Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: II. Metal removal mechanisms and potential mobility

Column bioreactors were used for studying mechanisms of metal removal, assessment of long-term stability of spent reactive mixtures, as well as potential metal mobility after treating highly contaminated acid mine drainage (AMD; pH 2.9–5.7). Several physicochemical, microbiological, and mineralogical analyses were performed on spent reactive mixtures collected from 4 bioreactors, which were tested in duplicate for two hydraulic retention times (7.3d and 10d), with downward flow over an 11-month period. Consistent with the high metal concentrations in the AMD feed, and with low metal concentrations measured in the treated effluent, the physicochemical analyses indicated very high concentrations of metals (Fe, Mn, Cd, Ni, and Zn) in the top and bottom layers of the reactive mixtures from all columns. Moreover, the concentrations of Fe (50.8–57.8 g/kg) and Mn (0.53–0.70 g/kg) were up to twice as high in the bottom layers, whereas the concentrations of Cd (6.77–13.3 g/kg), Ni (1.80–5.19 g/kg) and Zn (2.53–13.2 g/kg) were up to 50-times higher in the top layers. Chemical extractions and elemental analysis gave consistent results, which indicated a low fraction of metals removed as sulfides (up to 15% of total metals recovered in spent reactive mixtures). Moreover, Fe and Mn were found in a more stable chemical form (residual fraction was 42–74% for Mn and 30–77% for Fe) relative to Cd, Ni or Zn, which seemed more weakly bound (oxidisable/reducible fractions) and showed higher potential mobility. Besides identifying (oxy)hydroxide and carbonate minerals, the mineralogical analyses identified metal sulfides containing Fe, Cd, Ni and Zn. Metal removal mechanisms were, therefore, mainly adsorption and other binding mechanisms with organic matter (for Cd, Ni and Zn), and the precipitation as (oxy)hydroxide minerals (for Fe and Mn). After 15 months, however, the column bioreactors did not lose their capacity for removing metals from the AMD. Although the metals were immobile during the bioreactor treatment, their mobility could increase from spent reactive mixtures, if stored inappropriately. Metal recovery by acidic leaching of spent substrates at the end of bioreactor operation could be an alternative.     

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.