Evaluation of silica-water surface chemistry using NMR spectroscopy

We have combined traditional batch and flow-through dissolution experiments, multinuclear nuclear magnetic resonance (NMR) spectroscopy, and surface complexation modeling to re-evaluate amorphous silica reactivity as a function of solution pH and reaction affinity in NaCl and CsCl solutions. The NMR data suggest that changes in surface speciation are driven by solution pH and to a lesser extent alkali concentrations, and not by reaction time or saturation state. The ²⁹Si cross-polarization NMR results show that the concentration of silanol surface complexes decreases with increasing pH, suggesting that silanol sites polymerize to form siloxane bonds with increasing pH. Increases in silica surface charge are offset by sorption of alkali cations to ionized sites with increasing pH. It is the increase in these ionized sites that appears to control silica polymorph dissolution rates as a function of pH. The ²³Na and ¹³³Cs NMR results show that the alkali cations form outersphere surface complexes and that the concentration of these complexes increases with increasing pH. Changes in surface chemistry cannot explain decreases in dissolution rates as amorphous silica saturation is approached. We find no evidence for repolymerization of the silanol surface complexes to siloxane complexes at longer reaction times and constant pH.     

The Colorado East River Community Observatory Data Collection

The U.S. Department of Energy's (DOE) Colorado East River Community Observatory (ER) in the Upper Colorado River Basin was established in 2015 as a representative mountainous, snow-dominated watershed to study hydrobiogeochemical responses to hydrological perturbations in headwater systems. The ER is characterized by steep elevation, geologic, hydrologic and vegetation gradients along floodplain, montane, subalpine, and alpine life zones, which makes it an ideal location for researchers to understand how different mountain subsystems contribute to overall watershed behaviour. The ER has both long-term and spatially-extensive observations and experimental campaigns carried out by the Watershed Function Scientific Focus Area (SFA), led by Lawrence Berkeley National Laboratory, and researchers from over 30 organizations who conduct cross-disciplinary process-based investigations and modelling of watershed behaviour. The heterogeneous data generated at the ER include hydrological, genomic, biogeochemical, climate, vegetation, geological, and remote sensing data, which combined with model inputs and outputs comprise a collection of datasets and value-added products within a mountainous watershed that span multiple spatiotemporal scales, compartments, and life zones. Within 5 years of collection, these datasets have revealed insights into numerous aspects of watershed function such as factors influencing snow accumulation and melt timing, water balance partitioning, and impacts of floodplain biogeochemistry and hillslope ecohydrology on riverine geochemical exports. Data generated by the SFA are managed and curated through its Data Management Framework. The SFA has an open data policy, and over 70 ER datasets are publicly available through relevant data repositories. A public interactive map of data collection sites run by the SFA is available to inform the broader community about SFA field activities. Here, we describe the ER and the SFA measurement network, present the public data collection generated by the SFA and partner institutions, and highlight the value of collecting multidisciplinary multiscale measurements in representative catchment observatories.     

Lake basin response to tectonic drainage diversion: Eocene Green River Formation, Wyoming

A previously unidentified major sequence boundary within the Eocene Green River Formation separates fluctuating profundal facies of the Tipton Shale Member from evaporative facies of the Wilkins Peak Member. During deposition of the Tipton Shale Member, rivers entered the basin from the north, across the subdued Wind River Mountains, and deposited the southward prograding deltaic complex of the Farson Sandstone Member. Boulder-rich alluvial fan deposits overlie the Farson Sandstone adjacent to the Continental Fault, and correlate basinward to hypersaline lacustrine deposits of the Wilkins Peak Member. The alluvial fan deposits record a period of reverse motion on the Continental Fault and uplift of the southeastern Wind River Range, which diverted drainage away from the greater Green River Basin. This decreased inflow caused Lake Gosiute to shrink, exposing its bed to desiccation and erosion, and contributed to hydrologically-closed conditions and periodic evaporite deposition thereafter. This study is one of the first to demonstrate a direct relationship between movement along a specific basin-bounding structure, and a change in the overall style of lacustrine sedimentation. The identification of similar relationships elsewhere may challenge conventional interpretations of climate as the dominant factor influencing the character of lake deposits, and provide an important, but previously unexploited, approach to interpreting continental deformation and regional drainage organization.     

