Influence of Redox Mediators and Electron Donors on the Anaerobic Removal of Color and Chemical Oxygen Demand from Textile Effluent

Color removal was evaluated in anaerobic assays using synthetic (SE) and real (RE) effluents containing the dye Direct Black 22 (DB22). The focus was on the individual influence of two electron donors (EDs), sucrose and ethanol; and their combination with two redox mediators (RMs), lawsone and riboflavin. In addition to SE assays, the EDs were combined with sulfate which was present in the RE. Distinct behavior was observed with both assays. In the case of SE, using the EDs sucrose and ethanol resulted in DB22 removal efficiency of 93 and 83%, respectively; but only 27% in the control. The respective removal rates were 27.8‐ and 4.4‐fold higher than that of the control. Using the EDs with the RM lawsone resulted in color removal higher than that with riboflavin. Interestingly, in the ethanol + sulfate assay, late release of the last was observed, possibly due to the desulfonation reaction of the aromatic structures during the DB22 molecule breakdown. In the case of RE, no improvement was observed with either EDs; and some combinations with the RMs even resulted in decreased color removal. Therefore, the used EDs and RMs showed positive effect on color removal in SEs; but unexpectedly not in REs.     

The early Miocene (~25 Ma) volcanism in the northern Kyushu-Palau Ridge,enriched mantle source injection during rifting prior to the Shikoku backarc basin opening

The northern Kyushu-Palau Ridge (KPR), remnant conjugate arc of the Izu-Ogasawara (Bonin)-Mariana (IBM) active arc, is dominated by basalt-andesite except for the Komahashi-Daini Seamount where acidic plutonic rocks of 38 Ma were recovered. These mafic to intermediate volcanics are produced by the rifting volcanism in the proto-IBM arc associated with spreading of the Shikoku Basin. The HFSE and HREE contents and ratios of these volcanics indicate enriched source mantle composition compared to recent volcanic front. The LILE ratios exhibit similar characteristics to reararc volcanism of the recent Izu arc, and some enriched volcanics exhibit high abundance of sediment melt inputs. Based on these observations and compilations of the published data set, the replacement event of the wedge mantle under the IBM arc occurred two times. The first event occurred between 45 and 38 Ma, with Pacific type mantle being replaced by depleted Indian type mantle. The second event occurred between 36 and 25 Ma, enriched mantle flowed from reararc side. The slab component during the proto-IBM arc rifting was a similar characteristic to recent reararc volcanism of the Izu arc, and sediment melt added in a local area.     

A comparative study of the modelling of cement hydration and cement-rock laboratory experiments

The use of cement and concrete as fracture grouting or as tunnel seals in a geological disposal facility for radioactive wastes creates potential issues concerning chemical reactivity. From a long-term safety perspective, it is desirable to be able model these interactions and changes quantitatively. The ‘Long-term Cement Studies’ (LCS) project was formulated with an emphasis on in situ field experiments with more realistic boundary conditions and longer time scales compared with former experiments. As part of the project programme, a modelling inter-comparison has been conducted, involving the modelling of two experiments describing cement hydration on one hand and cement-rock reaction on the other, with teams representing the NDA (UK), Posiva (Finland), and JAEA (Japan).This modelling exercise showed that the dominant reaction pathways in the two experiments are fairly well understood and are consistent between the different modelling teams, although significant differences existed amongst the precise parameterisation (e.g. reactive surface areas, dependences of rate upon pH, types of secondary minerals), and in some instances, processes (e.g. partition of alkali elements between solids and liquid during cement hydration; kinetic models of cement hydration). It was not conclusive if certain processes such as surface complexation (preferred by some modellers, but not by others) played a role in the cement-rock experiment or not. These processes appear to be more relevant at early times in the experiment and the evolution at longer timescales was not affected. The observed permeability profile with time could not be matched. The fact that no secondary minerals could be observed and that the precipitated mass calculated during the simulations is minor might suggest that the permeability reduction does not have a chemical origin, although a small amount of precipitates at pore throats could have a large impact on permeability.The modelling exercises showed that there is an interest in keeping the numerical models as simple as possible and trying to obtain a reasonable fit with a minimum of processes, minerals and parameters. However, up-scaling processes and model parameterisation to the timescales appropriate to repository safety assessment are of considerable concern. Future modelling exercises of this type should focus on a suitable natural or industrial analogue that might aid assessing mineral-fluid reactions at these longer timescales.     

