Interpretation of heterogeneity effects in synchrotron X-ray fluorescence microprobe data

Heterogeneity effects often limit the accuracy of synchrotron X-ray fluorescence microprobe elemental analysis data to ± 30%. The difference in matrix mass absorption at Kα and Kβ fluorescence energies of a particular element can be exploited to yield information on the average depth-position of the element or account for heterogeneity effects. Using this technique, the heterogeneous distribution of Cu in a simple layered sample could be resolved to a 2 × 2 × 10 (x, y, z, where z is the depth coordinate) micrometer scale; a depth-resolution limit was determined for the first transition metal series and several other elements in calcite and iron oxide matrices. For complex heterogeneous systems, determination of average element depth may be computationally limited but the influence of heterogeneity on fluorescence data may still be assessed. We used this method to compare solid-state diffusion with sample heterogeneity across the Ni-serpentine/calcite boundary of a rock from Panoche Creek, California. We previously reported that Ni fluorescence data may indicate solid state diffusion; in fact, sample heterogeneity in the depth dimension can also explain the Ni fluorescence data. Depth heterogeneity in samples can lead to misinterpretation of synchrotron X-ray microprobe results unless care is taken to account for the influence of heterogeneity on fluorescence data

Characterization of Microbial Communities in Subsurface Nuclear Blast Cavities of the Nevada Test Site

This U.S. Department of Energy (DOE) Environmental Remediation Sciences Project (ERSP) was designed to test fundamental hypotheses concerning the existence and nature of indigenous microbial populations of Nevada Test Site subsurface nuclear test/detonation cavities. Now called Subsurface Biogeochemical Research (SBR), this program’s Exploratory Research (ER) element, which funded this research, is designed to support high risk, high potential reward projects. Here, five cavities (GASCON, CHANCELLOR, NASH, ALEMAN, and ALMENDRO) and one tunnel (U12N) were sampled using bailers or pumps. Molecular and cultivation-based techniques revealed bacterial signatures at five sites (CHANCELLOR may be lifeless). SSU rRNA gene libraries contained diverse and divergent microbial sequences affiliated with known metal- and sulfur-cycling microorganisms, organic compound degraders, microorganisms from deep mines, and bacteria involved in selenate reduction and arsenite oxidation. Close relatives of Desulforudis audaxviator, a microorganism thought to subsist in the terrestrial deep subsurface on H2 and SO42- produced by radiochemical reactions, was detected in the tunnel waters. NTS-specific media formulations were used to culture and quantify nitrate-, sulfate-, iron-reducing, fermentative, and methanogenic microorganisms. Given that redox manipulations mediated by microorganisms can impact the mobility of DOE contaminants, our results should have implications for management strategies at this and other DOE sites

Radionuclide Reaction Chemistry as a Function of Temperature at the Cheshire Site

The goals of this task were to evaluate the availability of published temperature-dependent thermodynamic data for radionuclides and sorbing minerals and to evaluate the applicability of published estimation methods for temperature-dependent aqueous complexation, radionuclide mineral precipitation, and sorption. This task fills a gap in the hydrologic source term (HST) modeling approach, which, with few exceptions, has neglected the effects of temperature on radionuclide aqueous complexation, using 25 C complexation data for all temperatures without evaluating the consequences of this assumption. In this task, we have compiled thermodynamic data available in the literature and evaluated the options and benefits of applying temperature-dependent radionuclide speciation to future HST modeling. We use the recent experience of HST modeling at Cheshire (Pawloski et al., 2001) to focus our evaluation. Our literature search revealed that few thermodynamic data or extrapolation methods could be used to define the temperature-dependent speciation of key HST radionuclides Np, Pu, Am, and U, particularly for the higher valence-state (e.g., 5+ and 6+), the oxidation states most pertinent to NTS groundwater conditions at Cheshire. This suggests that using 25 C data for all temperatures may be the best modeling approach currently available. We tested established estimation techniques such as the Criss-Cobble method and other correlation algorithms to calculate thermodynamic parameters needed to extrapolate aqueous complexation data to higher temperatures. For some reactions, the isocoulombic method does allow calculation of free energy data and equilibrium values at higher temperatures. Limitations in algorithms and input data for pentavalent and hexavalent cations prevent extending temperature ranges for reactions involving radionuclides in these oxidation states and their complexes. In addition, for many of the radionuclides of interest, carbonate complexes appear to be the dominant complexes formed in NTS groundwaters, and data for these types of complexes are lacking for radionuclides as well as analog species. For the few species where enough data are available, the effect of temperature on radionuclide aqueous complexation has been calculated. These calculations allow partial estimation of the potential error that may be involved in ignoring speciation changes as a function of temperature, as was done in the Cheshire HST model (Pawloski et al., 2001). In some cases, differences between the most recent 25 C data available in the literature and data used in Pawloski et al. (2001) were more significant than calculated speciation changes as a function of temperature. To incorporate radionuclide speciation as a function of temperature, a robust set of temperature-dependent reaction constants is necessary. Based on our literature search and the few reactions that could be extrapolated to higher temperatures, the change in dominant complexes with temperature cannot be adequately addressed at this time. However, the effect of temperature on speciation can be qualitatively examined. In general, the log K values for radionuclide complexation reactions considered here increase with increasing temperature, suggesting that increasing temperature may enhance radionuclide aqueous complexation. However, complexation reactions often involve H{sup +} and reactant species such as carbonate which exhibit their own temperature-dependent speciation. Thus, any change in the value of a radionuclide complexation log K may be offset or enhanced by temperature effects on pH and carbonate speciation. In addition, sorption processes that involve surface complexation change with increasing temperature, and these reactions may enhance or negate the mobility effects of any increase in aqueous complexation with temperature. While increasing temperature may increase complexation, it also may reduce or increase ligand concentrations through shifts in speciation. Similarly, higher temperatures may favor or reduce sorption and/or co-precipitation in mineral phases. Consequently, the net effect on radionuclide mobility of increasing temperature depends on the effects of temperature on a number of geochemical processes. Thus, it is even difficult to make qualitative assumptions about the direction much less the magnitude of temperature effects on radionuclide mobility. Until sufficient data become available in the literature to precisely capture the effects of temperature on radionuclide complexation, it appears unwarranted to invest in complex estimation techniques based on extrapolations from available data

