Leaching of metals from copper smelter flue dust (Mufulira,Zambian Copperbelt)

The leaching behaviour of electrostatic precipitator dust from the Mufulira Cu smelter (Copperbelt, Zambia) was studied using a 48-h pH-static leaching experiment (CEN/TS 14997). The release of metals (Cd, Co, Cu, Ni, Pb and Zn) and changes in mineralogical composition using X-ray diffraction and PHREEQC-2 modelling were investigated in the pH range of 3–7. The highest concentrations of metals were released at pH 3–4.5, which encompasses the natural pH of the dust suspension (～4.3). About 40% of the total Cu was leached at pH 3, yielding 107 g/kg. Chalcanthite (CuSO₄·5H₂O), magnetite (Fe₃O₄) and delafossite (CuFeO₂) represented the principal phases of the studied dust. In contact with water, chalcanthite was dissolved and hydrated Cu sulphates precipitated at pH 4–7. Gypsum (CaSO₄·2H₂O) and secondary Fe or Al phases were observed in the leached residues. Serious environmental impact due to leaching may occur in dust-contaminated soil systems in the vicinity of the smelting plants.     

Increased Terrestrial to Ocean Sediment and Carbon Fluxes in the Northern Chesapeake Bay Associated With Twentieth Century Land Alteration

We calculated Chesapeake Bay (CB) sediment and carbon fluxes before and after major anthropogenic land clearance using robust monitoring, modeling and sedimentary data. Four distinct fluxes in the estuarine system were considered including (1) the flux of eroded material from the watershed to streams, (2) the flux of suspended sediment at river fall lines, (3) the burial flux in tributary sediments, and (4) the burial flux in main CB sediments. The sedimentary maximum in Ambrosia (ragweed) pollen marked peak land clearance (~1900 a.d.). Rivers feeding CB had a total organic carbon (TOC)/total suspended solids of 0.24?±?0.12, and we used this observation to calculate TOC fluxes from sediment fluxes. Sediment and carbon fluxes increased by 138–269% across all four regions after land clearance. Our results demonstrate that sediment delivery to CB is subject to significant lags and that excess post-land clearance sediment loads have not reached the ocean. Post-land clearance increases in erosional flux from watersheds, and burial in estuaries are important processes that must be considered to calculate accurate global sediment and carbon budgets.     

Sensitivity of interfacial hydraulics to the microtopographic roughness of water‐lain gravels

Flow within the interfacial layer of gravel‐bed rivers is poorly understood, but this zone is important because the hydraulics here transport sediment, generate flow structures and interact with benthic organisms. We hypothesized that different gravel‐bed microtopographies generate measurable differences in hydraulic characteristics within the interfacial layer. This was tested using a high density of spatially and vertically distributed, velocity time series measured in the interfacial layers above three surfaces of contrasting microtopography. These surfaces had natural water‐worked textures, captured in the field using a casting procedure. Analysis was repeated for three discharges, with Reynolds numbers between 165000 and 287000, to evaluate whether discharge affected the impact of microtopography on interfacial flows. Relative submergence varied over a small range (3.5 to 8.1) characteristic of upland gravel‐bed rivers. Between‐surface differences in the median and variance of several time‐averaged and turbulent flow parameters were tested using non‐parametric statistics. Across all discharges, microtopographic differences did not affect spatially averaged (median) values of streamwise velocity, but were associated with significant differences in its spatial variance, and did affect spatially averaged (median) turbulent kinetic energy. Sweep and ejection events dominated the interfacial region above all surfaces at all flows, but there was a microtopographic effect, with Q2 and Q4 events less dominant and structures less persistent above the surface with the widest relief distribution, especially at the highest Reynolds number flow. Results are broadly consistent with earlier work, although this analysis is unique because of the focus on interfacial hydraulics, spatially averaged ‘patch scale’ metrics and a statistical approach to data analysis. An important implication is that observable differences in microtopography do not necessarily produce differences in interfacial hydraulics. An important observation is that appropriate roughness parameterizations for gravel‐bed rivers remain elusive, partly because the relative contributions to flow resistance of different aspects of bed microtopography are poorly constrained. © 2014 The Authors. Earth Surface Processes and Landforms Published by John Wiley & Sons Ltd.     

