The chemistry of ultrasonic degradation of organic compounds

The destruction of toxic organic molecules using advanced oxidation processes (AOPs) is a potent tool for pollution control and environmental protection. Ultrasound is a convenient and effective method of generating hydroxyl radicals which is the key oxidant in AOPs. This review describes the use of ultrasound and associated chemical reactions, with and without additives, as a powerful means of remediating water contaminated with organic pollutants. After a brief introduction to ultrasound and sonochemistry, their application for the oxidation of polycyclic aromatic hydrocarbons, phenol and substituted phenols is considered. Next is the decomposition of chlorinated phenols, and other chlorinated organics, then removal of recalcitrant smaller organic molecules. A discussion follows of recent work that has investigated the effects of initial concentration of substrates; the use of different ultrasonic frequencies; the inclusion of oxidising species, inorganic particles, or salts and their contribution to enhanced degradation. Finally, brief comments are made on the status of ultrasound as an AOP treatment

Phenol degradation using 20, 300 and 520 kHz ultrasonic reactors with hydrogen peroxide, ozone and zero valent metals

The extent of phenol degradation by the advanced oxidation process in the presence of zero valent iron (ZVI) and zero valent copper (ZVC) was studied using 20, 300 and 520 kHz ultrasonic (US) reactors. Quantification of hydrogen peroxide has also been performed with an aim of investigating the efficacy of different sonochemical reactors for hydroxyl radical production. It has been observed that the 300 kHz sonochemical reactor has the maximum efficacy for hydroxyl radical production. Phenol degradation studies clearly indicate that degradation of phenol is intensified in the presence of the catalyst and hydrogen peroxide, which can be attributed to enhanced production of hydroxyl radicals in the system. Experimental data shows that with ZVI, when the reaction was subjected to 300 kHz, complete phenol removal and 37% TOC mineralization was achieved within 25 min, whereas, in the case of 20 kHz US treatment no phenol was detected after 45 min and 39% TOC mineralization was observed. This novel study also investigated the use of zero valent copper (ZVC) and results showed that with 20, 300 and 520 kHz ultrasonic rectors, phenol removal was 10–98%, however, the maximum TOC mineralization achieved was only 26%. A comparative study between hydrogen peroxide and ozone as a suitable oxidant for Fenton-like reactions in conjunction with zero valent catalysts showed that an integrated approach of US/Air/ZVC/H2O2 system works better than US/ZVC/O3 (the ZOO process)

Intensification of oxidation capacity using chloroalkanes as additives in hydrodynamic and acoustic cavitation reactors

The effect of the presence and absence of the chloroalkanes, dichloromethane (CH2Cl2), chloroform (CHCl3) and carbon tetrachloride (CCl4) on the extent of oxidation of aqueous I- to I3- has been investigated in (a) a liquid whistle reactor (LWR) generating hydrodynamic cavitation and (b) an ultrasonic probe, which produces acoustic cavitation. The aim has been to examine the intensification achieved in the extent of oxidation due to the generation of additional free radicals/oxidants in the reactor as a result of the presence of chloroalkanes. It has been observed that the extent of increase in the oxidation reaction is strongly dependent on the applied pressure in the case of the LWR. Also, higher volumes of the chloroalkanes favour the intensification and the order of effectiveness is CCl4> CHCl3 > CH2Cl2. However, the results with the ultrasonic probe suggest that an optimum concentration of CH2Cl2 or CHCl3 exists beyond which there is little increase in the extent of observed intensification. For CCl4, however, no such optimum concentration was observed and the extent of increase in the rates of oxidation reaction rose with the amount of CCl4 added. Stage wise addition of the chloroalkanes was found to give marginally better results in the case of the ultrasonic probe as compared to bulk addition at the start of the run. Although CCl4 is the most effective, its toxicity and carcinogenicity may mean that CH2Cl2 and CHCl3 offer a safer viable alternative and the present work should be useful in establishing the amount of chloroalkanes required for obtaining a suitable degree of intensification

Enhancement of the advanced Fenton process (Fe0/H2O2) by ultrasound for the mineralization of phenol

