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.     

Geochemical transport modelling of drainage from experimental mine tailings cells covered by capillary barriers

The use of covers with capillary barrier effects (CCBEs) for reducing acid mine drainage (AMD) from sulphidic mine tailings is simulated using the MIN3P finite volume model for coupled groundwater flow, O₂ diffusion and multi-component reactive transport. The model is applied to simulate five pilot-scale in situ test cells containing reactive tailings from the Manitou mine site, Val d’Or, Que., Canada. Four of the cells were constructed with CCBEs over the tailings, while the fifth tailings cell was left uncovered. Observed and simulated discharge from the base of each cell showed that the capillary barrier covers significantly reduced sulphide oxidation and AMD. Compared to acidic discharge from the uncovered cell, discharge from the four CCBE-covered cells had neutral pH levels and 1–7 orders of magnitude lower concentrations of SO₄, Fe, Zn, Cu and Al. The simulations showed that the moisture retaining layer of the CCBEs reduced AMD by inhibiting O₂ diffusion into the underlying reactive wastes. Provided the moisture-retention layer of the CCBE remains close to saturation, its thickness had a relatively minor effect. Under such near-saturated conditions, O₂ availability is limited by its diffusion rate through the bulk porous medium and not by the diffusion rate through the oxidized grain shells. The model is providing important new insights for comparing design alternatives for reducing or controlling AMD.     

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.     

Lower Tertiary volcanic rocks off Kristiansund — Mid Norway

Grab samples from the Norwegian continental shelf show that diapiric structures occurring within a sequence of Mesozoic and Tertiary sediments represent volcanic rocks consisting of porphyritic olivine-nephelinite. The KAr age of 55.7 ± 0.9 m.y. shows that the area affected by Lower Tertiary magmatism in the North Atlantic region also included the continental shelf off Mid Norway. The highly undersaturated nature of these volcanic rocks, however, indicates that they are unlikely to be closely related to the widespread tuff horizons of the same age known from the North Sea.     

Geophysical and geochemical observations on actively seeping hydrocarbon gases on the south-eastern Yellow Sea continental shelf

In the southeastern Yellow Sea, active seepage of hydrocarbon gases has been observed by high-resolution (3.5 kHz) seismic profiling both in 1987 and 2001, occurring through a large number of plumes from the topmost pre-Holocene sedimentary layer. It is strong enough to compensate for current speed, extending vertically up to the sea surface. The gas seepage often appears to be explosive to form craters and diapirs, although pockmarks are rare due to the redistribution of mobile palimpsest sands. In core-top seawater and sediments, the gases are characterized by high amounts of C₂, homogenous ¹³C₁ values and a large difference (19.7 on average) between ¹³C₁ (–55.2 to –53.6 PDB) and ¹³C₂ (–36.8 to –32.5 PDB) values. The gases are considered to be generated with a smaller amount of C₁ at the early thermal cracking stage of labile source materials, after which the C₂ gas is enriched in ¹³C by diffusion or biological alternation at the generation or accumulation site. The homogenous ¹³C₁ values may be one of the geochemical characteristics of gases acquired at depth which are less altered in the case of rapid diffusive gas migration to the seafloor.     

A map series of the Southern East Pacific Rise and its flanks, 15° S to 19° S

Four large-scale bathymetric maps of the Southern East Pacific Rise and its flanks between 15° S and 19° S display many of the unique features of this superfast spreading environment including abundant seamounts (the Rano Rahi Field), axial discontinuities, discontinuity migration, and abyssal hill variation. Along with a summary of the regional geology, these maps will provide a valuable reference for other sea-going programs on-and off-axis in this area, including the Mantle ELectromagnetic and Tomography (MELT) experiment.     