Cathodoluminescence of high-pressure feldspar minerals as a shock barometer

Cathodoluminescence (CL) analyses were carried out on maskelynite and lingunite in L6 chondrites of Tenham and Yamato-790729. Under CL microscopy, bright blue emission was observed in Na-lingunite in the shock veins. Dull blue-emitting maskelynite is adjacent to the shock veins, and aqua blue luminescent plagioclase lies farther away. CL spectroscopy of the Na-lingunite showed emission bands centered at ~330, 360–380, and ~590 nm. CL spectra of maskelynite consisted of emission bands at ~330 and ~380 nm. Only an emission band at 420 nm was recognized in crystalline plagioclase. Deconvolution of CL spectra from maskelynite successfully separated the UV–blue emission bands into Gaussian components at 3.88, 3.26, and 2.95 eV. For comparison, we prepared K-lingunite and experimentally shock-recovered feldspars at the known shock pressures of 11.1–41.2 GPa to measure CL spectra. Synthetic K-lingunite has similar UV–blue and characteristic yellow bands at ~550, ~660, ~720, ~750, and ~770 nm. The UV–blue emissions of shock-recovered feldspars and the diaplectic feldspar glasses show a good correlation between intensity and shock pressure after deconvolution. They may be assigned to pressure-induced defects in Si and Al octahedra and tetrahedra. The components at 3.88 and 3.26 eV were detectable in the lingunite, both of which may be caused by the defects in Si and Al octahedra, the same as maskelynite. CL of maskelynite and lingunite may be applicable to estimate shock pressure for feldspar-bearing meteorites, impactites, and samples returned by spacecraft mission, although we need to develop more as a reliable shock barometer.     

Implications for behavior of volatile elements during impacts—Zinc and copper systematics in sediments from the Ries impact structure and central European tektites

Moldavites are tektites genetically related to the Ries impact structure, located in Central Europe, but the source materials and the processes related to the chemical fractionation of moldavites are not fully constrained. To further understand moldavite genesis, the Cu and Zn abundances and isotope compositions were measured in a suite of tektites from four different substrewn fields (South Bohemia, Moravia, Cheb Basin, Lusatia) and chemically diverse sediments from the surroundings of the Ries impact structure. Moldavites are slightly depleted in Zn (~10–20%) and distinctly depleted in Cu (>90%) relative to supposed sedimentary precursors. Moreover, the moldavites show a wide range in δ⁶⁶Zn values between 1.7 and 3.7‰ (relative to JMC 3‐0749 Lyon) and δ⁶⁵Cu values between 1.6 and 12.5‰ (relative to NIST SRM 976) and are thus enriched in heavy isotopes relative to their possible parent sedimentary sources (δ⁶⁶Zn = ?0.07 to +0.64‰; δ⁶⁵Cu = ?0.4 to +0.7‰). In particular, the Cheb Basin moldavites show some of the highest δ⁶⁵Cu values (up to 12.5‰) ever observed in natural samples. The relative magnitude of isotope fractionation for Cu and Zn seen here is opposite to oxygen‐poor environments such as the Moon where Zn is significantly more isotopically fractionated than Cu. One possibility is that monovalent Cu diffuses faster than divalent Zn in the reduced melt and diffusion will not affect the extent of Zn isotope fractionation. These observations imply that the capability of forming a redox environment may aid in volatilizing some elements, accompanied by isotope fractionation, during the impact process. The greater extent of elemental depletion, coupled with isotope fractionation of more refractory Cu relative to Zn, may also hinge on the presence of carbonyl species of transition metals and electromagnetic charge, which could exist in the impact‐induced high‐velocity jet of vapor and melts.     

