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J. F. Whelan

Publications and source records attributed to J. F. Whelan.

At least 19 recordsLinked to original sources

Limited hydrologic response to Pleistocene climate change in deep vadose zones - Yucca Mountain, Nevada

Understanding the movement of water through thick vadose zones, especially on time scales encompassing long-term climate change, is increasingly important as societies utilize semi-arid environments for both water resources and sites viewed as favorable for long-term disposal or storage of hazardous waste. Hydrologic responses to Pleistocene climate change within a deep vadose zone in the eastern Mojave Desert at Yucca Mountain, Nevada, were evaluated by uranium-series dating of finely layered hyalitic opal using secondary ion mass spectrometry. Opal is present within cm-thick secondary hydrogenic mineral crusts coating floors of lithophysal cavities in fractured volcanic rocks at depths of 200 to 300 m below land surface. Uranium concentrations in opal fluctuate systematically between 5 and 550 μg/g. Age-calibrated profiles of uranium concentration correlate with regional climate records over the last 300,000 years and produce time-series spectral peaks that have distinct periodicities of 100- and 41-ka, consistent with planetary orbital parameters. These results indicate that the chemical compositions of percolating solutions varied in response to near-surface, climate-driven processes. However, slow (micrometers per thousand years), relatively uniform growth rates of secondary opal and calcite deposition spanning several glacial–interglacial climate cycles imply that water fluxes in the deep vadose zone remained low and generally buffered from the large fluctuations in available surface moisture during different climates.

Nevada

Thermal history of the unsaturated zone at Yucca Mountain, Nevada, USA

Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (Th) up to ???80 ??C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite ??18O values, and depositional timing is constrained by the 207Pb/235U ages of chalcedony or opal in the deposits. Fluid inclusion Th from 50 samples of calcite and four samples of fluorite range from ???35 to ???90 ??C. Calcite ??18O values range from ???0 to ???22??? (SMOW) but most fall between 12 and 20???. The highest Th and the lowest ??18O values are found in the older calcite. Calcite Th and ??18O values indicate that most calcite precipitated from water with ??18O values between -13 and -7???, similar to modern meteoric waters. Twenty-two 207Pb/235U ages of chalcedony or opal that generally postdate elevated depositional temperatures range from ???9.5 to 1.9 Ma. New and published 207Pb/235U and 230Th/Uages coupled with the Th values and estimates of temperature from calcite ??18O values indicate that maximum unsaturated zone temperatures probably predate ???10 Ma and that the unsaturated zone had cooled to near-present-day temperatures (24-26 ??C at a depth of 250 m) by 2-4 Ma. The evidence of elevated temperatures persisting in ash flow tuffs adjacent to parent calderas for as much as ???8 Ma is a new finding, but consistent with thermal modeling. Simulations using the HEAT code demonstrate that prolonged cooling of the unsaturated zone is consistent with magmatic heat inputs and deep-seated (sub-water table) hydrothermal activity generated by the large magma body ???8 km to the north that produced the 15-11 Ma ash flows and ash falls that make up Yucca Mountain. The evidence discussed in this and preceding papers strongly supports unsaturated zone deposition of the secondary minerals from descending meteoric waters. Although depositional temperatures reflect conductive (and possibly vapor-phase convective) heating of the unsaturated zone related to regional magmatic sources until perhaps 6 Ma, depositional conditions similar to the present-day unsaturated zone have prevailed for at least the past 2-4 Ma.

Applied Geochemistry

Impact of quaternary climate on seepage at Yucca Mountain, Nevada

Uranium-series ages, oxygen-isotopic compositions, and uranium contents were determined in outer growth layers of opal and calcitefrom 0.5- to 3-centimeter-thick mineral coatings hosted by lithophysal cavities in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a permanent repository for high-level radioactive waste. Micrometer-scale growth layering in the minerals was imaged using a cathodoluminescence detector on a scanning electron microscope. Determinations of the chemistry, ages, and delta oxygen-18 (??18O) values of the growth layers were conducted by electron microprobe analysis and secondary ion mass spectrometry techniques at spatial resolutions of 2 to about 20 micrometers (??m) and 25 to 40 ??m, respectively. Growth rates for the last 300 thousand years (k.y.) calculated from about 300 new high-resolution uranium-series ages range from approximately 0.5 to 1.5 ??m/k.y. for 1- to 3-centimeter-thick coatings, whereas coatings less than about 1-centimeter-thick have growth rates less than 0.5 ??m/k.y. At the depth of the proposed repository, correlations of uranium concentration and ??18O values with regional climate records indicate that unsaturated zone percolation and seepage water chemistries have responded to changes in climate during the last several hundred thousand years.

