A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.     

Mistreatment of the economic impacts of extreme events in the Stern Review Report on the Economics of Climate Change

The Stern Review on the Economics of Climate Change has focused debate on the costs and benefits of alternative courses of action on climate change. This refocusing has helped to move debate away from science of the climate system and on to issues of policy. However, a careful examination of the Stern Review's treatment of the economics of extreme events in developed countries, such as floods and tropical cyclones, shows that the report is selective in its presentation of relevant impact studies and repeats a common error in impacts studies by confusing sensitivity analyses with projections of future impacts. The Stern Review's treatment of extreme events is misleading because it overestimates the future costs of extreme weather events in developed countries by an order of magnitude. Because the Stern Report extends these findings globally, the overestimate propagates through the report's estimate of future global losses. When extreme events are viewed more comprehensively the resulting perspective can be used to expand the scope of choice available to decision makers seeking to grapple with future disasters in the context of climate change. In particular, a more comprehensive analysis underscores the importance of adaptation in any comprehensive portfolio of responses to climate change.     

Transformations of mercury, iron, and sulfur during the reductive dissolution of iron oxyhydroxide by sulfide

Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS⁻) was added at 40 to 250 μM h⁻¹ to 5 g L⁻¹ goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m⁻²) at pH 7.5. Dissolved Hg initially decreased from 10³ or 10⁴ nM (depending on initial conditions) to 10⁻¹ nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS_(s)) formed, based on identification using Hg L_III-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS_(s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g⁻¹) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg concentrations tracked those of all sulfide species [S(-II)]. These results suggest that S(-II) reacted with S(0) to form polysulfide, which then caused the dissolution of β-HgS_(s). A secondary Fe-bearing phase resembling poorly formed green rust was observed in sulfidized solids with scanning electron microscopy, although there was no clear evidence that either surface-bound or mineralized Fe(II) strongly affected Hg speciation. Examination of interrelated processes involving S(-II) and Fe(III) revealed new modes of Hg solubilization previously not considered in Hg reactivity models.     

Trace element partitioning between vapor, brine and halite under extreme phase separation conditions

Experiments were conducted to investigate the partitioning of Li, Br, Rb, Cs and B between vapor, brine and halite during subcritical and supercritical phase separation in the NaCl-H₂O system (388-550 °C, 250-350 bars). Results indicate that Li and Br partition preferentially into the low-salinity vapor fluids, while Rb and Cs become more enriched in the coexisting brines. Under more extreme conditions of pressure and temperature in the two-phase region, especially near the vapor-brine-halite boundary, strong salting-out effects imposed on neutral aqueous species enhance significantly partitioning of all trace elements into the low-salinity fluid. Dissolved boron is strongly affected by this and a particularly strong enrichment into vapors is observed, a trend that can be effectively correlated with changes in reduced density. Exclusion of Li, Br, Rb, Cs and B from halite, when precipitated, further increases the solubility of these species in the coexisting Cl-poor fluid. In general, the lack of distortion in the partitioning behavior of trace elements between vapor, brine and/or halite with the transition from subcritical to supercritical conditions in the NaCl-H₂O system precludes the need for special reference to the critical point of seawater when interpreting phase relations in submarine hydrothermal systems. The combination of experimentally determined trace element partitioning data with constraints imposed by mineral solubility provides a means to better understand the origin and evolution of hot spring vent fluids. For example, in Brandon hydrothermal system (21°S EPR) supercritical phase separation and subseafloor mixing appear to be the main heat and mass transport mechanisms fueled by a shallow magmatic intrusion, with boron systematics ruling out major contributions from magmatic degassing processes accompanying the near-seafloor volcanism.     

The effects of soil type and chemical treatment on nickel speciation in refinery enriched soils: A multi-technique investigation

Aerial deposition of Ni from a refinery in Port Colborne, Ontario, Canada has resulted in the enrichment of 29 km² of land with Ni concentrations exceeding the Canadian Ministry of the Environment’s remedial action level of 200 mg kg⁻¹. Several studies on these soils have shown that making the soils calcareous was effective at reducing chemically extractable Ni, as well as alleviating Ni phytotoxicity symptoms in vegetable crops grown in the vicinity of the refinery. Conversely, dolomitic limestone additions resulted in increased uptake of Ni in the Ni hyperaccumulator Alyssum murale ‘Kotodesh’, a plant whose use was proposed as a remediation strategy for this area. In this paper we use multiple techniques to directly assess the role soil type and lime treatments play in altering the speciation of Ni in the Welland loam and Quarry muck soils around the refinery and relate these findings to Ni mobility and bioavailability.Stirred-flow dissolution experiments using pH 4 HNO₃ showed that Ni release from the limed Quarry muck and Welland loam soils was reduced (∼0.10%) relative to the unlimed soils (∼2.0%). Electron microprobe analysis (EMPA) identified approximately spherical NiO and Ni metal particles, which are associated with no other metals, and range from 5 to 50 μm in diameter. Synchrotron micro-X-ray absorption fine structure and X-ray fluorescence spectroscopies showed that Ni and Al layered double hydroxide (Ni-Al LDH) phases were present in both the limed and unlimed mineral soils, with a tendency towards more stable (e.g., aged-LDH and phyllosilicate) Ni species in the limed soil, possibly aided by the solubilization of Si with increasing pH. In the muck soils, Ni-organic complexes (namely fulvic acid) dominated the speciation in both limed and unlimed soils.The results reported herein show that both soil type and treatment have a pronounced effect on the speciation of Ni in the soils surrounding the Port Colborne refinery. We provide the first evidence that Ni-Al LDH phases can form in anthropogenically enriched mineral field soils at circumneutral pH, and can lead to a reduction in Ni mobility. In the organic soils Ni is strongly complexed by soil organic matter; a property enhanced with liming. Interestingly, increased accumulation of Ni by A. murale grown in the limed muck and loam soils indicates that the plant may be capable of removing Ni from those fractions typically considered unavailable to most plants.     

