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.     

Paleogeographic regionalization of Triassic seas based on conodontophorids

Geographic differentiation of conodontophorids between northern and southern latitudes commenced in the Triassic since the early Induan. Cosmopolitan long-lived genera of predominantly smooth morphotypes without sculpturing were characteristic of high-latitude basins of the Panboreal Superrealm. Since the early Olenekian until the Carnian inclusive, this superrealm consisted of the Siberian Realm that extended over Northeast Asia and the Canada-Svalbard Realm that included the Svalbard Archipelago and northern regions of Canada. Throughout the Triassic period, conodontophorids characteristic of the Tethys-Panthalassa Superrealm spanning the Tethys and low-latitude zones of the Pacific were highly endemic, very diverse in taxonomic aspect, having well-developed sculpturing and tempos of morphological transformations. Distinctions between the Early-Middle Triassic conodontophorids from northern and southern zones were not as great as afterward, and their impoverished assemblages from southern Tethyan basins were close in some respects to the Boreal ones. Their habitat basins of that time can be grouped into the Mediterranean-Pacific and India-Pakistan realms. Hence, the extent of geographic differentiation of conodontophorids was not constant and gradually grew, as their taxonomic diversity was reducing in northern basins but relatively increasing in southern ones. The Panboreal e Tethys-Panthalassa superrealms of conodontophorids, which are most clearly recognizable, are close to first-rank paleobiochores (superrealms) established earlier for ammonoids and bivalve mollusks. Main factor that controlled geographic differentiation of Triassic conodontophorids was climatic zoning. Initially lower diversity of southern Tethyan assemblages points probably to relatively cooler water regime in the peri-Gondwanan part of the Tethys. The established patterns in geographic distribution of conodontophorids characterize most likely the real trend of their differentiation and evolution, i.e., the distribution area contraction prior to complete extinction at the end of the Triassic     

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.     

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.