Calculating surface water PCO2 from foraminiferal organic δC

The δ¹³C of organic matter bound within the crystal lattice of foraminiferal calcite tests may provide a potential tracer of the isotopic composition of the surface water primary photosynthate. Using δ¹³C of the organic matter extracted from the crystal lattice and the calcite test, it is theoretically possible to estimate the paleo-surface water pCO₂. We have tailored this technique initially for the subpolar planktonic foraminifera species Globigerina bulloides. Initial surface water pCO₂ estimates from deep-sea core BOFS 5K (50°41.3′N, 21°51.9′W, water depth 3547 m) indicate that the northeast Atlantic Ocean may have been a greater sink for CO₂ during the last glacial than during the Holocene. Greatly reduced benthic foraminifera abundances, especially phytodetritus feeders, in BOFS 5K during the last glacial indicates low surface productivity. This rules out a productivity-driven CO₂ sink. The enhanced glacial CO₂ sink must, therefore, have results from a southwards shift of the centre of deep water formation.     

Catabolic and anabolic energy for chemolithoautotrophs in deep-sea hydrothermal systems hosted in different rock types

Active deep-sea hydrothermal vents are hosted by a range of different rock types, including basalt, peridotite, and felsic rocks. The associated hydrothermal fluids exhibit substantial chemical variability, which is largely attributable to compositional differences among the underlying host rocks. Numerical models were used to evaluate the energetics of seven inorganic redox reactions (potential catabolisms of chemolithoautotrophs) and numerous biomolecule synthesis reactions (anabolism) in a representative sampling of these systems, where chemical gradients are established by mixing hydrothermal fluid with seawater. The wide ranging fluid compositions dictate demonstrable differences in Gibbs energies (ΔG_r) of these catabolic and anabolic reactions in three peridotite-hosted, six basalt-hosted, one troctolite-basalt hybrid, and two felsic rock-hosted systems. In peridotite-hosted systems at low to moderate temperatures (<∼45 °C) and high seawater:hydrothermal fluid (SW:HF) mixing ratios (>10), hydrogen oxidation yields the most catabolic energy, but the oxidation of methane, ferrous iron, and sulfide can also be moderately exergonic. At higher temperatures, and consequent SW:HF mixing ratios <10, anaerobic processes dominate the energy landscape; sulfate reduction and methanogenesis are more exergonic than any of the aerobic respiration reactions. By comparison, in the basalt-hosted and felsic rock-hosted systems, sulfide oxidation was the predominant catabolic energy source at all temperatures (and SW:HF ratios) considered. The energetics of catabolism at the troctolite-basalt hybrid system were intermediate to these extremes. Reaction energetics for anabolism in chemolithoautotrophs—represented here by the synthesis of amino acids, nucleotides, fatty acids, saccharides, and amines—were generally most favorable at moderate temperatures (22-32 °C) and corresponding SW:HF mixing ratios (∼15). In peridotite-hosted and the troctolite-basalt hybrid systems, ΔG_r for primary biomass synthesis yielded up to ∼900 J per g dry cell mass. The energetics of anabolism in basalt- and felsic rock-hosted systems were far less favorable. The results suggest that in peridotite-hosted (and troctolite-basalt hybrid) systems, compared with their basalt (and felsic rock) counterparts, microbial catabolic strategies—and consequently variations in microbial phylotypes—may be far more diverse and some biomass synthesis may yield energy rather than imposing a high energetic cost.     

