Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts

Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO₂) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Zn²⁺) and Cu²⁺/Cu⁺ with increasing fO₂ between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO₂ implies a reciprocal relationship between a(Fe²⁺O) and a(Fe³⁺O_1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO₂ in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO₂ in silicic, but less so in mafic bulk systems.     

Characterizing site response in the Attock Basin,Pakistan, using microtremor measurement analysis

The Attock Basin is situated close to the northwest of Pakistan. Recent seismic event of October 2015 (7.5M_w) near the Pakistan Afghanistan border has proved that the area of interest is seismically active and triggered a series of aftershocks of magnitude even greater than 6.5M_w. This seismic activity has posed danger to the future of the people and infrastructure especially to the northwestern part of the country. Therefore, site response analysis is essential for estimating local site conditions in response to seismic events. Ambient noise recordings were made at 50 sites within urban and semi-urban settlements in the Attock Basin to analyze the site response of the small but densely populated basin. At each of these sites, the fundamental frequency of the soft sediments (f ₀), the amplitude (A ₀) of corresponding H/V spectral ratios, the thickness of soft sediment (H) lying over competent lithology, and the soil vulnerability index (K _g) were studied. Results were correlated with sparsely available borehole data to enhance the credibility of the study conducted for microzonation and predicting the site response to earthquake seismicity in the Attock Basin. The soil vulnerability index was found to range from moderate to high. Results clearly showed that the study area exhibits low to moderate fundamental frequency with greater soft sediment thicknesses distributed throughout the study area. Moreover, higher impedance contrasts were found at most of the sites within the central part of the Attock Basin, thus reflecting a moderate to high susceptibility of damage in those regions in response to seismic events.     

Assessing the bioaugmentation potentials of individual isolates from landfill on metal-polluted soil

Heavy metals from leachate are persistent pollutants in soil, especially when landfills lack liners and basic structural system that prevents overflow of leachate beyond restricted areas. It is not ideal to rely only on physical and chemical options for the reclamation/restoration of such contaminated soil. Therefore, it is imperative to adopt bioremediation through the enhancement of microbial potentials. The present study investigated the use of individual isolates for the remediation of soil contaminated by leachate-metals. This is a way to understand the discrete potentials of the gram-positive bacteria species. Environmental isolates taken from contaminated soil were used to remedy soil characterized with various concentrations of metals (Al, Cd, Cr, Fe, Ni, Pb and Zn). Treatments A, B, and C amended with Bacillus sp., Lysinibacillus sp., and Rhodococcus sp., respectively, demonstrated better metal reduction potentials than the control experiment (Treatment D; zero microbial amendment) that depended solely on natural attenuation. With the exception of Ni, the degree of reduction of other metals was less than 50% for all treatments. This study suggests that such result reflects the potential ability of the microbes to metabolize selectively in the presence of metal pollution. However, it is difficult for the individual microbes to attain higher metal reduction efficiency (above 50%) except when blended in the appropriate formulation.     

A simulation study of capillary transport,preferential retention and distribution of salts in historic sandstone buildings

Salt crystallisation is a major problem of deterioration in historic stone buildings, monuments and sculptures. The capillary rise of soil water is one of the primary sources of salts in stone structures, which evaporates leaving the salts behind. It has been noted that the spatial distribution profile of different species of salts crystallised in historic stone buildings is not homogeneous, i.e. different salts crystallise at different locations. The capillary transport and inhomogeneous spatial distribution of different salts in the porous building materials has been considered to be a result of solubility-dependent crystallisation; however, the factors responsible for this phenomenon are not clearly known. This paper aims to investigate the factors influencing the differential distribution of salts during capillary rise of soil water. In this study, the capillary transport of salts was simulated on two different sandstones—Locharbriggs, a Permo–Triassic, red sandstone and Stoke Hall, a Carboniferous, buff sandstone. The experiments were carried out under controlled environmental conditions to eliminate the possibility of evaporation-driven crystallisation of salts depending on their solubilities. The results indicate that fractionation or differential distribution of salts takes place even in the absence of evaporation and crystallisation. The sandstones exhibit properties like an ion exchange column, and ionic species present in the salt solution show differential distribution within the porous network of sandstone.     