Thermoanaerosceptrum fracticalcis gen. nov. sp. nov., a novel fumarate-fermenting microorganism from a deep fractured carbonate aquifer of the US Great Basin

Deep fractured rock ecosystems across most of North America have not been studied extensively. However, the US Great Basin, in particular the Nevada National Security Site (NNSS, formerly the Nevada Test Site), has hosted a number of influential subsurface investigations over the years. This investigation focuses on resident microbiota recovered from a hydrogeologically confined aquifer in fractured Paleozoic carbonate rocks at 863 – 923 m meters below land surface. Analysis of the microorganisms living in this oligotrophic environment provides a perspective into microbial metabolic strategies required to endure prolonged hydrogeological isolation deep underground. Here we present a microbiological and physicochemical characterization of a deep continental carbonate ecosystem and describe a bacterial genus isolated from the ecosystem. Strain DRI-13T is a strictly anaerobic, moderately thermophilic, fumarate-respiring member of the phylum Firmicutes. This bacterium grows optimally at 55°C and pH 8.0, can tolerate a concentration of 100 mM NaCl, and appears to obligately metabolize fumarate to acetate and succinate. Culture-independent 16S rRNA gene sequencing indicates a global subsurface distribution, while the closest cultured relatives of DRI-13T are Pelotomaculum thermopropionicum (90.0% similarity) and Desulfotomaculum gibsoniae (88.0% similarity). The predominant fatty acid profile is iso-C15:0, C15:0, C16:0 and C14:0. The percentage of the straight-chain fatty acid C15:0 is a defining characteristic not present in the other closely related species. The genome is estimated to be 3,649,665 bp, composed of 87.3% coding regions with an overall average of 45.1% G+C content. Strain DRI-13T represents a novel genus of subsurface bacterium isolated from a previously uncharacterized rock-hosted geothermal habitat. The characterization of the bacterium combined with the sequenced genome provides insights into metabolism strategies of the deep subsurface biosphere. Based on our characterization analysis we propose the name Thermoanaerosceptrum fracticalcis (DRI-13T = DSM 100382T = ATCC TSD-12T)

Evaluation of the Transient Hydrologic Source Term for the Cambric Underground Nuclear Test at Frenchman Flat, Nevada test Site

The objective of Phase II HST work is to develop a better understanding of the evolution of the HST for 1,000 years at the CAMBRIC underground nuclear test site in Frenchman Flat at the NTS. This work provides a better understanding of activities as they actually occurred, incorporates improvements based on recent data acquisition, and provides a basis to use the CAMBRIC site for model validation and monitoring activities as required by the UGTA Project. CAMBRIC was the only test in Frenchman Flat detonated under the water table and best represents a fully saturated environment. These simulations are part of a broad Phase II Frenchman Flat Corrective Action Unit (CAU) flow and transport modeling effort being conducted by the Department of Energy (DOE) Underground Test Area (UGTA) Project. HST simulations provide, either directly or indirectly, the source term used in the CAU model to calculate a contaminant boundary. Work described in this report augments Phase I HST calculations at CAMBRIC conducted by Tompson et al. (1999) and Pawloski et al. (2001). Phase II HST calculations have been organized to calculate source terms under two scenarios: (1) A representation of the transient flow and radionuclide release behavior at the CAMBRIC site that is more specific than Tompson et al. (1999). This model reflects the influence of the background hydraulic gradient, residual test heat, pumping experiment, and ditch recharge, and takes into account improved data sources and modeling approaches developed since the previous efforts. Collectively, this approach will be referred to as the transient CAMBRIC source term. This report describes the development of the transient CAMBRIC HST. (2) A generic release model made under steady-state flow conditions, in the absence of any transient effects, at the same site with the same radiologic source term. This model is for use in the development of simpler release models for the other nine underground test sites in the Frenchman Flat CAU. This approach will be referred to as the steady-state (non-transient) CAMBRIC source term. This work is described in a separate report (Tompson et al., 2005)