In this study, a successful mineralization of phenol was achieved by means of coupling zero-valent iron (ZVI) particles, hydrogen peroxide and a short input of ultrasonic irradiation. This short sono-advanced Fenton process (AFP) provided a better performance of ZVI in a subsequent silent degradation stage, which involves neither extra cost of energy nor additional oxidant. The short input of ultrasound (US) irradiation enhanced the activity of the Fe0/H2O2 system in terms of the total organic carbon (TOC) removal. Then, the TOC mineralization continued during the silent stage, even after the total consumption of hydrogen peroxide, reaching values of ca. 90% TOC conversions over 24 h. This remarkable activity is attributed to the capacity of the ZVI/iron oxide composite formed during the degradation for the generation of oxidizing radical species and to the formation of another reactive oxidant species, such as the ferryl ion. The modification of the initial conditions of the sono-AFP system such as the ultrasonic irradiation time and the hydrogen peroxide dosage, showed significant variations in terms of TOC mineralization for the ongoing silent degradation stage. An appropriate selection of operation conditions will lead to an economical and highly efficient technology with eventual large-scale commercial applications for the degradation organic pollutants in aqueous effluents

Enhancing Biodiesel Production from Soybean Oil Using Ultrasonics

Our objective was to determine the effect of ultrasonics on biodiesel production from soybean oil. In this study, ultrasonic energy was applied in two different modes: pulse and continuous sonication. Soybean oil was mixed with methanol and a catalytic amount of sodium hydroxide, and the mixture was sonicated at three levels of amplitude (60, 120, and 180 μmpp) in pulse mode (5 s on/25 s off). In the continuous mode, the same reaction mixture was sonicated at 120 μmpp for 15 s. The reaction was monitored for biodiesel yield by stopping the reaction at selected time intervals and analyzing the biodiesel content by thermogravimetric analysis (TGA). The results were compared to a control group, in which the same reactant composition was allowed to react at 60 °C for intervals ranging from 5 min to 1 h without ultrasonic treatment. It was observed that ultrasonic treatment resulted in a 96% by weight isolated yield of biodiesel in less than 90 s using the pulse mode, compared to 30−45 min for the unsonicated control sample with comparable yields (83−86%). In the pulse mode, the highest yield (96%) was obtained by sonicating the mixture at 120 μmpp amplitude. In the continuous sonication mode, the highest biodiesel yield was 86% by weight, which was obtained in 15 s

Thermogravimetric Quantification of Biodiesel Produced via Alkali Catalyzed Transesterification of Soybean oil

The aim of this study was to demonstrate the use of thermogravimetric analysis (TGA) as a potential screening method for monitoring biodiesel production by transesterification of soybean oil with methanol. Soybean oil and commercially available biodiesel were mixed in varying proportions by weight as standards. In addition, mixtures of different biodiesel/soybean oil ratios were also created by periodically interrupting base-catalyzed transesterification of soybean oil with methanol. The mixtures produced by both approaches were analyzed with TGA over a temperature range of 25−500 °C. The results were then compared with analytical data obtained by proton nuclear magnetic resonance spectroscopy (1H NMR spectroscopy), an industry standard for biodiesel quantification. It was found in the TGA experiments that a significant weight loss at ca. 150 °C correlated to the volatilization of biodiesel. The relative weight losses in both sets of mixtures correlated well to the proportion of biodiesel present in the transesterification samples, and the results from both analytical methods were in good agreement (±1.5%). Thus, TGA is a simple, convenient, and economical method for monitoring biodiesel production

Novel Characterization Method of Biodiesel Produced from Soybean Oil using Thermogravimetric Analysis

The aim of this study was to demonstrate thermogravimetric analysis (TGA) as a potential method for monitoring biodiesel production. Soybean oil and commercial biodiesel were mixed in different proportions by weight. Mixtures of different biodiesel/soybean oil ratios were also created by interrupting a base-catalyzed transesterification process for producing biodiesel at various times. The mixtures produced by both approaches were analyzed with TGA. The results were then compared with data obtained by proton nuclear magnetic resonance spectroscopy ( 1HNMR spectroscopy). The relative weight losses in both sets of mixtures we generated correlated well to the proportion of biodiesel present in the sample. The results from both analytical methods were in good agreement and within a deviation of 5%. Thus, TGA is a simple, convenient and economical method for monitoring biodiesel production