Conference Paper

Characterization of seepage in the exploratory studies facility, Yucca Mountain, Nevada

Following a 5-month period of above-average precipitation during the winter of 2004-2005, water was observed seeping into the South Ramp section of the Exploratory Studies Facility of the proposed repository for high-level radioactive waste at Yucca Mountain, Nevada. Samples of the seepage were collected and analyzed for major ions, trace metals, and delta deuterium and delta oxygen-18 values in an effort to characterize the water and assess the interaction of seepage with anthropogenic materials used in the construction of the proposed repository. As demonstrated by the changes in the chemistry of water dripping from a rock bolt, interaction of seepage with construction materials can alter solution chemistry and oxidation state.

Conference Paper

Geochemical and C, O, Sr, and U-series isotopic evidence for the meteoric origin of calcrete at Solitario Wash, Crater Flat, Nevada, USA

Calcite-rich soils (calcrete) in alluvium and colluvium at Solitario Wash, Crater Flat, Nevada, USA, contain pedogenic calcite and opaline silica similar to soils present elsewhere in the semi-arid southwestern United States. Nevertheless, a ground-water discharge origin for the Solitario Wash soil deposits was proposed in a series of publications proposing elevation-dependent variations of carbon and oxygen isotopes in calcrete samples. Discharge of ground water in the past would raise the possibility of future flooding in the unsaturated zone at Yucca Mountain, Nevada, site of a proposed high-level nuclear waste repository. New geochemical and carbon, oxygen, strontium, and uranium-series isotopic data disprove the presence of systematic elevation-isotopic composition relations, which are the main justification given for a proposed ground-water discharge origin of the calcrete deposits at Solitario Wash. Values of ??13C (-4.1 to -7.8 per mil [???]), ??18O (23.8-17.2???), 87Sr/ 86Sr (0.71270-0.71146), and initial 234U/238U activity ratios of about 1.6 in the new calcrete samples are within ranges previously observed in pedogenic carbonate deposits at Yucca Mountain and are incompatible with a ground-water origin for the calcrete. Variations in carbon and oxygen isotopes in Solitario Wash calcrete likely are caused by pedogenic deposition from meteoric water under varying Quaternary climatic conditions over hundreds of thousands of years. ?? Springer-Verlag 2005.

Environmental Geology

Physical and stable-isotope evidence for formation of secondary calcite and silica in the unsaturated zone, Yucca Mountain, Nevada

Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite??fluorite??zeolites that is frequently capped by chalcedony??quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (??? 3 mm) with low-relief outer surfaces whereas shallow-dipping fractures and lithophysal cavities typically contain thicker, more coarsely crystalline deposits characterized by unusual thin, tabular calcite blades up to several cms in length. These blades may be capped with knobby or corniced overgrowths of late-stage calcite intergrown with opal. The observed textures in the fracture and cavity deposits are consistent with deposition from films of water fingering down fracture footwalls or drawn up faces of growing crystals by surface tension and evaporated at the crystal tips. Fluid inclusion studies have shown that most early-stage and some intermediate-stage calcite formed at temperatures of 35 to 85??C. Calcite deposition during the past several million years appears to have been at temperatures < 30??C. The elevated temperatures indicated by the fluid inclusions are consistent with temperatures estimated from calcite ??18O values. Although others have interpreted the elevated temperatures as evidence of hydrothermal activity and flooding of the tuffs of the potential repository, the authors conclude that the temperatures and fluid-inclusion assemblages are consistent with deposition in a UZ environment that experienced prolonged heat input from gradual cooling of nearby plutons. The physical restriction of the deposits (and, therefore, fluid flow) to fracture footwalls and cavity floors and the heterogeneous and limited distribution of the deposits provides compelling evidence that they do not reflect flooding of the thick UZ at Yucca Mountain. The textures and isotopic and chemical compositions of these mineral deposits are consistent with deposition in a UZ setting from meteoric waters percolating downward along fracture flow paths.

Applied Geochemistry

Carbon isotopes in biological carbonates: Respiration and photosynthesis

Respired carbon dioxide is an important constituent in the carbonates of most air breathing animals but is much less important in the carbonates of most aquatic animals. This difference is illustrated using carbon isotope data from freshwater and terrestrial snails, ahermatypic corals, and chemoautotrophic and methanotrophic pelecypods. Literature data from fish otoliths and bird and mammal shell and bone carbonates are also considered. Environmental CO 2 /O 2 ratios appear to be the major controlling variable. Atmospheric CO 2 /O 2 ratios are about thirty times lower than in most natural waters, hence air breathing animals absorb less environmental CO 2 in the course of obtaining 0 2 . Tissue CO 2 therefore, does not isotopically equilibrate with environmental CO 2 as thoroughly in air breathers as in aquatic animals, and this is reflected in skeletal carbonates. Animals having efficient oxygen transport systems, such as vertebrates, also accumulate more respired CO 2 in their tissues. Photosynthetic corals calcify mainly during the daytime when photosynthetic CO 2 uptake is several times faster than respiratory CO 2 release. Photosynthesis, therefore, affects skeletal δ 13 C more strongly than does respiration. Corals also illustrate how “metabolic” effects on skeletal isotopic composition can be estimated, despite the presence of much larger “kinetic” isotope effects.