Geographical and climatic limits of needle types of one- and two-needled pinyon pines

Aim The geographical extent and climatic tolerances of one- and two-needled pinyon pines (Pinus subsect. Cembroides) are the focus of questions in taxonomy, palaeoclimatology and modelling of future distributions. The identification of these pines, traditionally classified by one- versus two-needled fascicles, is complicated by populations with both one- and two-needled fascicles on the same tree, and the description of two more recently described one-needled varieties: the fallax-type and californiarum-type. Because previous studies have suggested correlations between needle anatomy and climate, including anatomical plasticity reflecting annual precipitation, we approached this study at the level of the anatomy of individual pine needles rather than species. Location Western North America. Methods We synthesized available and new data from field and herbarium collections of needles to compile maps of their current distributions across western North America. Annual frequencies of needle types were compared with local precipitation histories for some stands. Historical North American climates were modeled on a c. 1-km grid using monthly temperature and precipitation values. A geospatial model (ClimLim), which analyses the effect of climate modulated physiological and ecosystem processes, was used to rank the importance of seasonal climate variables in limiting the distributions of anatomical needle types. Results The pinyon needles were classified into four distinct types based upon the number of needles per fascicle, needle thickness and the number of stomatal rows and resin canals. The individual needles fit well into four categories of needle types, whereas some trees exhibit a mixture of two needle types. Trees from central Arizona containing a mixture of Pinus edulis and fallax-type needles increased their percentage of fallax-type needles following dry years. All four needle types occupy broader geographical regions with distinctive precipitation regimes. Pinus monophylla and californiarum-type needles occur in regions with high winter precipitation. Pinus edulis and fallax-type needles are found in regions with high monsoon precipitation. Areas supporting californiarum-type and fallax-type needle distributions are additionally characterized by a more extreme May–June drought. Main conclusions These pinyon needle types seem to reflect the amount and seasonality of precipitation. The single needle fascicle characterizing the fallax type may be an adaptation to early summer or periodic drought, while the single needle of Pinus monophylla may be an adaptation to summer–autumn drought. Although the needles fit into four distinct categories, the parent trees are sometimes less easily classified, especially near their ancestral Pleistocene ranges in the Mojave and northern Sonoran deserts. The abundance of trees with both one- and two-needled fascicles in the zones between P. monophylla, P. edulis and fallax-type populations suggest that needle fascicle number is an unreliable characteristic for species classification. Disregarding needle fascicle number, the fallax-type needles are nearly identical to P. edulis, supporting Little’s (1968) initial classification of these trees as P. edulis var. fallax, while the californiarum-type needles have a distinctive morphology supporting Bailey’s (1987) classification of this tree as Pinus californiarum

Radionuclide Transport in Tuff and Carbonate Fractures from Yucca Flat, Nevada Test Site

In the Yucca Flat basin of the Nevada Test Site (NTS), 747 shaft and tunnel nuclear detonations were conducted primarily within the tuff confining unit (TCU) or the overlying alluvium. The TCU in the Yucca Flat basin is hypothesized to reduce radionuclide migration to the regional carbonate aquifer (lower carbonate aquifer) due to its wide-spread aerial extent and chemical reactivity. However, shortcuts through the TCU by way of fractures may provide a migration path for radionuclides to the lower carbonate aquifer (LCA). It is, therefore, imperative to understand how radionuclides migrate or are retarded in TCU fractures. Furthermore, understanding the migration behavior of radionuclides once they reach the fractured LCA is important for predicting contaminant transport within the regional aquifer. The work presented in this report includes: (1) information on the radionuclide reactive transport through Yucca Flat TCU fractures (likely to be the primary conduit to the LCA), (2) information on the reactive transport of radionuclides through LCA fractures and (3) data needed to calibrate the fracture flow conceptualization of predictive models. The predictive models are used to define the extent of contamination for the Underground Test Area (UGTA) project. Because of the complex nature of reactive transport in fractures, a stepwise approach to identifying mechanisms controlling radionuclide transport was used. In the first set of TCU experiments, radionuclide transport through simple synthetic parallel-plate fractured tuff cores was examined. In the second, naturally fractured TCU cores were used. For the fractured LCA experiments, both parallel-plate and rough-walled fracture transport experiments were conducted to evaluate how fracture topography affects radionuclide transport. Tuff cores were prepared from archived UE-7az and UE-7ba core obtained from the USGS core library, Mercury, Nevada. Carbonate cores were prepared from archived ER-6-1 core, also obtained from the USGS core library, Mercury, Nevada