Controls on porphyroblast size along a regional metamorphic field gradient

Garnet-bearing schists from the Waterville Formation of south-central Maine provide an opportunity to examine the factors governing porphyroblast size over a range of metamorphic grade. Three-dimensional sizes and locations for all garnet porphyroblasts were determined for three samples along the metamorphic field gradient spanning lowest garnet through sillimanite grade, using high-resolution X-ray computed tomography. Comparison of crystal size distributions to previous data sets obtained by stereological methods for the same samples reveals significant differences in mode, mean, and shape of the distributions. Quantitative textural analysis shows that the garnets in each rock crystallized in a diffusion-controlled nucleation and growth regime. In contrast to the typical observation of a correlation between porphyroblast size and position along a metamorphic field gradient, porphyroblast size of the lowest-grade specimen is intermediate between the high- and middle-grade specimens’ sizes. Mean porphyroblast size does not correlate with peak temperatures from garnet-biotite Fe-Mg exchange thermometry, nor is post-crystallization annealing (Ostwald Ripening) required to produce the observed textures, as was previously proposed for these rocks. Robust pseudosection calculations fail to reproduce the observed garnet core compositions for two specimens, suggesting that these calc-pelites experienced metasomatism. For each of these two specimens, Monte Carlo calculations suggest potential pre-metasomatism bulk compositions that replicate garnet core compositions. Pseudosection analyses allow the estimation of the critical temperatures for garnet growth: ∼481, ∼477, and ∼485°C for the lowest-garnet-zone, middle-garnet-zone, and sillimanite-zone specimens, respectively. Porphyroblast size appears to be determined in this case by a combination of the heating rate during garnet crystallization, the critical temperature for the garnet-forming reaction and the kinetics of nucleation. Numerical simulations of thermally accelerated, diffusion-controlled nucleation, and growth for the three samples closely match measured crystal size distributions. These observations and simulations suggest that previous hypotheses linking the garnet size primarily to the temperature at the onset of porphyroblast nucleation can only partially explain the observed textures. Also important in determining porphyroblast size are the heating rate and the distribution of favorable nucleation sites.     

Reaction mechanism of uranyl in the presence of zero-valent iron nanoparticles

The current study provides an investigation of abiotic reduction of an oversaturated uranyl solution driven by iron nanoparticle oxidation. The reactivity of nano-scale zero-valent iron (ZVI) under mildly oxic conditions (1.2% O₂ and 0.0017% CO₂) was studied in 1000 ppm uranyl solution in the pH range 3-7, at reaction times from 10 min to 4 h. Reductive precipitation of UO₂ was observed as the main process responsible for the removal of uranium from solution with the kinetics of reaction becoming increasingly favourable at higher pH. Despite working with an oversaturated uranium solution, the precipitation of UO₂ occurred in preference to precipitation of UO₃·2H₂O (metaschoepite) at reaction times between 1 and 4 h and for uranyl solutions initially set up at pH ?5. Characterisation of both solid and solution phases was performed using X-ray photoelectron spectroscopy (XPS), focused ion beam (FIB) imaging, X-ray diffraction (XRD) and inductively coupled plasma atomic emission spectroscopy (ICP-AES).     

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

Microbial mass-dependent fractionation of chromium isotopes

Mass-dependent fractionation of Cr isotopes occurs during dissimilatory Cr(VI) reduction by Shewanella oneidensis strain MR-1. Cells suspended in a simple buffer solution, with various concentrations of lactate or formate added as electron donor, reduced 5 or 10 μM Cr(VI) to Cr(III) over days to weeks. In all nine batch experiments, ⁵³Cr/⁵²Cr ratios of the unreacted Cr(VI) increased as reduction proceeded. In eight experiments covering a range of added donor concentrations up to 100 μM, isotopic fractionation factors were nearly invariant, ranging from 1.0040 to 1.0045, with a mean value somewhat larger than that previously reported for abiotic Cr(VI) reduction (1.0034). One experiment containing much greater donor concentration (10 mM lactate) reduced Cr(VI) much faster and exhibited a lesser fractionation factor (1.0018). These results indicate that ⁵³Cr/⁵²Cr measurements should be effective as indicators of Cr(VI) reduction, either bacterial or abiotic. However, variability in the fractionation factor is poorly constrained and should be studied for a variety of microbial and abiotic reduction pathways.     

An operational multiscale system for hazards prediction, mapping, and response

By definition, a crisis is a situation that requires assistance to be managed. Hence, response to a crisis involves the merging of local and non-local emergency response personnel. In this situation, it is critical that each participant: (1) know the roles and responsibilities of each of the other participants; (2) know the capabilities of each of the participants; and (3) have a common basis for action. For many types of natural disasters, this entails having a common operational picture of the unfolding events, including detailed information on the weather, both current and forecasted, that may impact on either the emergency itself or on response activities. The Consequences Assessment Tool Set (CATS) is a comprehensive package of hazard prediction models and casualty and damage assessment tools that provides a linkage between a modeled or observed effect and the attendant consequences for populations, infrastructure, and resources, and, hence, provides the common operational picture for emergency response. The Operational Multiscale Environment model with Grid Adaptivity (OMEGA) is an atmospheric simulation system that links the latest methods in computational fluid dynamics and high-resolution gridding technologies with numerical weather prediction to provide specific weather analysis and forecast capability that can be merged into the geographic information system framework of CATS. This paper documents the problem of emergency response as an end-to-end system and presents the integrated CATS–OMEGA system as a prototype of such a system that has been used successfully in a number of different situations.     