A Middle Ordovician cephalopod fauna from Cuzco Province,southern Perú and its palaeobiogeographical significance

A small cephalopod assemblage collected during the 1930s by J. A. Douglas from the Middle Ordovician San José Formation of Cuzco Province is redescribed. Although small in number (four taxa) and poorly preserved, this assemblage contains a representative of the ellesmerocerid family Eothinoceratidae and a probable member of the Arionoceratidae (Orthocerida). One taxon may be closely related to Protocycloceras harringtoni Cecioni from northern Argentina. The presence of a particular group of eothinoceratids, here and elsewhere in South America indicate a link with western Gondwana. The relatively diminutive size of the arionoceratids suggests homeomorphy with those Silurian forms associated with a pelagic habitat and indicates a relatively offshore site for this assemblage. Copyright © 2006 John Wiley & Sons, Ltd.     

Geochemistry of Flooded Underground Mine Workings Influenced by Bacterial Sulfate Reduction

Unlike the majority of the water in the flooded mine complex of Butte Montana, which includes the highly acidic Berkeley pit lake, groundwater in the flooded West Camp underground mine workings has a circum-neutral pH and contains at least 8 μM aqueous sulfide. This article examines the geochemistry and stable isotope composition of this unusual H₂S-rich mine water, and also discusses problems related to the colorimetric analysis of sulfide in waters that contain FeS_(aq) cluster compounds. The West Camp mine pool is maintained at a constant elevation by continuous pumping, with discharge water that contains elevated Mn (90 μM), Fe (16 μM), and As (1.3 μM) but otherwise low metal concentrations. Dissolved inorganic carbon in the mine water is in chemical and isotopic equilibrium with rhodochrosite in the mineralized veins. The mine water is under-saturated with mackinawite and amorphous FeS, but is supersaturated with Cu- and Zn-sulfides. However, voltammetry studies show that much of the dissolved sulfide and ferrous iron are present as FeS_(aq) cluster molecules: as a result, the free concentration of the West Camp water is poorly constrained. Concentrations of dissolved sulfide determined by colorimetry were lower than gravimetric assays obtained by AgNO₃ addition, implying that the FeS_(aq) clusters are not completely extracted by the Methylene Blue reagent. In contrast, the clusters are quantitatively extracted as Ag₂S after addition of AgNO₃. Isotopic analysis of co-existing aqueous sulfide and sulfate confirms that the sulfide was produced by sulfate-reducing bacteria (SRB). The H₂S-rich mine water is not confined to the immediate vicinity of the extraction well, but is also present in flooded mine shafts up to 3 km away, and in samples bailed from mine shafts at depths up to 300 m below static water level. This illustrates that SRB are well established throughout the southwestern portion of the extensive (>15 km³) Butte flooded mine complex.     

Large-scale Mechanical Redistribution of Orthopyroxene and Plagioclase in the Basement Sill, Ferrar Dolerites, McMurdo Dry Valleys, Antarctica: Petrological, Mineral-chemical and Field Evidence for Channelized Movement of Crystals and Melt

