Solubility of KFe(CrO4)2·2H2O at 4–75°C

The solubility of KFe(CrO₄)₂·2H₂O, a precipitate recently identified in a Cr(VI)-contaminated soil, was studied in dissolution and precipitation experiments. Ten dissolution experiments were conducted at 4–75°C and initial pH values between 0.8 and 1.2 using synthetic KFe(CrO₄)₂·2H₂O. Four precipitation experiments were conducted at 25°C with final pH values between 0.16 and 1.39. The log K_SP for the reaction

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Distribution, characterization, and geochemical controls of elements of concern in uranium mine tailings, Key Lake, Saskatchewan, Canada

The distribution of As, Mo, Ni and Se in the aqueous and solid phases of U mine tailings in the Deilmann Tailings Management Facility (DTMF), located at the Key Lake mine in northern Saskatchewan, Canada, was defined using as-discharged tailings samples collected monthly starting in 1996 and core samples collected from the DTMF from 3 locations on 3 occasions between 2004 and 2009. These data indicated that the DTMF can be divided into two geochemical zones; tailings generated from the Deilmann ore body between 1996 and 2000 and tailings from the McArthur River ore body, mined after July 2000. The Deilmann tailings solids are generally characterized by greater elemental concentrations than those in the McArthur River tailings, particularly for As, Co and Ni. These elevated concentrations are attributed to the abundance of Ni–Co–As–S minerals in this ore. The mean aqueous concentrations of As, Mo, Ni, and Se are 3.7, 23.2, 0.14, and 0.02 mg L⁻¹, respectively, in the Deilmann porewaters and 0.20, 4.16, 0.06, and 0.03 mg L⁻¹, respectively, in the McArthur River porewaters. Similarly, the mean As, Mo, Ni, and Se solid phase concentrations are 5.89 × 10³, 69.9, 3.20 × 10³, and 17.4 μg g⁻¹, respectively, for the Deilmann tailings and 440, 13.6, 551, and 3.03 μg g⁻¹ in the McArthur River tailings. Statistically, pH remained unchanged from the time of discharge while Eh values have remained oxic with no significant change between the two tailings types over 15 a of residence time. Results from sequential extractions, thermodynamic modeling, and results of complimentary research indicated that ferrihydrite solubility is the dominant control on aqueous As concentrations and also plays a role in controlling dissolved Mo, Ni and Se.     

Provenance of the Bosnian Flysch

Sandwiched between the Adriatic Carbonate Platform and the Dinaride Ophiolite Zone, the Bosnian Flysch forms a c. 3000 m thick, intensely folded stack of Upper Jurassic to Cretaceous mixed carbonate and siliciclastic sediments in the Dinarides. New petrographic, heavy mineral, zircon U/Pb and fission-track data as well as biostratigraphic evidence allow us to reconstruct the palaeogeology of the source areas of the Bosnian Flysch basin in late Mesozoic times. Middle Jurassic intraoceanic subduction of the Neotethys was shortly followed by exhumation of the overriding oceanic plate. Trench sedimentation was controlled by a dual sediment supply from the sub-ophiolitic high-grade metamorphic soles and from the distal continental margin of the Adriatic plate. Following obduction onto Adria, from the Jurassic–Cretaceous transition onwards a vast clastic wedge (Vranduk Formation) was developed in front of the leading edge, fed by continental basement units of Adria that experienced Early Cretaceous synsedimentary cooling, by the overlying ophiolitic thrust sheets and by redeposited elements of coeval Urgonian facies reefs grown on the thrust wedge complex. Following mid-Cretaceous deformation and thermal overprint of the Vranduk Formation, the depozone migrated further towards SW and received increasing amounts of redeposited carbonate detritus released from the Adriatic Carbonate Platform margin (Ugar Formation). Subordinate siliciclastic source components indicate changing source rocks on the upper plate, with ophiolites becoming subordinate. The zone of the continental basement previously affected by the Late Jurassic–Early Cretaceous thermal imprint has been removed; instead, the basement mostly supplied detritus with a wide range of pre-Jurassic cooling ages. However, a c. 80 Ma, largely synsedimentary cooling event is also recorded by the Ugar Formation, that contrasts the predominantly Early Cretaceous cooling of the Adriatic basement and suggests, at least locally, a fast exhumation.     

Cathodoluminescence of authigenic albite

Authigenic albites in carbonate rocks typically grow in a high-grade diagenetic to low-grade metamorphic environment and often show Roc-Tourné-twinning sensu Füchtbauer. Based on an investigation of four Middle to South European occurrences, they show Mn²⁺- and Fe³⁺-activated cathodoluminescence (CL), as revealed by combined high resolution spectroscopy of cathodoluminescence emission (HRS-CL), electron paramagnetic resonance (EPR), and proton-induced X-ray emission (μPIXE).     

Methane and sulfide fluxes in permanent anoxia: In situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV) is located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea). The DMV was studied during the RV Meteor expedition M72/2 as an example of an active mud volcano system, to investigate the significance of submarine mud volcanism for the methane and sulfide budget of the anoxic Black Sea hydrosphere. Our studies included benthic fluxes of methane and sulfide, as well as the factors controlling transport, consumption and production of both compounds within the sediment. The pie-shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at its summit north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was repressed in this zone due to the upward flow of sulfate-depleted fluids through recently deposited subsurface muds, apparently limiting microbial methanotrophic activity. Consequently, the emission of dissolved methane into the water column was high, with an estimated rate of 0.46 mol m⁻² d⁻¹. On the wide plateau and edge of the mud volcano surrounding the summit, fluid flow and total methane flux were lower, allowing higher SR and AOM rates correlated with an increase in sulfate penetration into the sediment. Here, between 50% and 70% of the methane flux (0.07-0.1 mol m⁻² d⁻¹) was consumed within the upper 10 cm of the sediment. The overall amount of dissolved methane released from the entire mud volcano structure into the water column was significant with a discharge of 1.3 × 10⁷ mol yr⁻¹. The DMV maintains also high areal rates of methane-fueled sulfide production and emission of on average 0.05 mol m⁻² d⁻¹. This is a difference to mud volcanoes in oxic waters, which emit similar amounts of methane, but not sulfide. However, based on a comparison of this and other mud volcanoes of the Black Sea, we conclude that sulfide and methane emission into the hydrosphere from deep-water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.     

