An Injectable Apatite Permeable Reactive Barrier for In Situ 90Sr Immobilization

An injectable permeable reactive barrier (PRB) technology was developed to sequester ⁹⁰Sr in groundwater through the in situ formation of calcium‐phosphate mineral phases, specifically apatite that incorporates ⁹⁰Sr into the chemical structure. This injectable barrier technology extends the PRB concept to sites where groundwater contaminants are too deep or where site conditions otherwise preclude the application of more traditional trench‐emplaced barriers. An integrated, multiscale development and testing approach was used that included laboratory bench‐scale experiments, an initial pilot‐scale field test, and the emplacement and evaluation of a 300‐feet‐long treatability‐test‐scale PRB. The apatite amendment formulation uses two separate precursor solutions, one containing a Ca‐citrate complex and the other a Na‐phosphate solution, to form apatite precipitate in situ. Citrate is needed to keep calcium in solution long enough to achieve a more uniform and areally extensive distribution of precipitate formation. In the summer of 2008, the apatite PRB technology was applied as a 91‐m‐long (300 feet) PRB on the downgradient edge of a ⁹⁰Sr plume beneath the Hanford Site in Washington State. The technology was deployed to reduce ⁹⁰Sr flux discharging to the Columbia River. Performance assessment monitoring data collected to date indicate that the barrier is meeting treatment objectives (i.e., 90% reduction in ⁹⁰Sr concentration). The average reduction in ⁹⁰Sr concentrations at four downgradient compliance monitoring locations was 95% relative to the high end of the baseline range approximately 1 year after treatment, and continues to meet remedial objectives more than 4 years after treatment.     

In situ study of the $$ R\overline{3} c \to R\overline{3} m $$ orientational disorder in calcite

The temperature dependences of the crystal structure and intensities of the (113) and (211) reflections in calcite, CaCO₃, were studied using Rietveld structure refinements based on synchrotron powder X-ray diffraction data. Calcite transforms from to at about T _c = 1,240 K. A CO₃ group occupies, statistically, two positions with equal frequency in the disordered phase, but with unequal frequency in the partially ordered phase. One position for the CO₃ group is rotated by 180° with respect to the other. The unequal occupancy of the two orientations in the partially ordered phase is obtained directly from the occupancy factor, x, for the O1 site and gives rise to the order parameter, S = 2x − 1. The a cell parameter shows a negative thermal expansion at low T, followed by a plateau region at higher T, then a steeper contraction towards T _c, where the CO₃ groups disorder in a rapid process. Using a modified Bragg–Williams model, fits were obtained for the order parameter S, and for the intensities of the (113) and (211) reflections. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

A rapid method for converting medical Computed Tomography scanner topogram attenuation scale to Hounsfield Unit scale and to obtain relative density values

Medical Computed Tomography scanners permit to rapidly obtain qualitative and quantitative information on objects in a non-destructive manner in both longitudinal and transversal directions. CT-scan scales used to express attenuation on the images are different for longitudinal (topograms) and transversal (tomograms) views, restraining the complementary use of the information extracted from both views. Moreover, topograms are of full use in core analysis as they reveal fine-scale information on stratigraphical, sedimentological and physical properties of the material. This paper presents a method to convert CT-scan topogram intensity scale to Hounsfield Unit (HU; scale used on tomograms) and to later extract a relative density from it. The method is based on relationships between topogram and tomogram values, absolute density and effective atomic numbers obtained on a series of minerals. Results show excellent correlations between converted topogram values and HU values obtained on the tomograms, as well as between relative densities derived from the converted topogram values, and the absolute density of the minerals.     

Heterogeneously entrapped,vapor-rich melt inclusions record pre-eruptive magmatic volatile contents

Silicate melt inclusions (MI) commonly provide the best record of pre-eruptive H₂O and CO₂ contents of subvolcanic melts, but the concentrations of CO₂ and H₂O in the melt (glass) phase within MI can be modified by partitioning into a vapor bubble after trapping. Melt inclusions may also enclose vapor bubbles together with the melt (i.e., heterogeneous entrapment), affecting the bulk volatile composition of the MI, and its post-entrapment evolution. In this study, we use numerical modeling to examine the systematics of post-entrapment volatile evolution within MI containing various proportions of trapped vapor from zero to 95 volume percent. Modeling indicates that inclusions that trap only a vapor-saturated melt exhibit significant decrease in CO₂ and moderate increase in H₂O concentrations in the melt upon nucleation and growth of a vapor bubble. In contrast, inclusions that trap melt plus vapor exhibit subdued CO₂ depletion at equivalent conditions. In the extreme case of inclusions that trap mostly the vapor phase (i.e., CO₂–H₂O fluid inclusions containing trapped melt), degassing of CO₂ from the melt is negligible. In the latter scenario, the large fraction of vapor enclosed in the MI during trapping essentially serves as a buffer, preventing post-entrapment modification of volatile concentrations in the melt. Hence, the glass phase within such heterogeneously entrapped, vapor-rich MI records the volatile concentrations of the melt at the time of trapping. These numerical modeling results suggest that heterogeneously entrapped MI containing large vapor bubbles represent amenable samples for constraining pre-eruptive volatile concentrations of subvolcanic melts.     