Quantitative sinkhole hazard assessment. A case study from the Ebro Valley evaporite alluvial karst (NE Spain)

Quantitative sinkhole hazard assessments in karst areas allow calculation of the potential sinkhole risk and the performance of cost-benefit analyses. These estimations are of practical interest for planning, engineering, and insurance purposes. The sinkhole hazard assessments should include two components: the probability of occurrence of sinkholes (sinkholes/km² year) and the severity of the sinkholes, which mainly refers to the subsidence mechanisms (progressive passive bending or catastrophic collapse) and the size of the sinkholes at the time of formation; a critical engineering design parameter. This requires the compilation of an exhaustive database on recent sinkholes, including information on the: (1) location, (2) chronology (precise date or age range), (3) size, and (4) subsidence mechanisms and rate. This work presents a hazard assessment from an alluvial evaporite karst area (0.81 km²) located in the periphery of the city of Zaragoza (Ebro River valley, NE Spain). Five sinkholes and four locations with features attributable to karstic subsidence where identified in an initial investigation phase providing a preliminary probability of occurrence of 0.14 sinkholes/km² year (11.34% in annual probability). A trenching program conducted in a subsequent investigation phase allowed us to rule out the four probable sinkholes, reducing the probability of occurrence to 0.079 sinkholes/km² year (6.4% in annual probability). The information on the severity indicates that collapse sinkholes 10–15 m in diameter may occur in the area. A detailed study of the deposits and deformational structures exposed by trenching in one of the sinkholes allowed us to infer a modern collapse sinkhole approximately 12 m in diameter and with a vertical throw of 8 m. This collapse structure is superimposed on a subsidence sinkhole around 80 m across that records at least 1.7 m of synsedimentary subsidence. Trenching, in combination with dating techniques, is proposed as a useful methodology to elucidate the origin of depressions with uncertain diagnosis and to gather practical information with predictive utility about particular sinkholes in alluvial karst settings: precise location, subsidence mechanisms and magnitude, and timing and rate of the subsidence episodes.     

Drought and institutional adaptation in the Great Plains of Alberta and Saskatchewan, 1914–1939

Agriculture in the southern Great Plains of Canada has been particularly vulnerable to prolonged episodes of drought. Using climate data and a precipitation minus potential evapotranspiration index, the extent of the region’s exposure to drought is examined. Between 1914 and 1917, the Dry Belt was particularly vulnerable to drought, whereas after 1928, a much larger region known as the Palliser Triangle covering most of southern Alberta and Saskatchewan was much more exposed to drought. These droughts provoked major institutional adaptation, in particular the establishment of the Special Areas Board by the Government of Alberta, and the creation of the Prairie Farm Rehabilitation Administration by the Government of Canada. Both organizations have proved to be relatively permanent public adaptations to the natural hazard of drought in the region. Moreover, these earlier experiences with prolonged drought as well as institution-building may be of value in helping the residents of the Palliser Triangle adapt to predicted climate changes in the future as well as anticipate some of the barriers to effective institutional adaptation.     

Tidal inundation mapping under enhanced land subsidence in Semarang,Central Java Indonesia

Tidal inundation by high tide under enhanced land subsidence is a damaging phenomenon and a major threat to the Semarang urban area in Indonesia. It impacts on economic activities, as well as the cost of an emergency program and causes interruption of pubic services, danger of infectious diseases and injury to human lives. This study examines a spatial analysis tool on the GIS-raster system for the tidal inundation mapping based on the subsidence-benchmark data and modified detail digital elevation model. Neighborhood operation and iteration model as a spatial analysis tool have been applied in order to calculate the encroachment of the tidal inundation on the coastal area. The resulting map shows that the tidal flood spreads to the lowland area and causes the inundation of coastal settlement, infrastructure, as well as productive agricultural land, i.e., the fish-pond area. The monitoring of the vulnerable area due to the tidal inundation under the scenario of extended land subsidence plays an important role in long-term coastal zone management in Semarang.     

Deep-seated gravitational slope deformations and their influence on consequent mass movements (case studies from the highest part of the Czech Carpathians)

Gravitational spreading of mountain ridges displays primary disequilibrium of flysch mountain areas of the Czech Carpathians. The progression of various types of mass movements is a product of long-term ridge disintegration and is predisposed by the geological structure of the area and the upper Tertiary-Quaternary morphogenesis of the mountain area. Deep-seated slope deformations are spatially interconnected by the occurrence of some other types of slope deformations (e.g. debris flows, debris slides, slumps, rock avalanches, etc.), which pose a considerable risk for the existence of human society. An important causative factor in these dynamically developing hazardous processes is, among other factors, the way in which land has been used in the last three centuries. Therefore, the occurrence of various types of slope deformations is studied in terms of their relation to deep-seated gravitational deformations and in terms of other limiting factors (structural geological, morphological and climatic factors, manmade impacts, etc.). The paper presents several case studies of slope deformations (Velká Čantoryje Mt, Lysá hora Mt, Ropice Mt and Smrk Mt) in the area of the Outer Carpathians within the territory of the Czech Republic and also adverts to some consequences in terms of the socioeconomic structure of the landscape.