Evaporative evolution of a Na–Cl–NO<Subscript>3</Subscript>–K–Ca–SO<Subscript>4</Subscript>–Mg–Si brine at 95 °C: Experiments and modeling relevant to Yucca Mountain,Nevada

A synthetic Topopah Spring Tuff water representative of one type of pore water at Yucca Mountain, NV was evaporated at 95°C in a series of experiments to determine the geochemical controls for brines that may form on, and possibly impact upon the long-term integrity of waste containers and drip shields at the designated high-level, nuclear-waste repository. Solution chemistry, condensed vapor chemistry, and precipitate mineralogy were used to identify important chemical divides and to validate geochemical calculations of evaporating water chemistry using a high temperature Pitzer thermodynamic database. The water evolved toward a complex "sulfate type" brine that contained about 45 mol % Na, 40 mol % Cl, 9 mol % NO₃, 5 mol % K, and less than 1 mol % each of SO₄, Ca, Mg, ∑CO₂(aq), F, and Si. All measured ions in the condensed vapor phase were below detection limits. The mineral precipitates identified were halite, anhydrite, bassanite, niter, and nitratine. Trends in the solution composition and identification of CaSO₄ solids suggest that fluorite, carbonate, sulfate, and magnesium-silicate precipitation control the aqueous solution composition of sulfate type waters by removing fluoride, calcium, and magnesium during the early stages of evaporation. In most cases, the high temperature Pitzer database, used by EQ3/6 geochemical code, sufficiently predicts water composition and mineral precipitation during evaporation. Predicted solution compositions are generally within a factor of 2 of the experimental values. The model predicts that sepiolite, bassanite, amorphous silica, calcite, halite, and brucite are the solubility controlling mineral phases.     

A photometric perturbation of the counterglow

A weakening of the radiance of the counterglow in the anti-solar direction relative to the regions 5°–15° away is interpreted as evidence for a cloud of scattering material in the general region of the Earth-Moon system. Further evidence is indicated, by the relative brightening at ?180° in the vicinity of the L4 libration point, that the cloud is significantly denser there than in adjacent locations.     

Permeability of Wellbore-Cement Fractures Following Degradation by Carbonated Brine

Fractures in wellbore cement and along wellbore-cement/host-rock interfaces have been identified as potential leakage pathways from long-term carbon sequestration sites. When exposed to carbon-dioxide-rich brines, the alkaline cement undergoes a series of reactions that form distinctive fronts adjacent to the cement surface. However, quantifying the effect of these reactions on fracture permeability is not solely a question of geochemistry, as the reaction zones also change the cement’s mechanical properties, modifying the fracture geometry as a result.This paper describes how these geochemical and geomechanical processes affect fracture permeability in wellbore cement. These competing influences are discussed in light of data from a core-flood experiment conducted under carbon sequestration conditions: reaction chemistry, fracture permeability evolution over time, and comparative analysis of X-ray tomography of unreacted and reacted cement samples. These results are also compared to predictions by a complementary numerical study that couples geochemical, geomechanical and hydrodynamic simulations to model the formation of reaction fronts within the cement and their effect on fracture permeability.     

The anticipated role of the large format camera in future earth observation strategies

The development of the National Aeronautics and Space Administration's Large Format Camera has added a new dimension to remote sensing. Offering inexpensive large area coverage imagery with excellent geometric fidelity, the LFC was successfully flown in late 1984 aboard the Space Shuttle. The success of this initial flight has encouraged scientists to propose that the LFC be included as part of the earth observation sensor bed on the planned space station.