Geomorphic controls on deposition of salt in the Greater Tamar Catchment,northeast Tasmania

In Tasmania, most salts in the landscape originate from rainfall and accumulate in landscapes after evaporation occurs. The distribution and quantity of salt in rainfall from an array of bulk deposition collectors in the Greater Tamar Catchment were assessed for the period September 2013 to August 2014. The bulk deposition samples were analysed for pH, electrical conductivity, major ions (Ca, Mg, Na, SO₄ and Cl) and a selection of trace ions. The average salt flux across the study area was 79 ± 10 kg/ha/yr region, ranging from 170 ± 12 kg/ha/yr near the coast in the north to 42 ± 6 kg/ha/yr inland. Deposition of most ions decreased from the northwest to the south and east, and peaked in winter and spring. Geomorphic factors such as elevation and topography have an important effect on the volume of rainfall and flux of salt from windblown dust and oceanic aerosols. A comparison of measured chloride and salt deposition in Tasmania with other Australian atmospheric studies indicates that continental-scale models of salt flux are not appropriate for Tasmania. New models are proposed that take into account the influence of the Southern Ocean, Tasman Sea and topographic variation in the study area. The results provide improved estimates of rainfall-derived salt inputs to catchments in northeast Tasmania and enable more accurate salt budget modelling. Improved understanding of volumes and distribution of salts has implications for the management of soils and infrastructure that degrade as a result of dryland salinity in Tasmania.     

Forest fire,bank strength and channel instability: the ‘unusual’ response of Fishtrap Creek,British Columbia

In August 2003, the McLure forest fire burned 62% of the drainage basin of Fishtrap Creek. Streamflow has been measured there since the early 1970s, and suspended sediment concentration and channel morphology have been monitored since the fire. Although the short post‐fire period (four years) limits our ability to draw firm conclusions about streamflow changes, there has been no obvious increase in peak flows since the fire. However, the total runoff during the freshet period does appear to have increased and the onset of snowmelt appears to occur about two weeks earlier than it did prior to the fire. Suspended sediment records from Fishtrap Creek and from an unburnt reference stream nearby are similar, suggesting that the burnt areas have remained relatively stable and that the sediment supply to Fishtrap Creek has not been dramatically altered. In contrast, the stream channel morphology has changed, widening by over 100% of the original width in some places and transforming from a laterally stable plane‐bed morphology to a laterally active riffle‐pool morphology. The timing and magnitude of the observed morphologic changes are consistent with the predicted decline in bank strength due to root decay, implying that the observed changes are associated with an internal instability associated with changes to the stream boundaries, rather than with the more typically reported externally driven instabilities caused by changes in streamflow or sediment supply. This delayed response in the absence of large changes in streamflow or sediment supply, while ‘unusual’ in that it has not been documented in the previous literature, may be a common mode of response, particularly in wat'ersheds with nival flow regimes. Copyright © 2010 John Wiley & Sons, Ltd.     

Mechanisms for transition in eruptive style at a monogenetic scoria cone revealed by microtextural analyses (Lathrop Wells volcano, Nevada, U.S.A.)

Explosive activity at Lathrop Wells volcano, Nevada, U.S.A. originated with weak Strombolian (WS) eruptions along a short fissure, and transitioned to violent Strombolian (VS) activity from a central vent, with lava effusion during both stages. The cause for this transition is unknown; it does not reflect a compositional change, as evidenced by the consistent bulk geochemistry of all the eruptive products. However, comparison of agglutinate samples from the early, WS events with samples of scoria from the later, VS events reveal differences in the abundance and morphology of groundmass phases and variable textures in the rims of olivine phenocrysts. Scanning electron microscope (SEM) examination of thin sections from the WS samples show euhedral magnetite microlites in the groundmass glass and olivine phenocrysts show symplectite lamellae in their rims. Secondary ion mass spectrometry (SIMS) depth profiles of these symplectites indicate they are diffusion-controlled. The calculated D_Fe-Mg allows an estimation of the oxygen fugacity (fO₂) and indicates an increased fO₂ during eruption of the WS products. Conversely, the VS samples show virtually no magnetite microlites in the groundmass glass, a lack of symplectites in the olivines, and a lower calculated fO₂. These microtextural features suggest that the Lathrop Wells trachybasalt experienced increased oxidation during WS activity. As magma ascended through the original fissure, exsolved bubbles were concentrated in the wider part(s) (the protoconduit) and this bubble flux drove convective circulation that oxidized the magma through exposure to atmosphere and recirculation. This oxidation resulted in groundmass crystallization of magnetite within the melt and formation of symplectites within the olivine phenocrysts. Bubble-driven convection mixed magma vertically within the protoconduit, keeping it fluid and driving Strombolian bursts, while microlite crystallization in narrower parts of the fissure helped to focus flow. Development of a central conduit increased the magma ascent velocity (due to a greater product volume in the later eruptive stages) and caused the shift in eruption intensity. Consequently, variations in microtextures of the Lathrop Wells products reveal how a combination of fluid dynamic and crystallization processes in the ascending magma resulted in different styles of activity while the products maintained a consistent bulk composition.     