The Jurassic Ferrar dolerite sills of the McMurdo Dry Valleys,Antarctica represent the plumbing system for flood basalt eruptionsassociated with the breakup of Gondwana. Among the Ferrar sills,the 350–450 m thick cumulate-textured Basement Sill isdifferentiated into a Lower Marginal Zone (LMZ) gabbronorite,a thick Lower Zone (LZ) orthopyroxene–plagioclase orthocumulatepyroxenite, a strongly layered mela- to leuco-gabbronorite MiddleZone (MZ), a thick Upper Zone (UZ) gabbronorite with ferrogabbroicpods, and an Upper Marginal Zone (UMZ) gabbronorite. Texturesand mineral compositions in the LZ pyroxenite and MZ–UZgabbronorites are nearly identical, the main distinction beingthe greater relative proportion of plagioclase in the MZ–UZgabbronorites, and of pigeonite in the UZ. Most orthopyroxenein the LZ, MZ and UZ occurs as sub-euhedral, normally zonedprimocrysts, commonly with rounded plagioclase inclusions. Plagioclaseis usually sub-euhedral and normally zoned, but can containsodic cores interpreted to be xenocrystic. Orthopyroxene andfeldspar compositions thoughout the sill are generally fairlyuniform, and resemble the compositions of micro-phenocrystsin the chilled margins. We infer that the sill was filled bya c. 1250°C slurry of orthopyroxene + plagioclase phenocrystsor primocrysts that subsequently unmixed in response to buoyancyforces. The LZ websterite contains numerous anorthosite to gabbronoriteschlieren, veins and pipes (< 2 m diameter), which we interpretas fossil segregation channels. Textures and mineral compositionsin these felsic channels are very similar both to UZ and MZgabbronorites, and to the groundmass separating accumulatedorthopyroxene primocrysts in the LZ and MZ. We infer that plagioclase-charged,hydrous pore melt from the pyroxenite may have segregated, pooledand ascended through these conduits to feed growth of the UZgabbronorite. Detailed mapping shows that the pipes are separatedby about 15 m on average. Calculations suggest that this numberdensity of conduits could have drained the LZ cumulates of theirinterstitial melt + plagioclase in about 8 days. Sequences (eachc. 5–10 m thick) of layered leuco-gabbronorite in theMZ could represent intra-cumulate sills that formed from plagioclase-richslurries ascending in segregation channels. Fe–Ti-richpyroxenitic veins and pods (some pegmatitic) and an unusualcoarse-grained plagioclase facies occur at the contacts betweenmassive leuco-gabbronorite layers in the MZ. Discordant ferro-pegmatitepods and dykes occur throughout the UZ. We interpret these Fe-richpegmatoidal rocks as evolved residual melts expelled from thecompacting gabbronoritic cumulates of the MZ and UZ. KEY WORDS: Ferrar; cumulates; differentiation; Antarctica; layering     

Tides and mixing in the northwestern East China Sea Part I: Rotating and reversing tidal flows

Bottom-mounted ADV and ADCP instruments in combination with CTD profiling measurements taken along the Chinese coast of the East China Sea were used to study the vertical structure of temperature, salinity, and velocity in reversing tidal currents on a shallow inner shelf and in rotating tidal flows over a deeper sloping bottom of the outer shelf. These two regimes of barotropic tide affect small-scale dynamics in the lower part of the water column differently. The reversing flow was superimposed by seiches of ∼2.3 h period generated in semienclosed Jiaozhou Bay located nearby. As the tidal vector rotates over the sloping bottom, the height of the near-bottom logarithmic layer is subjected to tidal-induced variations. A maximum of horizontal velocity U_max appears at the upper boundary of the log layer during the first half of the current vector rotation from the minor to the major axis of tidal ellipse. In rotating tidal flow, vertical shear generated at the seafloor, propagated slowly to the water interior up to the height of U_max, with a phase speed of ∼5 m/h. The time-shifted shear inside the water column, relative to the shear at the bottom, was associated with periodically changing increases and decreases of the tidal velocity above the log layer toward the sea surface. In reversing flows, the shear generated near the bottom and the shear at the upper levels were almost in phase.     

Reprint of “Multi-step and two-step experiments in heterogeneous porous media to evaluate the relevance of dynamic effects”

The determination of hydraulic properties in non-stationary experiments is suspected to be affected by dynamic effects. This is based on thermodynamic considerations on the pore scale displacement of wetting and non-wetting phase. But also macroscopic heterogeneities at the continuum scale may influence the dynamics of water during drainage and wetting. In this paper we investigate both aspects. Firstly, we present the results of typical multi-step outflow experiments in heterogeneous sand columns which are compared with two-step outflow experiments covering the same pressure range. The discrepancies caused by pressure steps of different size reveal the impact of dynamic effects due to the non-stationarity of the experiments.