Organotemplate silica deposition in Neoproterozoic deep-marine environments: evidence from the Penganga Group, Adilabad, India

Silica in bedded cherts interstratified with manganese carbonates in a deep‐water carbonate ramp succession of the Neoproterozoic Penganga Group, India, displays film‐like, spherical to rod‐shaped, and tubular branching microstructures. The microstructures resemble mineralized extracellular polysaccharides, biofilms and bacterial morphologies. The microstructures suggest silicification by nucleation of silica on organic‐templates or indirectly as sorbed species accumulating on organic templates. Given that similar microstructures have also been documented in Archean cherts it is proposed that organotemplates might have been an important sink for the deposition of silica in Precambrian deep‐water marine environments.     

Geometry and kinematics of recent deformation in the Mondy–Tunka area (south-westernmost Baikal rift zone, Mongolia–Siberia)

We used satellite imagery and field data to investigate the south‐westernmost Baikal rift zone. We focus our study in the Mondy and Ikhe Ukhgun valleys, site of an Mw = 6.9 seismic event in 1950. Surface deformations are observed along the E–W‐trending Mondy strike‐slip fault and along the Ikhe Ukhgun thrust. The Mondy fault system is 80 km long and is composed of four segments 10–15 km long. These segments are characterized by subvertical planes with left‐lateral movements. The Ikhe Ukhgun thrust is 20 km long, dips 40° to the south and shows reverse movement with a left‐lateral component. These observations are consistent with the present‐day regional NNE–SSW compression and with the focal mechanism of the 1950 Mondy earthquake that was recently re‐evaluated. These features, like those observed in the Tunka basin, demonstrate a recent change of regional strain regime from transtension to transpression that we place before the Late Pleistocene.     

Wavelet analysis of inter‐annual variability in the runoff regimes of glacial and nival stream catchments,Bow Lake,Alberta

Continuous wavelet analyses of hourly time series of air temperature, stream discharge, and precipitation are used to compare the seasonal and inter‐annual variability in hydrological regimes of the two principal streams feeding Bow Lake, Banff National Park, Alberta: the glacial stream draining the Wapta Icefields, and the snowmelt‐fed Bow River. The goal is to understand how water sources and flow routing differ between the two catchments. Wavelet spectra and cross‐wavelet spectra were determined for air temperature and discharge from the two streams for summers (June–September) 1997–2000, and for rainfall and discharge for the summers of 1999 and 2000. The diurnal signal of the glacial runoff was orders of magnitude higher in 1998 than in other years, indicating that significant ice exposure and the development of channelized glacial drainage occurred as a result of the 1997–98 El Niño conditions. Early retreat of the snowpack in 1997 and 1998 led to a significant summer‐long input of melt runoff from a small area of ice cover in the Bow River catchment; but such inputs were not apparent in 1999 and 2000, when snow cover was more extensive. Rainfall had a stronger influence on runoff and followed quicker flow paths in the Bow River catchment than in the glacial catchment. Snowpack thickness and catchment size were the primary controls on the phase relationship between temperature and discharge at diurnal time scales. Wavelet analysis is a fast and effective means to characterize runoff, temperature, and precipitation regimes and their interrelationships and inter‐annual variability. The technique is effective at identifying inter‐annual and seasonal changes in the relative contributions of different water sources to runoff, and changes in the time required for routing of diurnal meltwater pulses through a catchment. However, it is less effective at identifying changes/differences in the type of the flow routing (e.g. overland flow versus through flow) between or within catchments. Copyright © 2003 John Wiley & Sons, Ltd.     

TEM evidence for intracellular accumulation of lead by bacteria in subsurface environments

We monitored near-surface atmospheric fallout (15-cm above ground) and soil solution (at 15, 35 and 55 cm below ground) derived nanoparticles over an 8-month period by collecting the particles directly onto TEM grids in anthropogenically-influenced (vineyard) and pristine (native forest) sites in France. Particle clusters trapped on the grid were selected randomly and individual particles were binned into eight different groups (euhedral clays, weathered clays, salts, oxi-hydroxides, bacteria, non-living organic matter, aggregates and undetermined). Bacteria represent 9–23% of the collected nanoparticle area (ave. 9.4% and 18% for two atmospheric collection sites and ave. 23% for soil infiltration samples). Bacteria were most often associated with non-living organic matter and comprised a variety of morpho-types. Interestingly, 45% of all the bacteria analyzed by transmission electron microscopy and electron dispersive spectroscopy (TEM-EDX) showed the presence of intracellular grains significantly enriched in lead and phosphorus. Intracellular sequestration of Pb into polyphosphate bodies has been observed in the laboratory, but this is the first observation of this phenomenon in a natural environment. Furthermore, this suggests that microbial-bound Pb may be an important transport mechanism in subsurface environments.     

Formation of Zn–Ca phyllomanganate nanoparticles in grass roots

It is now well established that a number of terrestrial and aquatic microorganisms have the capacity to oxidize and precipitate Mn as phyllomanganate. However, this biomineralization has never been shown to occur in plant tissues, nor has the structure of a natural Mn(IV) biooxide been characterized in detail. We show that the graminaceous plant Festuca rubra (red fescue) produces a Zn-rich phyllomanganate with constant Zn:Mn and Ca:Mn atomic ratios (0.46 and 0.38, respectively) when grown on a contaminated sediment. This new phase is so far the Zn-richest manganate known to form in nature (chalcophanite has a Zn:Mn ratio of 0.33) and has no synthetic equivalent. Visual examination of root fragments under a microscope shows black precipitates about ten to several tens of microns in size, and their imaging with backscattered and secondary electrons demonstrates that they are located in the root epidermis. In situ measurements by Mn and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) with a micro-focused beam can be quantitatively described by a single-phase model consisting of Mn(IV) octahedral layers with 22% vacant sites capped with tetrahedral and octahedral Zn in proportions of 3:1. The layer charge deficit is also partly balanced by interlayer Mn and Ca. Diffracting crystallites have a domain radius of 33 Å in the ab plane and contain only 1.2 layers (8.6 Å) on average. Since this biogenic Mn oxide consists mostly of isolated layers, basal 00l reflections are essentially absent despite its lamellar structure. Individual Mn layers are probably held together in the Mn–Zn precipitates by stabilizing organic molecules. Zinc biomineralization by plants likely is a defense mechanism against toxicity induced by excess concentrations of this metal in the rhizosphere.     