Bistability in the Tunnelling Current through a Ring of NN Coupled Quantum Dots

We study bistability in the electron transport through a ring of N coupled quantum dots with two orbitals in each dot. One orbital is localized (called b orbital) and coupling of the b orbitals in any two dots is negligible; the other is delocalized in the plane of the ring (called d orbital), due to coupling of the d orbitals in the neighboring dots, as described by a tight-binding model. The d orbitals thereby form a band with finite width. The b and d orbitals are connected to the source and drain electrodes with a voltage bias V, allowing the electron tunnelling. Tunnelling current is calculated by using a nonequilibrium Green function method recently developed to treat nanostructures with multiple energy levels. We find a bistable effect in the tunnelling current as a function of bias V, when the size N>50; this effect scales with the size N and becomes sizable at N~100. The temperature effect on bistability is also discussed. In comparison, mean-field treatment tends to overestimate the bistable effect.Comment: Published in JPSJ; minor typos correcte

Sismicità all’Etna dal 1989 al 2010: evidenze sull’evoluzione spazio-temporale dell’attività sismica

Il Monte Etna, uno dei più attivi vulcani basaltici tra i più monitorati al mondo, è sede di una notevole attività sismica e vulcanica. Esso è ubicato in Sicilia orientale in un complesso quadro geodinamico, dove le principali strutture tettoniche regionali giocano un ruolo chiave nei processi dinamici del vulcano. La sismicità dell’Etna si manifesta con un elevato rate di terremoti di bassa e moderata energia che, a volte, a causa dell’estrema superficialità della sorgente, provocano danni ai centri abitati prossimi all’area epicentrale. Il monitoraggio sistematico dell’attività sismica etnea è effettuato sin dal 1989, mediante una rete sismica locale permanente che nel tempo è stata oggetto di importanti miglioramenti. La prima configurazione di rete era costituita da circa 10 stazioni analogiche con sensori a corto periodo gestita dall’Istituto Internazionale di Vulcanologia (IIV-CNR). Nel 1994, una rete sismica costituita da circa 40 stazioni (analogiche con sensori a corto periodo) fu installata sull’Etna nell’ambito del Progetto Poseidon. Nel 2001, le reti gestite dall’IIV-CNR e dal Progetto Poseidon confluirono nell’Istituto Nazionale di Geofisica e Vulcanologia (INGV); attualmente la rete sismica, costituita da circa 50 stazioni digitali equipaggiate con sismometri broadband a tre componenti, è gestita dalla Sezione di Catania dell’INGV. Nel periodo 1989-1999, il catalogo dei terremoti risulta costituito da circa 2000 eventi con soglia di completezza per magnitudo pari a 2.0; dal 1999 ad oggi contiene circa 6000 terremoti con soglia di completezza per magnitudo 1.5. La capacità di detezione della rete è migliorata nel tempo permettendo di registrare e localizzare anche gli eventi meno energetici (M≥1.0). In questo lavoro, vengono presentati i caratteri predominanti della sismicità etnea negli ultimi 20 anni, con un maggiore dettaglio della distribuzione spazio-temporale della sismicità verificatasi dal 1999. L’analisi della attività sismica rappresenta un utile strumento per l’interpretazione delle dinamiche che hanno contraddistinto numerose ed importanti eruzioni (2001, 2002-03, 2004, 2006, 2008-09). In particolare, la variazione del rilascio energetico della sismicità ha contribuito in maniera significativa ad identificare i probabili processi geodinamici legati alla ricarica del sistema magmatico del vulcano. La distribuzione spaziale della sismicità ha consentito di evidenziare inoltre l’esistenza di diverse aree sismogenetiche caratterizzate da un differente rate sismico, profondità focali e cinematica delle strutture associate. Infine, osservando le caratteristiche della sismicità nel lungo periodo, differenti settori del vulcano sono risultati maggiormente attivi in relazione ai più importanti recenti eventi eruttivi

Bounds on the Complexity of Halfspace Intersections when the Bounded Faces have Small Dimension

We study the combinatorial complexity of D-dimensional polyhedra defined as the intersection of n halfspaces, with the property that the highest dimension of any bounded face is much smaller than D. We show that, if d is the maximum dimension of a bounded face, then the number of vertices of the polyhedron is O(n^d) and the total number of bounded faces of the polyhedron is O(n^d^2). For inputs in general position the number of bounded faces is O(n^d). For any fixed d, we show how to compute the set of all vertices, how to determine the maximum dimension of a bounded face of the polyhedron, and how to compute the set of bounded faces in polynomial time, by solving a polynomial number of linear programs