Mercury Redox Chemistry in the Negro River Basin, Amazon: The Role of Organic Matter and Solar Light

Pristine water bodies in the Negro River basin, Brazilian Amazon, show relatively high concentrations of mercury. These waters are characterized by acidic pH, low concentrations of suspended solids, and high amounts of dissolved organic matter and are exposed to intense solar radiation throughout the year. This unique environment creates a very dynamic redox chemistry affecting the mobility of mercury due to the formation of the dissolved elemental species (Hg⁰). It has been shown that in this so-called black water, labile organic matter from flooded forest is the major scavenger of photogenerated H₂O₂. In the absence of hydrogen peroxide, these black waters lose their ability to oxidize Hg⁰ to Hg²⁺, thus increasing Hg⁰ evasion across the water/atmosphere interface, with average night time values of 3.80 pmol m^?2 h^?1. When the dry period starts, labile organic matter inputs gradually diminish, allowing the increasing concentration of H₂O₂ to re-establish oxidative water conditions, inhibiting the metal flux across the water/atmosphere interface and contributing to mercury accumulation in the water column.     

The effect of iron on montmorillonite stability. (II) Experimental investigation

Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 °C, P_sat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl₂ which were reacted at temperatures of 80, 150, and 250 °C, P_sat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 °C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.     

The origin of groundwater arsenic and fluorine in a volcanic sedimentary basin in central Mexico: a hydrochemistry hypothesis

A groundwater sampling campaign was carried out in the summer of 2013 in a low-temperature geothermal system located in Juventino Rosas (JR) municipality, Guanajuato State, Mexico. This groundwater presents high concentrations of As and F^? and high Rn counts, mainly in wells with relatively higher temperature. The chemistry of major elements was interpreted with different methods, like Piper and D’Amore diagrams. These diagrams allowed for classification of four groundwater types located in three hydrogeological environments. The aquifers are hosted mainly in alluvial-lacustrine sediments and volcanic rocks in interaction with fault and fracture systems. The subsidence, faults and fractures observed in the study area can act as preferential channels for recharge and also for the transport of deep fluids to the surface, especially in the basin plain. The formation of a piezometric dome and the observed hydrochemical behavior of groundwater suggest a possible origin of the As and F^?. Geochemical processes occurring during water–rock interaction are related to high concentrations of As and F^?. High temperatures and alteration processes (like rock weathering) induce dissolution of As and F^?-bearing minerals, increasing the content of these elements in groundwater.     

A model of boiling for fluid inclusion studies: Application to the Bolaños Ag–Au–Pb–Zn epithermal deposit,Western Mexico

Boiling can be inferred from fluid inclusion microthermometry studies when a progressive increase in apparent salinity is observed along with a decrease of homogenization temperature (T_H) and depth, thus reflecting the partitioning of non-volatile solutes into the liquid phase during steam loss. We propose a model for fluid evolution during boiling based on mass and heat balance equations, which establishes paths in the T_H-salinity space that can be compared with fluid inclusion data to confirm or discard boiling. Additionally, the model allows calculating paleo-depths, for which the effect of steam bubbles lowering the hydrostatic pressure is taken into account.     

Type I and Type II chlorophyll-a transformation products associated with algal senescence

Microalgal culture experiments to track chlorophyll-a (chl-a) transformation during senescence were characterised by the production of demetallated Type I chl-a transformation products in Pavlova gyrans and by the production of oxidative Type I transformation products in Isochrysis galbana. Dark-induced senescence in I. galbana produced a different distribution of Type I products from nutrient depletion induced senescence. Several novel Type I compounds were detected, including a chl-d like compound in I. galbana and a chl-a precursor like compound in P. gyrans. Type II chl-a transformation products were detected in the dissolved phase of I. galbana cultures; this is the first report of such compounds associated with marine algae.     

Systematic tapping of independent magma chambers during the 1 Ma Kidnappers supereruption

The 1.0 Ma Kidnappers supereruption (~ 1200 km³ DRE) from Mangakino volcanic centre, Taupo Volcanic Zone, New Zealand, produced a large phreatomagmatic fall deposit followed by an exceptionally widespread ignimbrite. Detailed sampling and analysis of glass shards and mineral phases have been undertaken through a proximal 4.0 m section of the fall deposit, representing the first two-thirds of erupted extra-caldera material. Major and trace element chemistries of glass shards define three distinct populations (types A, B and C), which systematically change in proportion through the fall deposit and are inferred to represent three magma types. Type B glass and biotite first appear at the same level (~ 0.95 m above base) in the fall deposit suggesting later tapping of a biotite-bearing magma. Plagioclase and Fe–Ti oxide compositions show bimodal distributions, which are linked to types A and B glass compositions. Temperature and pressure (T–P) estimates from hornblende and Fe–Ti oxide equilibria from each magma type are similar and therefore the three magma bodies were adjacent, not vertically stacked, in the crust. Most hornblende model T–P estimates range from 770 to 840 °C and 90 to 170 MPa corresponding to storage depths of ~ 4.0–6.5 km. Hornblende model T–P estimates coupled with in situ trace element fingerprinting imply that the magma bodies were individually well mixed, and not stratified. Compositional gaps between the three glass compositional types imply that no mixing between these magmas occurred. We interpret these data, coupled with the systematic changes in shard compositional proportions through the fall deposit, to reflect that three independent melt-dominant bodies of magma contributed large (A, ~ 270 km³), medium (B, ~ 90 km³) and small (C, ~ 40 km³) volumes (as reflected in the fall deposits) and were systematically tapped during the eruption. We propose that the systematic evacuation of the three independent magma bodies implies that there was tectonic triggering and linkage of eruptions. Our results show that supereruptions can be generated by near simultaneous multiple eruptions from independent magma chambers rather than the evacuation of a large single unitary magma chamber.     