Diet shifts of Caribbean grunts (Haemulidae) and snappers (Lutjanidae) and the relation with nursery-to-coral reef migrations

The spatial size distribution of grunts and snappers have previously indicated the separation of juveniles in nursery habitats from the adults on the coral reef. This implies life cycle migrations from nursery habitats (such as seagrass beds and mangroves) to the coral reef. If diet shifts are related to such migrations, then the diets of these fish must change before or around the fish size at which such migrations take place. A wide size range of juveniles of two grunt species (Haemulon sciurus and Haemulon flavolineatum) and of two snapper species (Lutjanus apodus and Ocyurus chrysurus) were caught in seagrass beds and mangroves, and their gut contents identified and quantified. Regression analysis between fish size and dietary importance of small crustaceans showed a negative relationship in all four species. Positive relations were found for H. sciurus, L. apodus and O. chrysurus between fish length and the dietary importance of decapods, and for L. apodusand O. chrysurus between fish length and prey fish importance. Critical changes in the fish diets with fish size were examined by application of a Canonical Correspondence Analysis (CCA). The CCA yielded three clusters of size-classes of fishes with similar diets, and application of a Mantel test showed that each of these clusters had significantly different diets, and that each cluster diet was significantly specialised. The size at which a fish species ‘switched’ from one cluster to another was compared with size-at-maturity data and with the typical size at which these species migrate from the nursery habitats to the coral reef. H. sciurus and H. flavolineatum may be prompted to migrate from the nursery habitats to coral reef habitats because of dietary changes, or because of the development of the gonads. For L. apodus and O. chrysurus, a dietary changeover forms a more likely explanation for nursery-to-reef migrations than does sexual maturation because these species reach maturity at sizes much larger than the maximum size of individuals found in nursery habitats. Although other factors may theoretically initiate or promote the migration patterns, the results of this study indicate that ontogenetic dietary changes may crucially influence the nursery-to-coral reef migrations of these reef fish species.     

Active spreading and hydrothermalism in North Fiji Basin (SW Pacific). Results of Japanese French Cruise Kaiyo 87

The aim of the Japanese-French Kaiyo 87 cruise was the study of the spreading axis in the North Fiji Basin (SW Pacific). A Seabeam and geophysical survey allowed us to define the detailed structure of the active NS spreading axis between 16° and 22° S and its relationships with the left lateral motion of the North Fiji Fracture Zone. Between 21° S and 18°10′ S, the spreading axis trends NS. From 18°10 S to 16°40 S the orientation of the spreading axis changes from NS to 015°. North of 16°40′ S the spreading axis trends 160°. These two 015° and 160° branches converge with the left lateral North Fiji fracture zone around 16°40′ S to define an RRFZ triple junction. Water sampling, dredging and photo TV deep towing give new information concerning the hydrothermal activity along the spreading axis. The discovery of hydrothermal deposits associated with living communities confirms this activity.     

Sediment transport pattern at the Barra Nova inlet, south Portugal: a conceptual model

The Barra Nova inlet, in south Portugal, is known to migrate progressively southeastwards under wave action. The morphodynamics of this system during a representative year suggests that this long-term evolution is dependent on a seasonal behavior of the tidal inlet which can be described through a three-stage model of post-storm, transition and extended fair-weather conditions. Processes involved in this evolution indicate that the historical migration of the Barra Nova is not dependent on the longshore drift forcing constricting the channel on the updrift coast, but rather on the adjustment of the system to a major erosion of the downdrift coast during short storm events.     

Mediterranean outflow through the Strait of Gibraltar since 18,000 Years B.P.: Mineralogical and geochemical arguments

Data obtained from mineralogical and geochemical analyses of piston and gravity cores, recovered from an area off Lisbon (Portugal) to the Alboran Sea (Mediterranean), serve as a basis for better understanding the past 18,000 years of hydrological exchanges at Gibraltar. Tracers used in this study are smectite, kaolinite, Ta, Th, La. One of the primary sources of particles both into and out of the Mediterranean is the Guadalquivir River. These particles are transported back into the Atlantic in the Mediterranean outflow water, and deposited along the Iberian slope. No evidence for reversal of this outflow current was found in those cores, since 18,000 years B.P.