to define the extent of brine-contaminated soils at the USGS petroleum environmental research site "B", Osage County, northeastern Oklahoma

Soils at an active oil production site with a history of surface releases of produced water were investigated to determine the chemical signature of salt contamination and the spatial distribution of soil salinity in relation to areas of obvious salt scarring. Grab samples of shallow soil (0-15 cm) and selected soil profiles to depths of 0.6 to 1.7 m were collected onsite and offsite using a 5-cm diameter stainless steel soil auger. Air dried and disaggregated soil from 15 cm intervals (100 g) was mixed with 100 ml of distilled-deionized water to dissolve readily soluble salts. After 24 hours the water was separated by centrifugation followed by filtration through a 0.45 micrometer membrane. Specific conductance was measured immediately. Dissolved chloride (Cl) and sulfate (SO4) were initially estimated with Cl titration strips and turbidimetric measurements respectively. More accurate measurements of dissolved Cl, SO4, and bromide (Br) were later performed by ion chromatography. Brine-contaminated soil was indicated by (1) unusually elevated Cl concentrations or relatively low ratios of conductance/Cl in aqueous leachates compared to leachates of uncontaminated soils, and (2) ratios of Cl/Br in leachates (250± 30) that fall within the range of Cl/Br ratios measured in local produced waters (220-320). Leachates of background soils from the area were characterized by low conductance (sandy soils) or dissolved solids dominated by sulfates (shaley soils). At the study site, the surface (0-15 cm) distribution of elevated soil salinity was largely confined to areas of obvious salt scarring. Within the area of salt scars, elevated salinity persisted to depths of refusal by manual augering. The technique will be applied to deeper samples obtained by mechanical augering or direct push techniques.

Oklahoma↗