Bulk density effects on soil hydrologic and thermal characteristics: A numerical investigation

Soil bulk density (ρ_b) is commonly treated as static in studies of land surface dynamics. Magnitudes of errors associated with this assumption are largely unknown. Our objectives were to (a) quantify ρ_b effects on soil hydrologic and thermal properties and (b) evaluate effects of ρ_b on surface energy balance and heat and water transfer. We evaluated 6 soil properties, volumetric heat capacity, thermal conductivity, soil thermal diffusivity, water retention characteristics, hydraulic conductivity, and vapour diffusivity, over a range of ρ_b, using a combination of 6 models. Thermal conductivity, water retention, hydraulic conductivity, and vapour diffusivity were most sensitive to ρ_b, each changing by fractions greater than the associated fractional changes in ρ_b. A 10% change in ρ_b led to 10–11% change in thermal conductivity, 6–11% change in saturated and residual water content, 49–54% change in saturated hydraulic conductivity, and 80% change in vapour diffusivity. Subsequently, 3 field seasons were simulated with a numerical model (HYDRUS‐1D) for a range of ρ_b values. When ρ_b increased 25% (from 1.2 to 1.5 Mg m^?3), soil temperature variation decreased by 2.1 °C in shallow layers and increased by 1 °C in subsurface layers. Surface water content differed by 0.02 m³ m^?3 for various ρ_b values during drying events but differences mostly disappeared in the subsurface. Matric potential varied by >100 m of water. Surface energy balance showed clear trends with ρ_b. Latent heat flux decreased 6%, sensible heat flux increased 9%, and magnitude of ground heat flux varied by 18% (with a 25% ρ_b increase). Transient ρ_b impacted surface conditions and fluxes, and clearly, it warrants consideration in field and modelling investigations.     

Layout design of rockbolts for natural ground reinforcement

The present study addresses a layout design of rockbolts for reinforcing natural ground structures applying a special optimization method, called multiphase layout optimization. Rockbolts are used to tighten loosed natural ground, and the layout of rockbolts are determined without sufficient information about the physical properties of the ground materials. Because of this uncertainty, unexpected deformation often occurs at the excavation surface of natural ground. In that case, it is requested to determine an effective layout of the additional rockbolts promptly with respect to the actual deformation at the construction site. However, it is not easy to determine the optimal layout because of its complexity, and consequently, it has no choice but to determine the layout in an empirical way. This study introduces a numerical approach to determine an optimal layout of rockbolts with respect to arbitrarily possible deformation of natural ground. The objective is to maximize the stiffness of the overall ground structure reinforced with rockbolts. For optimization, a gradient‐based optimization scheme is applied because of its numerical efficiency. It was verified from a series of numerical examples that this method has great potential to improve the stiffness of the overall ground structure and shows a certain applicability to a practical design. Copyright © 2013 John Wiley & Sons, Ltd.     

Late Paleozoic serpentinites and mafic schists from the Coast Range accretionary complex,central Chile: their relation to aeromagnetic anomalies

Regional structural trends within the poorly exposed metamorphic basement complex of central Chile between 39°30' and 41°30'S latitudes are evident on total intensity aeromagnetic maps. Field and laboratory measurements of magnetic susceptibility indicate that anomalies are related to relic magnetite and rare ilmenite phase concentrations in serpentinites and lower greenschist facies mafic schists.Serpentinites and mafic schists representing fragmented ophiolites are common throughout a broad, highly magnetic central zone which separates a low-magnetic metaturbidites terrain in the Northeast from a southwestern, low susceptibility, metavolcanic rich area with isolated anomalies. One of the isolated anomalies represents a polyphase deformed serpentinite emplacement overlain by coarse grained eclogitic blueschist, highly magnetic undeformed serpentinites and amphibolite boulders thought to have been transported within the ultramafic body.The trend of the regional magnetic anomaly pattern is controlled by the main foliation, a crenulation cleavage (S2), rather than by primary factors, such as emplacement pattern of the ultramafics. This structural grain was established during the early Carboniferous event which culminated pre-Andean accretion in the area. The overall zonation, however, seems to reflect the composition of slices in a composite prism accreted during oblique subduction along the margin of Gondwanaland.