The relatively low costs associated with LFC photography provide an opportunity for developing countries to learn more about the capabilities and advantages of exploiting remotely sensed imagery. In particular, by using LFC imagery to study an array of local and global phenomena, these developing countries can quickly increase their knowledge of earth observation techniques and join the “community”; of nations currently active in remote sensing efforts.     

Zeeman-Doppler imaging of late-type stars: The surface magnetic field of II Peg

Late-type stars in general possess complicated magnetic surface fields which makes their detection and in particular their modeling and reconstruction challenging. In this work we present a new Zeeman-Doppler imaging code which is especially designed for the application to late-type stars. This code uses a new multi-line cross-correlation technique by means of a principal component analysis to extract and enhance the quality of individual polarized line profiles. It implements the full polarized radiative transfer equation and uses an inversion strategy that can incorporate prior knowledge based on solar analogies. Moreover, our code utilizes a new regularization scheme which is based on local maximum entropy to allow a more appropriate reproduction of complex surface fields as those expected for late-type stars. In a first application we present Zeeman-Doppler images of II Pegasi which reveal a surprisingly large scale surface structure with one predominant (unipolar) magnetic longitude which is mainly radially oriented. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Shell layer variation in trace element concentration for the freshwater bivalve Elliptio complanata

While the elemental chemistry of marine mollusk shells contains valuable environmental information, extending these interpretations to freshwater bivalve shells may be problematic, given the wide range of aqueous chemistries that exist in freshwater environments. To better understand the significance of these records, 20 bivalves were collected from four freshwater streams to determine the geochemical relationships that exist between the bivalve shell and their sources streams. The concentrations of manganese (Mn), copper (Cu), strontium (Sr), barium (Ba), and calcium (Ca) were analyzed by laser ablation inductively coupled plasma mass spectrometry across the inner (INL) and outer nacreous layer (ONL) of each shell for comparison to stream data collected over the period of shell growth. Within an individual shell, the content of Mn, Sr, and Ba were significantly higher in the INL than the ONL, while Cu concentrations were similar. Strontium and Ba concentrations co-varied between the two layers in 1:1 relationships, while Mn displayed a preferential enrichment in the INL that increased from 2:1 to 5:1 as the Mn content of the shell decreased. Each elemental profile can be correlated between shell layers, except for the trace element Cu, which appeared to be more closely related to the organic content of the shell. These results suggest that the major element geochemistry of the shell layers differentially reflect the aqueous chemistry of the water in which a bivalve lived, but that these records are most likely overprinted by physiological processes specific to the mantle tissue from which a particular shell layer is secreted. Distribution coefficients (shell _{M /Ca}:water _{M /Ca}, where M?=?trace element of interest) were calculated using the median molar elemental concentration for each shell (by layer), and the appropriate water concentration. Bivalves from a contaminated site were excluded from this analysis because their shells were anomalous in size and color. For the remaining 15 shells, distribution coefficients (INL and ONL) were: Mn (0.50 and 0.21), Sr (0.26 and 0.17), and Ba (0.05: INL only). Inner nacreous layer values were comparable to the upper end of published estimates for freshwater bivalves and fish otoliths, while the ONL values were comparable to the lower range of values. Inclusion of shells from the contaminated site resulted in the calculation of distribution coefficients that fell outside the range of published estimates. These results suggest that exposure to pollutants may have a bearing on the biological factors that control the elemental concentration of bivalve shells in freshwater environments. While researchers generally avoid sampling shell material from the INL because of the potential for shell dissolution, the similarity in elemental profile trends observed here suggests that both the INL and ONL record accurate geochemical information, but in distinct forms. An obvious advantage of INL analysis is the relative increase in elemental concentration, but this is afforded at the expense of spatial resolution. Considered collectively, these results suggest that valuable information can be gleaned from the elemental concentration of freshwater bivalve shells when care is taken in the choice of material from which these records are extracted.