Geochemical tracers to evaluate hydrogeologic controls on river salinization

The salinization of rivers, as indicated by salinity increases in the downstream direction, is characteristic of arid and semiarid regions throughout the world. Historically, salinity increases have been attributed to various mechanisms, including (1) evaporation and concentration during reservoir storage, irrigation, and subsequent reuse; (2) displacement of shallow saline ground water during irrigation; (3) erosion and dissolution of natural deposits; and/or (4) inflow of deep saline and/or geothermal ground water (ground water with elevated water temperature). In this study, investigation of salinity issues focused on identification of relative salinity contributions from anthropogenic and natural sources in the Lower Rio Grande in the New Mexico-Texas border region. Based on the conceptual model of the system, the various sources of water and, therefore, salinity to the Lower Rio Grande were identified, and a sampling plan was designed to characterize these sources. Analysis results for boron (delta(11)B), sulfur (delta(34)S), oxygen (delta(18)O), hydrogen (delta(2)H), and strontium ((87)Sr/(86)Sr) isotopes, as well as basic chemical data, confirmed the hypothesis that the dominant salinity contributions are from deep ground water inflow to the Rio Grande. The stable isotopic ratios identified the deep ground water inflow as distinctive, with characteristic isotopic signatures. These analyses indicate that it is not possible to reproduce the observed salinization by evapotranspiration and agricultural processes alone. This investigation further confirms that proper application of multiple isotopic and geochemical tracers can be used to identify and constrain multiple sources of solutes in complex river systems.     

Exploring landscape and geologic controls on spatial patterning of streambank groundwater discharge in a mixed land use watershed

Preferential groundwater discharge features along stream corridors are ecologically important at local and stream network scales, yet we lack quantification of the multiscale controls on the spatial patterning of groundwater discharge. Here we identify physical attributes that best explain variation in the presence and lateral extent of preferential groundwater discharges along two 5th order streams, the Housatonic and Farmington Rivers, and 32 1st to 4th order reaches across the Farmington River network. We mapped locations of preferential groundwater discharge exposed along streambanks using handheld thermal infrared cameras paired with high-resolution topographic and land use land cover datasets, surficial soil characteristic maps, and depth-to-bedrock geophysical measurements. The unconfined Housatonic River, MA, USA (12 km) had fewer discharge locations and less lateral extent (41 discharge locations with 38 m of active discharge/km of river) compared to the partially confined Farmington River, CT, USA (26 km; 169 discharge locations with 129 m of active discharge/km of river). Using a moving window analysis, we found along both rivers that discharge was more likely to occur where bank slopes were steeper, floodplain extent was narrower, and degree of confinement was higher. Along the Farmington River, groundwater discharge was more likely to occur where saturated hydraulic conductivity was higher and depth-to-bedrock was shallower. Among the 32 stream reaches surveyed (33.2 km of total stream length) within the Farmington River watershed, preferential discharge was observed in all but two stream reaches, varied from 0 to 25% of lateral extent along stream banks (mean = 6%), and was more likely to occur where stream reach slopes were steep, saturated hydraulic conductivity was high, and watershed urbanization was low. Our results show that, though both surface (e.g., topographic, land use land cover) and subsurface (e.g., soil characteristics, bedrock depth) factors control the prevalence of streambank preferential groundwater discharge, the dominant controls vary across valley settings and stream sizes.     

Recent sea ice increase and temperature decrease in the Bering Sea area,Alaska

We analyzed the sea ice conditions in the Bering Sea for the time period 1979–2012, for which good data based on microwave satellite imagery, being able to look through clouds and darkness, are available. The Bering Sea, west of Alaska, is ice-free in summer, but each winter, an extensive sea ice cover is established, reaching its maximum normally in March. We found a slight increase in ice area over the time period, which is in stark contrast to the significant retreat observed in the Beaufort Sea north of Alaska and the Arctic Ocean as a whole. Possible explanation might be found in the Pacific Decadal Oscillation (PDO), which went from dominantly positive values to more negative values in the last decade. The PDO is related to the sea surface temperature (SST) in the North Pacific, negative values indicated cooler temperatures and cooler SST weakening the semipermanent Aleutian Low. When comparing the circulation pattern obtained from the National Centers for Environmental Prediction/National Center for Atmospheric Research reanalyzed data set for years of heavy ice against light ice years, an additional vectorial northerly wind component could be deduced from the pressure data. Hence, less relatively warm air is advected into the Bering Sea, which becomes of special importance in winter, when solar radiation is at its minimum. Surface observations confirmed these findings. Atmospheric pressure increased in Cold Bay, located close to the center of the semi-permanent Aleutian Low, the N–S pressure gradient (Nome–Cold Bay) in the Bering Sea decreased, wind speeds of the coastal stations became weakened, and the temperature of coastal stations decreased.