Effects of land use on water column bacterial activity and enzyme stoichiometry in stream ecosystems

Fifty streams, located in southern Ontario, Canada, were visited in September 2008 to investigate the effect of varying land use, land cover, and associated resource inputs on water column bacterial abundance (BACT), production (BP), and extracellular enzyme activity and stoichiometry. Principle components analysis was used to summarize landscape data, producing three components (PCs), which explained 79.2% of the variability in the data. The PCs grouped into the following gradients: (PC1) urban land use and continuous annual cropping to wetland-like cover, (PC2) rotational cropping to forest-like cover, and (PC3) increasing rural and agricultural land uses with increasing watershed size. These landscape gradients created imbalanced resource availability. Nutrient resources were more abundant in streams with more intensive anthropogenic land uses, but carbon availability was primarily controlled by the abundance of natural land covers (wetland and wooded areas). BACT, BP, and enzyme activities were positively related primarily to nutrient availability and/or anthropogenic land use (Stepwise R ² range: 0.33?C0.73). The ratio of ??-glucosidase to alkaline phosphatase activity approached a 1:1 balance with increasing anthropogenic land use, decreased wetland and forest cover, and increased total dissolved nitrogen. The ratio of leucine-aminopeptidase to alkaline phosphatase activity approached 1:1 with both increased dissolved organic carbon and nitrogen. Moreover, enzyme C:N:P ratios moved closer to 1:1:1 with faster water column bacterial turnover times. These results suggest that water column microbial communities are better able to balance resource availability with growth in streams receiving nutrient subsidies from anthropogenic sources and under these conditions when carbon resources increase.     

Silica ‘chimneys’ related to paleo-brine discharge from the Williston Basin

Siliceous ‘solution chimneys’are described from a region unaffected by volcanism or high temperature fluid flow. The features are interpreted as low temperature dissolution/replacement structures formed in Paleozoic carbonates. The features are thought to be paleo-brine spring discharge sites similar to modern springs found within the same area which host a mid-continent marine ecosystem. Geochemical modeling shows mixing of spring waters with shallow groundwater could generate conditions of undersaturation with respect to calcite and silica oversaturation.     

Using numerical deformation–fluid-flow simulations to understand and target gold mineralisation around basalt domes in the Stawell Zone, Central Victoria, Australia

We present 3-D deformation–fluid-flow numerical models which place constraints on the importance of basalt dome shape and syn-mineralising shortening direction in localising structurally controlled gold mineralisation around basalt domes near Stawell, Victoria, Australia. Gold mineralisation in the Magdala ore-body at the Stawell Mine occurs predominantly within a thin altered unit named the Magdala Facies which blankets the basalt domes. In numerical models of the Magdala Dome models only the east–northeast–west–northwest and east–west shortened models record high fluid-flow rates in areas of known mineralisation which is consistent with the syn-mineralisation shortening directions. In models of the Kewell Dome (a prospect to the north), the position of areas of high fluid-flow rate when shortened in the east–northeast–west–northwest and east–west direction, combined with information from limited drilling indicated the potential for gold mineralisation at the south-west end of the dome. Diamond drill holes in this area yielded significant gold values.     

Characterization of a karstic aquifer using magnetic resonance sounding and electrical resistivity tomography: a case-study of Esta?a Lakes (northern Spain)

The geophysical characterization of a previously unstudied endorheic karstic system is presented. The studied area, known as the Esta?a Lakes, is located in the Pyrenean Marginal Sierras, northern Spain. The Esta?a Lakes are a set of natural water ponds on a bedrock of Triassic evaporites, lutites and carbonates. This wetland is included in the Natura 2000 European network of nature protection areas as a “Site of Community Importance”. Two geophysical techniques were used, magnetic resonance sounding (MRS) and electrical resistivity tomography (ERT), to map the subsurface geology and characterize the aquifer layers and the hydraulic links between the aquifers and lakes. The geophysical data were integrated with the surface geology and data from six boreholes. Ten electrical profiles were performed to identify the thickness of the units and lithological changes, whereas the MRS was used to determine the top of the saturated zone. As result, the aquifer in the Esta?a Lakes system and surrounding area has been identified as Middle Triassic carbonates, which does not correspond with the regional aquifer in the area (Upper Cretaceous and Eocene). This work shows the power of geophysical methods in poorly understood and tectonically complex areas in addition to the standard aquifer tests to evaluate hydraulic properties.