Nevada

Isotopic discontinuities in ground water beneath Yucca Mountain, Nevada

Analytical data for stable isotopes in ground water from beneath Yucca Mountain, when examined in map view, show areal patterns of heterogeneity that can be interpreted in terms of mixing of at least three end members. One end member must be isotopically heavy in terms of hydrogen and oxygen and have a young apparent 14C age such as water found at the north end of Yucca Mountain beneath Fortymile Wash. A second end member must contain isotopically heavy carbon and have an old apparent 14C age such as water from the Paleozoic aquifer. The third end member cannot be tightly defined. It must be isotopically lighter than the first with respect of hydrogen and oxygen and be intermediate to the first and second end members with respect to both apparent 14C age and ?? 13C. The variable isotopic compositions of hydrogen and oxygen indicate that two of the end members are waters, but the variable carbon isotopic composition could represent either a third water end member or reaction of water with a carbon-bearing solids such as calcite.

Conference Paper

Stable isotope geochemistry of sphalerite and other mineral matter in coal beds of the Illinois and Forest City basins

Cleat and clastic dikes of Middle Pennsylvanian-age coal beds of the Illinois and Forest City basins of Illinois, Iowa, Missouri, and Kansas locally contain appreciable amounts of sphalerite within a kaolinite-pyrite-sphalerite (+ or - pyrite)-calcite paragenetic sequence. The sphalerite and associated minerals are of interest as a partial record of the history of fluids in the sedimentary basin and as possible indicators of Mississippi Valley-type mineralization. Moreover, zinc from the sphalerite may represent an exploitable by-product of coal mining and combustion.Pyrite is abundant in these coals both as fine-grained disseminated framboids that formed during early diagenesis and as coarser grained cleat fillings, etc., that formed much later. The delta 34 S values of this later pyrite, the sphalerite, and the coal organic matter range from -12 to 19 per mil. Within individual samples, however, pyrite, sphalerite, and organic matter sulfur delta 34 S values are nearly identical. This similarity strongly suggests related origins. The delta 34 S values of pyrite, sphalerite, and organic matter from coals of the Illinois basin and the central and southern Forest City basin range from -12 to 0 per mil. This range is not unique to the sphalerite-bearing coals; pyrite and organic matter from sphalerite-free high sulfur coals have similar delta 34 S values (Price and Shieh, 1979). We believe that sulfur produced by the breakdown of organosulfur compounds in the coal is incorporated into the epigenetic sulfides. In the northern Forest City basin, however, many samples have delta 34 S values between 8 and 19 per mil. These are similar to the delta 34 S values of sphalerite and pyrite from the Upper Mississippi Valley Zn-Pb district which lies northeast of the Forest City basin and north of the Illinois basin. This similarity suggests input from a Mississippi Valley-type hydrothermal system.Cleat kaolinite has delta D values of -36 to -24 per mil and delta 18 O values of 19.2 to 20.2 per mil. Assuming that clearing postdated the lignite rank of coalification implies that kaolinite was deposited between 40 degrees and 100 degrees C. At the lower temperatures, the kaolinite fluid would have had an isotopic composition similar to seawater; at the higher temperatures, it would have had a composition similar to the sphalerite-depositing fluid. Sphalerite was deposited from a fluid that was chemically and isotopically similar to the fluids responsible for the main-stage ores of the Upper Mississippi Valley Zn-Pb district (75 degrees -113 degrees C, approximately 21 equiv wt % NaCl, delta D = -65 to -3ppm, and delta 18 O = -0.9-9.9ppm). The isotopic compositions (delta 13 C = -12.4 to -2.7ppm and delta 18 O = 21.1-25.8ppm) and paragenetic positions of the cleat calcite samples are similar to those of the late-stage calcite of the Upper Mississippi Valley Zn-Pb and Illinois-Kentucky fluorspar districts. Calcite inclusion fluids had delta D (sub H 2 O) values of -80 and -58 per mil, implying a meteoric water source. At probable temperatures of 15 degrees to 75 degrees C, this calcite formed from fluids having calculated delta 18 O (sub H 2 O) values of -9 to 1 per mil, implying slight to moderate exchange with sedimentary rocks. The diagenetic-epigenetic history of fluids recorded by the cleat minerals probably began with a slightly evolved seawater, followed by a metal-bearing deep basin brine, and concluded with a cooler, slightly evolved, meteoric-water fluid.

Economic Geology