A potential application of sludge-based catalysts for the anaerobic bio-decolorization of tartrazine dye.

Two highly efficient (K2CO3/sludge carbon and ZnCl2/sludge carbon) solids were prepared by chemical addition following carbonization at 800 °C and were tested for anaerobic reduction of tartrazine dye in a continuous upflow packed-bed biological reactor, and their performance was compared to that of commercial activated carbon (CAC). The chemical and structural information of the solids was subjected to various characterizations in order to understand the mechanism for anaerobic decolorization, and efficiency for SBCZN800 and SBCPC800 materials was 87% and 74%, respectively, at a short space time (τ) of 2.0 min. A first-order kinetic model fitted the experimental points and kinetic constants of 0.40, 0.92 and 1.46 min(-1) were obtained for SBCZN800, SBCPC800 and CAC, respectively. The experimental results revealed that performance of solids in the anaerobic reduction of tartrazine dye can depend on several factors including chemical agents, carbonization, microbial population, chemical groups and surface chemistry. The Langmuir and Freundlich models are successfully described in the batch adsorption data. Based on these observations, a cost-effective sludge-based catalyst can be produced from harmful sewage sludge for the treatment of industrial effluents.

Intersystem crossing rates of S1 state keto-amino cytosine at low excess energy

The amino-keto tautomer of supersonic jet-cooled cytosine undergoes intersystem crossing (ISC) from the v = 0 and low-lying vibronic levels of its S1(¹ππ*) state. We investigate these ISC rates experimentally and theoretically as a function of S1 state vibrational excess energy Eexc. The S1 vibronic levels are pumped with a ~5 ns UV laser, the S1 and triplet state ion signals are separated by prompt or delayed ionization with a second UV laser pulse. After correcting the raw ISC yields for the relative S1 and T1ionization cross sections, we obtain energy dependent ISC quantum yields Q corr ISC =1% –5%. These are combined with previously measured vibronic state-specific decay rates, giving ISC rates kISC = 0.4–1.5 ⋅ 10⁹ s⁻¹, the corresponding S1⇝S0internal conversion (IC) rates are 30–100 times larger. Theoretical ISC rates are computed using SCS-CC2 methods, which predict rapid ISC from the S1; v = 0 state with kISC = 3 ⋅ 10⁹ s⁻¹ to the T1(³ππ*) triplet state. The surprisingly high rate of this El Sayed-forbidden transition is caused by a substantial admixture of ¹nOπ* character into the S1(¹ππ*) wave function at its non-planar minimum geometry. The combination of experiment and theory implies that (1) below Eexc = 550 cm⁻¹ in the S1 state, S1⇝S0internal conversion dominates the nonradiative decay with kIC ≥ 2 ⋅ 10¹⁰ s⁻¹, (2) the calculated S1⇝T1 (¹ππ*⇝³ππ*) ISC rate is in good agreement with experiment, (3) being El-Sayed forbidden, the S1⇝T1 ISC is moderately fast (kISC = 3 ⋅ 10⁹ s⁻¹), and not ultrafast, as claimed by other calculations, and (4) at Eexc ~ 550 cm⁻¹ the IC rate increases by ~50 times, probably by accessing the lowest conical intersection (the C5-twist CI) and thereby effectively switching off the ISC decay channels.

Volcanic terrain and the possible periglacial formation of "excess ice" at the mid-latitudes of Utopia Planitia, Mars

At the mid-latitudes of Utopia Planitia (UP), Mars, a suite of spatially-associated landforms exhibit geomorphological traits that, on Earth, would be consistent with periglacial processes and the possible freeze-thaw cycling of water. The suite comprises small-sized polygonally-patterned ground, polygon-junction and -margin pits, and scalloped, rimless depressions. Typically, the landforms incise a dark-toned terrain that is thought to be ice-rich. Here, we investigate the dark-toned terrain by using high resolution images from the HiRISE as well as near-infrared spectral-data from the OMEGA and CRISM. The terrain displays erosional characteristics consistent with a sedimentary nature and near-infrared spectra characterised by a blue slope similar to that of weathered basaltic-tephra. We also describe volcanic terrain that is dark-toned and periglacially-modified in the Kamchatka mountain-range of eastern Russia. The terrain is characterised by weathered tephra inter-bedded with snow, ice-wedge polygons and near-surface excess ice. The excess ice forms in the pore space of the tephra as the result of snow-melt infiltration and, subsequently, in-situ freezing. Based on this possible analogue, we construct a three-stage mechanism that explains the possible ice-enrichment of a broad expanse of dark-toned terrain at the mid-latitudes of UP: (1) the dark-toned terrain accumulates and forms via the regional deposition of sediments sourced from explosive volcanism; (2) the volcanic sediments are blanketed by atmospherically-precipitated (H2O) snow, ice or an admixture of the two, either concurrent with the volcanic-events or between discrete events; and, (3) under the influence of high obliquity or explosive volcanism, boundary conditions tolerant of thaw evolve and this, in turn, permits the migration, cycling and eventual formation of excess ice in the volcanic sediments. Over time, and through episodic iterations of this scenario, excess ice forms to decametres of depth. (C) 2015 Elsevier B.V. All rights reserved.