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Zusammenfassung Reliktische präkinematische (prä-S2) Magnetitanreicherungen kommen in Serpentiniten und Metabasiten der Grünschieferfazies des spätpaläozoischen Grundgebirges der Küstenkordillere Chiles häufig vor. Zwischen 39°30' und 41 °30' südlicher Breite wurden magnetische Messungen in situ in diesen Gesteinen durchgeführt, die deren enge räumliche Beziehung zu regionalen NW-SO streichenden Anomalien bestätigen.Die Serpentinite stellen Teile eines zerscherten Ophiolithkomplexes dar, der zwischen einer schwach-magnetischen Metaturbidit-Zone und einer schlecht aufgeschlossenen Metapyroklastit-Zone diapirartig intrudierte. Ein mehrfach deformierter Serpentinitkörper ist von Gerollen aus eklogitischem Blauschiefer überlagert, die höchstwahrscheinlich ursprünglichen tektonischen Einschlüssen entsprechen.Der regionale Trend der Anomalien ist eher vom Streichen und Einfallen der Hauptschieferung als von primären Strukturen kontrolliert. Es handelt sich um eine Krenulationsschieferung (S2) die durch eine frühkarbonische Phase entstanden ist. Sie stellt den Höhepunkt einer prä-Andinen Schrägakkretion dar. Die regionale lithologische Gliederung scheint jedoch die Zusammensetzung der einzelnen Akkretionskeile widerzuspiegeln.

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Résumén Serpentinitas y esquistos máficos metamorfizados en condiciones de facies esquistos verdes baja forman parte del basamento metamorfico de la Cordillera de la Costa de Chile central entre los 39°30' y los 41°30'l.s. Mediciones in situ y en laboratorio de suceptibilidad magnética muestran que sus concentraciones de magnetita pretectonica con respecto a la foliación principal son responsables de anomalías de rumbo NW-SE.Las serpentinitas constituyen parte de una asociación »ofiolítica« fragmentada que aflora dentro de una ancha banda entre metaturbiditas débilmente magnéticas al NE y metapiroclastitas con aisladas anomalías al SW. Una serpentinita del último sector presenta evidencias de deformación polifásica y esta recubierta por bolones de esquistos azules eclogíticos y anfibolitas, los cuales podrían representar inclusiones originalmente transportadas por el cuerpo ultramáfico.El diseño regional de las anomalías magnéticas está controlado por la actitud de la foliación principal, más que por el diseño del emplazamiento original. Esta, un clivaje de crenuación S2, se originó durante un evento carbonífero temprano que representa el climax de la acreción pre-andina en el área. La zonación litológica regional, sin embargo, parece reflejar más bien la composición de lonjas individuales dentro de un prisma compuesto acrecionado mediante subducción oblicua.

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- (prä-S2) . 39°30 41°30 in situ , , NW-SO. , , . , , , , , . , . (S2), . - . .

     

Effect of divalent cations on the kinetics of Fe(III) complexation by organic ligands in natural waters

We have investigated the kinetics of Fe(III) complexation by several organic ligands including fulvic acid, citrate and ethylenediaminetetraacetic acid (EDTA). Particular attention was given to examination of the effect of competitive divalent cations (Me: Ca²⁺ and Mg²⁺) at concentrations typical of seawater on the complexation rate. All experiments were conducted in 0.5 M NaCl solution buffered with 2 mM bicarbonate at pH 8.0 in the absence and presence of Me (25 μM-250 mM). The rate constants of complex formation determined by using the competitive ligand (5-sulfosalicylic acid) method combined with visible spectrophotometry ranged from 3.3 × 10⁴ to 3.2 × 10⁶ M⁻¹ s⁻¹. The mechanism of complexation was then examined based on a kinetic model. When EDTA was used as a ligand, Me at concentrations comparable to the ligand markedly retarded the rate of iron complex formation due to the predominance of an adjunctive pathway (where iron-ligand complex is formed via direct association of iron to Me-ligand complex). In contrast, the competing effect of Me on iron complexation by citrate and fulvic acid was observed only when the Me concentration was in excess of the ligand by more than a factor of 10-1000. The kinetic model suggests that iron complexation by fulvic acid occurs predominantly via a disjunctive pathway (where iron complexation by ligand occurs after dissociation of Me from Me-ligand complex) at concentrations of divalent cations and natural organic matter typical of natural waters including seawater and freshwater.