Stability and dynamics of the continental tectosphere

Continental cratons overlie thick, high-viscosity, thermal and chemical boundary layers, where the chemical boundary layers are less dense than they would be due to thermal effects alone, perhaps because they are depleted in basaltic constituents. If the continental tectosphere is the same age as the overlying Archaean crust, then the continental tectosphere must be able to survive for several billion years without undergoing a convective instability, despite being both cold and thick. Since platforms and shields correlate only weakly with Earth's gravity and geoid anomalies, acceptable models of the continental tectosphere must also satisfy this gravity constraint. We investigate the long-term stability of the continental tectosphere by carrying out a number of numerical convection experiments within a two-dimensional Cartesian domain. We initiate our experiments with a tectosphere (thermal and chemical boundary layers) immersed in a region of uniform composition, temperature, and viscosity, and consider the effects on the stability of the tectosphere of (1) activation energy (used to define the temperature dependence of viscosity), (2) compositional buoyancy, and (3) linear or non-linear rheology. The large lateral thermal gradients required to match oceanic and tectosphere structures initiate the dominant instability, a “drip” which develops at the side of the tectosphere and moves to beneath its center. High activation energies and high background viscosities restrict the amount and rate of entrainment. Compositional buoyancy does not significantly change the flow pattern. Rather, compositional buoyancy slows the destruction process somewhat and reduces the stress within the tectosphere. With a non-Newtonian rheology, this reduction in stress helps to stiffen the tectosphere. In these experiments, dynamical systems that adequately model the present ocean-continent structures have activation energy E*≥180 kJ mole⁻¹ — a value about one third the estimate of activation energy for olivine, E*≈520 kJ mole⁻¹. Although for E*≈520 kJ mole⁻¹, compositional buoyancy is not required for the tectosphere to survive, the joint application of longevity and gravity constraints allows us to reject all models not containing compositional buoyancy, and to predict that the ratio of compositional to thermal buoyancy within the continental tectosphere is approximately unity.     

Numerical modeling of fracking fluid migration through fault zones and fractures in the North German Basin

Gas production from shale formations by hydraulic fracturing has raised concerns about the effects on the quality of fresh groundwater. The migration of injected fracking fluids towards the surface was investigated in the North German Basin, based on the known standard lithology. This included cases with natural preferential pathways such as permeable fault zones and fracture networks. Conservative assumptions were applied in the simulation of flow and mass transport triggered by a high pressure boundary of up to 50 MPa excess pressure. The results show no significant fluid migration for a case with undisturbed cap rocks and a maximum of 41 m vertical transport within a permeable fault zone during the pressurization. Open fractures, if present, strongly control the flow field and migration; here vertical transport of fracking fluids reaches up to 200 m during hydraulic fracturing simulation. Long-term transport of the injected water was simulated for 300 years. The fracking fluid rises vertically within the fault zone up to 485 m due to buoyancy. Progressively, it is transported horizontally into sandstone layers, following the natural groundwater flow direction. In the long-term, the injected fluids are diluted to minor concentrations. Despite the presence of permeable pathways, the injected fracking fluids in the reported model did not reach near-surface aquifers, either during the hydraulic fracturing or in the long term. Therefore, the probability of impacts on shallow groundwater by the rise of fracking fluids from a deep shale-gas formation through the geological underground to the surface is small.     

Decomposition of Hudson estuary macrophytes: Photosynthetic pigment transformations and decay constants

Plant pigment decay constants were determined for four macrophytes collected from the Hudson Estuary.Typha angustifolia andScirpus fluviatilis were used as representatives of emergent aquatic vegetation (EAV), andPotamogeton sp. andVallisneria americana were used to represent submerged aquatic vegetation (SAV). Litter bags were maintained in an environmental chamber in the dark for 104 d. The fastest rate of total mass loss was in the SAVV. americana and slowest in the EAVT. angustifolia. Changes in carotenoid and chloropigment concentration resulting from microbial and meiofaunal heterotrophy in each of the macrophytes were quantified using reverse-phase, high-performance liquid chromatography (RP-HPLC) techniques. Chlorophyllc and the carotenoid, fucoxanthin, provided useful biomarkers in determining the presence of epiphytic diatom growth, which only occurred on the SAV. The highest concentrations of phaeophorbidea, commonly used as an indication of metazoan grazing, were found in the SAVV. americana. Low concentrations of phaeophorbidea in the SAVPotamogeton sp. indicate inefficient use of this SAV by meiofaunal grazers. Lutein decayed slower than all other carotenoids in both EAV and SAV. Microcosm studies such as this are necessary to further understand the mechanisms and kinetics of photosynthetic pigment transformations in natural systems.     

A MIXTURE MODEL OF ANNUAL PRECIPITATION IN PERU*

A two component mixed log-normal distribution effectively models annual precipitation totals at two stations in Peru characterized by widely differing interannual patterns of precipitation. Physical evidence supports the division of station records into two subsamples. Years with ENSO events and years without ENSO events identify the components of a mixed probability model. The mixed model produces a superior fit to the two parameter log-normal distribution. Model application provides a reliable means of precipitation prediction and also quantitatively describes the highly variable temporal and spatial pattern of annual precipitation in western Peru.