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)

Multi-epoch intra-night optical monitoring of 8 radio-quiet BL Lac candidates

For a new sample of 8 weak-line-quasars (WLQs) we report a sensitive search in 20 intranight monitoring sessions, for blazar-like optical flux variations on hour-like and longer time scale (day/month/year$-$like). The sample consists exclusively of the WLQs that are not radio$-$loud and have either been classified as `radio-weak probable BL Lac candidates' and/or are known to have exhibited at least one episode of large, blazar$-$like optical variability. Whereas only a hint of intra$-$night variability is seen for two of these WLQs, J104833.5$+$620305.0(z = 0.219) and J133219.6$+$622715.9 (z = 3.15), statistically significant inter$-$night variability at a few per cent level is detected for three of the sources, including the radio-intermediate WLQ J133219.6$+$622715.9 (z = 3.15) and the well known bona$-$fide radio$-$quiet WLQs J121221.5$+$534128.0 (z = 3.10) and WLQ J153259.9$-$003944.1 (z = 4.62). In the rest$-$frame, this variability is intra-day and in the far$-$UV band. On the time scale of a decade, we find for three of the WLQs large brightness changes, amounting to 1.655$\pm$0.009, 0.163$\pm$0.010 and 0.144$\pm$0.018 mag, for J104833.5$+$620305.0, J123743.1$+$630144.9 and J232428.4$+$144324.4, respectively. Whereas the latter two are confirmed radio-quiet WLQs, the extragalactic nature of J104833.5$+$620305.0 remains to be well established, thanks to the absence of any feature(s) in its available optical spectra. The present study forms a part of our ongoing campaign of intranight optical monitoring of radio quiet weak-line quasars, in order to improve the understanding of this enigmatic class of Active Galactic Nuclei and to look among them for a possible tiny, elusive population of radio-quiet BL Lacs.Comment: Accepted to MNRAS. 12 pages, 1 figure, 4 Tabl

MULTILATERAL GOVERNANCE OF FISHERIES: MANAGEMENT AND COOPERATION IN THE WESTERN AND CENTRAL PACIFIC TUNA FISHERIES

The tuna resources of the Western and Central Pacific are the world's largest and most valuable fisheries of their type and are of significant economic importance to the Pacific island countries through whose waters they migrate. Two major concerns exist with the current governance of this fishery. First, Pacific island countries receive only a small share of the resource rents from the tuna fisheries. Second, the current management structure of the fisheries will not ensure the long-term sustainability of the resources. This paper derives a model to show that the sustainability of the resource can be improved when a single policymaker acts as Stackelberg leader and sets a tax, or an equivalent quantity instrument, to maximize rents from the resource. A practical institutional mechanism is presented that mimics the model's rent maximization outcome and that offers substantial benefits to both Pacific island countries and distant water fishing nations.Resource /Energy Economics and Policy,

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

Limits on the time variation of the electromagnetic fine-structure constant in the low energy limit from absorption lines in the spectra of distant quasars

Most of the successful physical theories rely on the constancy of few fundamental quantities (such as the speed of light, $c$, the fine-structure constant, \alpha, the proton to electron mass ratio, \mu, etc), and constraining the possible time variations of these fundamental quantities is an important step toward a complete physical theory. Time variation of \alpha can be accurately probed using absorption lines seen in the spectra of distant quasars. Here, we present the results of a detailed many-multiplet analysis performed on a new sample of Mg II systems observed in high quality quasar spectra obtained using the Very Large Telescope. The weighted mean value of the variation in \alpha derived from our analysis over the redshift range 0.4<z<2.3 is \Delta\alpha/\alpha = (-0.06+/-0.06) x 10^{-5}. The median redshift of our sample (z=1.55) corresponds to a look-back time of 9.7 Gyr in the most favored cosmological model today. This gives a 3\sigma limit, -2.5 x 10^{-16} yr^-1 <(\Delta\alpha/\alpha\Delta t) <+1.2x10^{-16} yr^-1, for the time variation of \alpha, that forms the strongest constraint obtained based on high redshift quasar absorption line systems.Comment: uses revtex, 4 pages 3 figures. Accepted for publication in Physical Review Letter

Probing the time-variation of the fine-structure constant: Results based on Si IV doublets from a UVES sample

We report a new constraint on the variation of the fine-structure constant based on the analysis of 15 Si IV doublets selected from a ESO-UVES sample. We find \Delta\alpha/\alpha = (+0.15+/-0.43) x 10^-5 over a redshift range of 1.59< z < 2.92 which is consistent with no variation in \alpha. This result represents a factor of three improvement on the constraint on \Delta\alpha/\alpha based on Si IV doublets compared to the published results in the literature. The alkali doublet method used here avoids the implicit assumptions used in the many-multiplet method that chemical and ionization inhomogeneities are negligible and isotopic abundances are close to the terrestrial value.Comment: 12 Pages, 7 figures. Accepted for publication in A&A. In addition to minor corrections an appendix is added in this revised versio

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