Pathways and regulation of carbon, sulfur and energy transfer in marine sediments overlying methane gas hydrates on the Opouawe Bank (New Zealand)

This study combines sediment geochemical analysis, in situ benthic lander deployments and numerical modeling to quantify the biogeochemical cycles of carbon and sulfur and the associated rates of Gibbs energy production at a novel methane seep. The benthic ecosystem is dominated by a dense population of tube-building ampharetid polychaetes and conspicuous microbial mats were unusually absent. A 1D numerical reaction-transport model, which allows for the explicit growth of sulfide and methane oxidizing microorganisms, was tuned to the geochemical data using a fluid advection velocity of 14 cm yr⁻¹. The fluids provide a deep source of dissolved hydrogen sulfide and methane to the sediment with fluxes equal to 4.1 and 18.2 mmol m⁻² d⁻¹, respectively. Chemosynthetic biomass production in the subsurface sediment is estimated to be 2.8 mmol m⁻² d⁻¹ of C biomass. However, carbon and oxygen budgets indicate that chemosynthetic organisms living directly above or on the surface sediment have the potential to produce 12.3 mmol m⁻² d⁻¹ of C biomass. This autochthonous carbon source meets the ampharetid respiratory carbon demand of 23.2 mmol m⁻² d⁻¹ to within a factor of 2. By contrast, the contribution of photosynthetically-fixed carbon sources to ampharetid nutrition is minor (3.3 mmol m⁻² d⁻¹ of C). The data strongly suggest that mixing of labile autochthonous microbial detritus below the oxic layer sustains high measured rates of sulfate reduction in the uppermost 2 cm of the sulfidic sediment (100-200 nmol cm⁻³ d⁻¹). Similar rates have been reported in the literature for other seeps, from which we conclude that autochthonous organic matter is an important substrate for sulfate reducing bacteria in these sediment layers. A system-scale energy budget based on the chemosynthetic reaction pathways reveals that up to 8.3 kJ m⁻² d⁻¹ or 96 mW m⁻² of catabolic (Gibbs) energy is dissipated at the seep through oxidation reactions. The microorganisms mediating sulfide oxidation and anaerobic oxidation of methane (AOM) produce 95% and 2% of this energy flux, respectively. The low power output by AOM is due to strong bioenergetic constraints imposed on the reaction rate by the composition of the chemical environment. These constraints provide a high potential for dissolved methane efflux from the sediment (12.0 mmol m⁻² d⁻¹) and indicates a much lower efficiency of (dissolved) methane sequestration by AOM at seeps than considered previously. Nonetheless, AOM is able to consume a third of the ascending methane flux (5.9 mmol m⁻² d⁻¹ of CH₄) with a high efficiency of energy expenditure (35 mmol CH₄ kJ⁻¹). It is further proposed that bioenergetic limitation of AOM provides an explanation for the non-zero sulfate concentrations below the AOM zone observed here and in other active and passive margin sediments.     

Resistance of Lophelia pertusa to coverage by sediment and petroleum drill cuttings

In laboratory experiments, the cold-water coral Lophelia pertusa was exposed to settling particles. The effects of reef sediment, petroleum drill cuttings and a mix of both, on the development of anoxia at the coral surface were studied using O₂, pH and H₂S microsensors and by assessing coral polyp mortality. Due to the branching morphology of L. pertusa and the release of coral mucus, accumulation rates of settling material on coral branches were low. Microsensors detected H₂S production in only a few samples, and sulfate reduction rates of natural reef sediment slurries were low (<0.3 nmol S cm⁻³ d⁻¹). While the exposure to sediment clearly reduced the coral’s accessibility to oxygen, L. pertusa tolerated both partial low-oxygen and anoxic conditions without any visible detrimental short-term effect, such as tissue damage or death. However, complete burial of coral branches for >24 h in reef sediment resulted in suffocation.     

Segmented seismicity of the M w 6.2 Baladeh earthquake sequence (Alborz Mountains, Iran) revealed from regional moment tensors

The M _w 6.2 Baladeh earthquake occurred on 28 May 2004 in the Alborz Mountains, northern Iran. This earthquake was the first strong shock in this intracontinental orogen for which digital regional broadband data are available. The Baladeh event provides a rare opportunity to study fault geometry and ongoing deformation processes using modern seismological methods. A joint inversion for hypocentres and a velocity model plus a surface-wave group dispersion curve analysis were used to obtain an adapted velocity model, customised for mid- and long-period waveform modelling. Based on the new velocity model, regional waveform data of the mainshock and larger aftershocks (M _w ?≥3.3) were inverted for moment tensors. For the Baladeh mainshock, this included inversion for kinematic parameters. All analysed earthquakes show dominant thrust mechanisms at depths between 14 and 26 km, with NW–SE striking fault planes. The mainshock ruptured a 28° south-dipping area of 24 × 21 km along a north-easterly direction. The rupture plane of the mainshock does not coincide with the aftershock distribution, neither in map view nor with respect to depth. The considered aftershocks form two main clusters. The eastern cluster is associated with the mainshock. The western cluster does not appear to be connected with the rupture plane of the mainshock but, instead, indicates a second activated fault plane dipping at 85° towards the north.