Paleoenvironmental analysis of a middle Wisconsinan biota site, southwestern Virginia, U.S.A.

The Ratcliff Site in southwestern Virginia lies in a small second-order stream valley filled with approximately 3.5 m of organic-rich deposits that contain bones of mammoth, mastodon, deer (or antelope), logs, and plant macrofossils. Radiocarbon analyses indicate the age of the organic-rich sediment ranges from > 44,000 to 29,100 ¹⁴C yr BP, a time period with no fossil remains reported in this region of the Appalachians. Analyses of field observations, textural data, organic carbon content, and plant macrofossils indicate that the organic-rich sediments contain interbedded standing-water and debris-flow deposits. Up to 6 m of oxidized debris-flow sediments bury the organic-rich sediments. The presence of Rubus parviflorus (Thimble Berry) throughout the deposit indicates the site had a boreal environment from > 44,000 to 29,100 ¹⁴C yr BP. Plant macrofossil evidence indicates the uplands had stands of spruce/jack-pine forests while the valley contained ponds and associated wetlands. Three debris flows occurred at the site between approximately 38,000 and 29,000 ¹⁴C yr BP, suggesting a recurrence interval for major storms of approximately 3000 yr, even though the apparent stability of the boreal environment implies a climate not conducive to catastrophic rainstorms. This conflicting combination of features suggests that during the middle Wisconsinan this area experienced generally cool climates, dominated by polar air masses, but was punctuated by relatively brief warm periods marked by incursions of tropical air masses.     

Analysis of drought determinants for the Colorado River Basin

Ongoing drought in the Colorado River Basin, unprecedented urban growth in the watershed, and numerical model simulations showing higher temperatures and lower precipitation totals in the future have all combined to heighten interest in drought in this region. In this investigation, we use principal components analysis (PCA) to independently assess the influence of various teleconnections on Basin-wide and sub-regional winter season Palmer Hydrological Drought Index (PHDI) and precipitation variations in the Basin. We find that the Pacific Decadal Oscillation (PDO) explains more variance in PHDI than El Niño-Southern Oscillation (ENSO), the Atlantic Multidecadal Oscillation (AMO), and the planetary temperature combined for the Basin as a whole. When rotated PCA is used to separate the Basin into two regions, the lower portion of the Basin is similar to the Basin as a whole while the upper portion, which contains the high-elevation locations important to hydrologic yield for the watershed, demonstrates poorly defined relationships with the teleconnections. The PHDI for the two portions of the Basin are shown to have been out of synch for much of the twentieth century. In general, teleconnection indices account for 19% of the variance in PHDI leaving large uncertainties in drought forecasting.     

A 408-MHz variability study of two fields in the region 6h30m, +45°

Variability in 408-MHz flux density, over a 1-yr interval between 1995 and 1996, has been investigated using the DRAO Synthesis Telescope for a complete sample of 322 sources with S _408 MHz > 80 mJy at galactic latitude b  = 15°; four sources are found to show significant flux density variations. These results, taken with those from a similar study at b  = 58°, indicate that 408-MHz variability over a time-scale of 1 yr is more uncommon than has previously been thought; variations at a level >10 per cent could have been detected in a statistically complete sample of about 150 of these sources and none was found. Variability over a period of 18 yr has also been investigated by comparing the DRAO data with those from the B3 catalogue for 182 sources with S _408 MHz > 200 mJy; five variables are found. Large flux density variations over a period of 18 yr are much more common than over 1 yr, with roughly one source in 15 showing variations at the 15 per cent level or greater. The statistics are not good enough to show any conclusive evidence for a dependence of variability on galactic latitude. Roughly half of the variable sources have spectra that are steep at high frequencies and flatten at low frequencies; the other half have flat radio spectra over the entire frequency range. Simultaneous observations at 1420 MHz, also with the DRAO Synthesis Telescope, have been used to investigate variability at this frequency as well, and indicate that over a period of 1 yr roughly half of the flat-spectrum sources vary at the 5 per cent level or greater.     

State-of-the-art report — engineering practice in artificial ground freezing

In the present paper an attempt has been made to summarize the current state-of-theart of engineering practice in artifical ground freezing. The paper shows the tremendous increase in knowledge and diversified applications in ground freezing over the past ten years and, together with other papers ih the Symposium, provides a useful background against which practicing engineers may. gain an understanding of ground freezing. As discussed in this paper, there are gain an understanding of ground freezing. As discussed in this paper, there are However, it is the author's assessment that the current state of knowledge is sufficient for safe designs and that future refinements in the area of structural analysis will only lead to more accurate deformation predictions and to possibly thinnerdesign frozen sections. Since the sizes of frozen sections are often more a function of construction practicality rather than design requirements, it is questionable whether potentially thinner sections will have a significant impact on actual construction.

An area that promises to have tremendous impact on the competitive nature of freezing for soft-ground tunneling is in improved horizontal drilling techniques. Several contractors are currently developing drilling equipment for horizontal drilling over large distances, whereas today the maximum economical distance is in the range of 30–40 m.