Participation in payments for ecosystem services: Case studies from the Lacandon rainforest, Mexico

Understanding people’s willingness to participate in projects and programmes of payments for ecosystem services (PES) has not been a key analytical concern of the scholarly literature around this new field of environmental policy and practice. This paper analyses participation in four communities benefiting from payments for biodiversity and carbon fixation in Mexico, and contrasts the results for each case with neighbouring communities that do not receive payments. We take a holistic approach that accounts for procedural rules, actors’ interactions, institutions and values, and individuals’ characteristics. We show that the nature of PES rules and the effectiveness of communication with government officers and NGOs influence resource managers’ ability and willingness to participate. We highlight community size, resource managers’ ability to diversify livelihood activities and local perspectives on the conservation of common forests, particularly sacred values and intergenerational concerns on forest conservation, as critical participation drivers. This analysis provides insights on why and how these new institutions may be attractive for some resource managers and permits to draw some recommendations for the future design of PES projects and programmes.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: I. Effect of hydraulic retention time

Sulfate-reducing passive bioreactors have proved to be an effective technology for the treatment of acid mine drainage (AMD) contaminated waters over relatively short periods of time (1–5 a). However, long-term efficiency can be limited by several factors including problems related to the hydraulic properties of the reactive mixture. In this study, the effect of two hydraulic retention times (HRTs) of 7.3 d and 10 d on the performance of passive bioreactors was evaluated over an 11-month period for the treatment of a highly contaminated AMD. Evolution of the porosity and hydraulic conductivity of the reactive mixture was also evaluated during the 15-month operation of two bioreactors. Results indicated that bioreactors were effective at both HRTs for increasing the pH and alkalinity of contaminated water and for SO₄ and metal removal (60–82% for Fe and up to 99.9% for Cd, Ni and Zn). Although the quality of treated effluent was significantly improved with the 10 d HRT compared to the 7.3 d HRT, results showed that the higher HRT reduced the porosity and the permeability of the reactive mixture which might lead to hydraulic related problems and, eventually, to limited efficiency in long-term operation compared to a shorter HRT. The choice of HRT for a passive bioreactor must therefore consider both the desired quality of treated effluent and the potential for deterioration of hydraulic properties in the reactive mixture.     

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.     

Leaching of lead metallurgical slags and pollutant mobility far from equilibrium conditions

Lead metallurgical slags are partially vitrified materials containing residual amounts of Zn, Pb, Cr, Cd and As. These hazardous materials are generally buried on heaps exposed to weathering. In this study, leaching behavior of lead blast furnace slags has been tested using pure water and open flow experiments. It appears that in such far from equilibrium and slightly acidic conditions, the main phase to be altered is the vitreous phase. As for lunar, basaltic and nuclear glasses, alkalis/proton exchanges prevail and lead to the formation of a non-protective altered layer enriched in Si, Fe and Al. The composition of the altered layer is quite constant except for Si whose concentration decreases towards the leachate interface. Owing to their sizes, micrometric Pb droplets are not always totally dissolved at the slag surface. Nevertheless, nanometric Pb droplets are instantaneously dissolved while a surrounding altered layer is formed. This leads to high Pb releases in open flow systems. Leachate chemistry and dissolution rates of the vitreous phase are closely comparable to previous leaching tests with basaltic and nuclear glasses in conditions far from equilibrium. Moreover, this study confirms that Fe is a stable element in such conditions.     

Structural investigation of the synthetic CaAn(PO4)2 (An = Th and Np) cheralite-like phosphates

The crystallographic structures of the synthetic cheralite, CaTh(PO₄)₂, and its homolog CaNp(PO₄)₂ have been investigated by X-ray diffraction at room temperature. Rietveld analyses showed that both compounds crystallize in the monoclinic system and are isostructural to monazite LnPO₄ (Ln = La to Gd). The space group is P2₁/n (I.T. = 14) with Z = 2. The refined lattice parameters of CaTh(PO₄)₂ are a = 6.7085(8) Å, b = 6.9160(6) Å, c = 6.4152(6) Å, and β = 103.71(1)° with best fit parameters R _wp = 4.87%, R _p = 3.69% and R _B = 3.99%. For CaNp(PO₄)₂, we obtained a = 6.6509(5) Å, b = 6.8390(3) Å, c = 6.3537(8) Å, and β = 104.12(6)° and R _wp = 6.74%, R _p = 5.23%, and R _B = 6.05%. The results indicate significant distortions of bond length and angles of the PO₄ tetrahedra in CaTh(PO₄)₂ and to a lesser extent in CaNp(PO₄)₂. The structural distortions were confirmed by Raman spectroscopy of CaTh(PO₄)₂. A comparison with the isostructural compounds LnPO₄ (Ln = Ce and Sm) confirmed that the substitution of the large rare earth trivalent cations with Ca²⁺ and Th⁴⁺ introduces a distortion of the PO₄ tetrahedra.