Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

National-scale estimation of potentially harmful element ambient background concentrations in topsoil using parent material classified soil:stream–sediment relationships

Regulatory authorities require estimates of ambient background concentrations (ABCs) of potentially harmful elements (PHEs) in topsoil; such data are currently not available in many countries. High resolution soil geochemical data exist for only part of England and Wales, whilst stream sediment data cover the entire landscape. A novel methodology is presented for estimating soil equivalent ABCs for PHEs from high-resolution (HR) stream sediment geochemical data grouped by common parent materials (PM), using arsenic (As) as an example. Geometric mean (GM) values for local PM groups are used to investigate different approaches for transforming sediment to soil equivalent concentrations. Holdout validation is used to assess: (i) the optimum number of samples for calculating local GM values, and (ii) the optimum scale at which to group data when using linear regression analysis to estimate GM soil ABCs from local sediment geochemical values. Holdout validation showed that the smallest differences were generally observed when five observations were used to calculate the GM and that these should be grouped over the smallest possible area in order to encompass soils over PMs with elevated GM As concentrations. Geometric mean ABCs are estimated and mapped for As in mineral soil across all of England and Wales within delineations of PM polygons. Errors for the estimation of soil equivalent GM As ABCs based on sediment data for an independent validation set were of a similar magnitude to those from holdout validation applied to the original data suggesting the approach is robust. The estimates of soil equivalent ABCs suggest that As exceeds the regulatory threshold used in risk assessments for residential land use (20 mg kg⁻¹) across 16% of the landscape of England and Wales. The applicability of the method for cognate landscapes, and potential refinements is discussed.     

First U–Pb SHRIMP age of the Hauterivian stage, Neuquén Basin, Argentina

A high-resolution ion-microprobe (SHRIMP) U–Pb zircon age from a tuff layer intercalated in the ammonoid bearing sedimentary succession of the Neuquén Basin in Argentina provides a robust geochronologic date to add to the absolute ages and to improve the relative chronology of the Early Cretaceous Hauterivian stage. The tuff layer appears interbedded between shales of the upper member (Agua de la Mula) of the Agrio Formation within the Spitidiscus riccardii ammonoid zone (base of the Late Hauterivian) yielding a date of 132.5 ± 1.3 Ma. This date confirms and supports an accurate correlation between the ammonoid biostratigraphy of the Neuquén Basin with the Western Mediterranean Province of the Tethys during the Early Cretaceous and matches with the most recently published time scale. It also casts doubts on the validity of K–Ar ages on glauconite-grains recently reported from the Lower Cretaceous of the Vocontian Basin of France.     

Feasibility of pre-earthquake strengthening of buildings based on cost-benefit and life-cycle cost analysis, with the aid of fragility curves

There are two fundamental questions this article aims to deal with. First, whether a pre-earthquake strengthening of a large and heterogeneous building stock (the emphasis here is on building types common in S. Europe), is economically feasible or not, and second what is the optimal retrofit level for mitigating the seismic risk. To this purpose contemporary decision making tools, namely cost-benefit and life-cycle cost analyses, are tailored to the needs of the present study, and implemented with the aid of an ad-hoc developed new software application (COBE06). A method for estimating the reduction in structural vulnerability due to retrofit is proposed, as well as a methodology to determine the optimum retrofit level using the fragility curve approach. Finally, the proposed methodology is used in a pilot application that concerns the city of Thessaloniki, and results are drawn for the feasibility of strengthening the reinforced concrete building stock in this city.     

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.     

Flood hazard delineation combining geomorphological and hydrological methods: an example in the Northern Iberian Peninsula

Flood mapping requires the combination and integration of geomorphological and hydrological-hydraulic methods; however, despite this, there is very little scientific literature that compares and validates both methods. Two types of analysis are addressed in the present article. On the one hand, maps of flood plains have been elaborated using geomorphological evidence and historical flood data in the mountainous area of northwestern Spain, covering an area of more then 232 km² of floodplains. On the other hand, a hydrometeorological model has been developed (Clark semidistributed unit hydrograph) in the Sarria River basin (155 km², NW Spain). This basin is not gauged, hence the model was subjected to a goodness-of-fit test of its parameter (curve number) by means of Monte Carlo simulation. The peak flows obtained by means of the hydrological model were used for hydraulic modeling (one-phase, one-dimensional and steady flow) in a 4 km² urban stretch of the river bed. The delineation of surface areas affected by floods since 1918, as well as those analyzed subsequent to the geomorphological study, reveals a high degree of reliability in the delineation of the flooded areas with frequent recurrence intervals (<50 years). If we compare these flooded surface areas with the estimate obtained by the hydrological-hydraulic method we can see that the latter method overestimates the extent of the surface water by 144% for very frequent recurrence intervals (>10 years) and underestimates it as the recurrence interval increases, by up to 80% less floodplain for exceptional events (>500 years). Finally, a management map is put forth combining the most reliable results available by integrating both methods. Originally presented at the Sixth International Conference on Geomorphology.     

Defect properties of albite

Knowledge of the defect properties of Lunar and Mercurian minerals has recently become important, with the advent of models which attempt to explain the formation of the thin exosphere of these celestial bodies. Here, we have calculated the formation energies of sodium and oxygen vacancies in the mineral albite (NaAlSi₃O₈), as well as the Schottky defect energy for the removal of a Na₂O unit. We have employed both the supercell and Mott–Littleton approaches, using Kohn–Sham density functional theory and classical interatomic potential methods. As well as reporting the defect energies and structures, we comment upon the relative merits of the methods used.