Comparison of hydroxyl radical formation in aqueous solutions at different ultrasound frequencies and powers using the salicylic acid dosimeter

Ultrasonic frequencies of 20 kHz, 382 kHz, 584 kHz, 862 kHz (and 998 kHz) have been compared with regard to energy output and hydroxyl radical formation utilising the salicylic acid dosimeter. The 862 kHz frequency inputs 6 times the number of Watts into water, as measured by calorimetry, with the other frequencies having roughly the same value under very similar conditions. A plausible explanation involving acoustic fountain formation is proposed although enhanced coupling between this frequency and water cannot be discounted. Using the salicylic acid dosimeter and inputting virtually the same Wattages it is established that 862 kHz is around 10% more efficient at generating hydroxyl radicals than the 382 kHz but both of these are far more effective than the other frequencies. Also, it is found that as temperature increases to 42 °C then the total dihydroxybenzoic acid (Total DHBA) produced is virtually identical for 382 kHz and 862 kHz, though 582 kHz is substantially lower, when the power levels are set at approximately 9 W for all systems. An equivalent power level of 9 W could not be obtained for the 998 kHz transducer so a direct comparison could not be made in this instance. These results have implications for the optimum frequencies chosen for both Advanced Oxidation Processes (AOPs) and organic synthesis augmented by ultrasound

The preparation of ketene dithioacetals and thiophenes from chloropyridines containing an active methylene group

The base catalysed reaction of carbon disulphide with the active methylene groups of chloropyridines 4 and 7, followed by alkylation with reagents which also contain active methylene groups, lead to ketene dithioacetals. Further reaction with base afforded highly substituted thiophenes

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)

A comparison of the use of vacuum metal deposition versus cyanoacrylate fuming for visualisation of fingermarks and grab impressions on fabrics

Both vacuum metal deposition (VMD) and cyanoacrylate fuming (CAF) are techniques used to visualise latent fingermarks on smooth non-porous surfaces such as plastic and glass. VMD was initially investigated in the 1970s as to its effectiveness for visualising prints on fabrics, but was abandoned when radioactive sulphur dioxide was found to be more effective. However, interest in VMD was resurrected in the 1990s when CAF was also used routinely. We now report on studies to determine whether VMD or CAF is the more effective technique for the detection of marks on fabrics. Four different fabrics, nylon, polyester, polycotton and cotton, were utilised during this study, along with 15 donors who ranged in their age and ability to leave fingermarks, from good to medium to poor, thus reflecting the general population. Once samples were collected they were kept for a determined time (1, 2, 3, 4, 5, 6, 7, 14, 21 or 28 days) and then treated using either the gold and zinc metal VMD process or standard cyanoacrylate fuming.The smoother fabrics, such as nylon, consistently produced greater ridge detail whereas duller fabrics, like cotton tended only to show empty prints and impressions of where the fabric had been touched, rather than any ridge details. The majority of fabrics did however allow the development of touch marks that could be targeted for DNA taping which potentially could lead to a DNA profile. Of the two techniques VMD was around 5 times more effective than CAF, producing a greater amount of ridge detail, palmar flexion creases and target areas on more samples and fabrics

Mineralisation of surfactants using ultrasound and the Advanced Fenton Process

The destruction of the surfactants, sodium dodecylbenzene sulfonate (DBS) and dodecyl pyridinium chloride (DPC), using an advanced oxidation process is described. The use of zero valent iron (ZVI) and hydrogen peroxide at pH = 2.5 (the advanced Fenton process), with and without, the application of 20 kHz ultrasound leads to extensive mineralisation of both materials as determined by total organic carbon (TOC)measurements. For DBS, merely stirring with ZVI and H2O2 at 20°C leads to a 51% decrease in TOC, but using 20 kHz ultrasound at 40°C, maintaining the pH at 2.5 throughout and adding extra amounts of ZVI and H2O2 during the degradation, then the extent of mineralisation of DBS is substantially increased to 93%. A similar result is seen for DPC where virtually no degradation occurs at 20°C, but if extra amounts of both ZVI and hydrogen peroxide are introduced during the reaction at 40°C and the pH is maintained at 2.5, then an 87% mineralisation of DPC is obtained. The slow latent remediation of both surfactants and the mechanism of degradation are also discussed

Mineralisation of 2,4-dichlorophenoxyacetic acid by acoustic or hydrodynamic cavitation in conjunction with the advanced Fenton process

The mineralisation of 2,4-dichlorophenoxyacetic acid (2,4-D) in the presence of zero-valent iron and hydrogen peroxide (the Advanced Fenton process – AFP) whilst being subjected to acoustic or hydrodynamic cavitation is reported. If the reaction is merely stirred then there is 57% removal of TOC whilst on irradiation the figure is 64% although the latter reaction is more rapid. Use of ultrasound alone results in only 11% TOC removal in 60 min of treatment time. Addition of iron powder marginally enhances the extent of degradation but an appreciable increase is observed in the presence of hydrogen peroxide which acts as a source for hydroxyl radicals by Fenton chemistry as well as by dissociation in the presence of ultrasound. The use of hydrodynamic cavitation in conjunction with the advanced Fenton process has also been found to be a useful tool for continuous remediation of water contaminated with 2,4-D. After 20 minutes of treatment the residual TOC is reduced to 30% and this probably represents the remaining highly recalcitrant small organic molecules

The effect of different frequencies of ultrasound on the activity of horseradish peroxidase

Ultrasound technology has been studied by food researchers as an alternative method for thermal processing. The use of ultrasound as a way to inactivate and/or activate enzymes has been widely studied at low frequencies (20–40 kHz), however, little research on the effect of high frequencies has been reported. Thus, the effect of high and low frequency ultrasound on commercial horseradish peroxidase with a concentration of 0.005 mg mL−1 is described. Experiments were performed for 60 min using 20, 378, 583, 862, 995, 1144 and 1175 kHz ultrasound at power levels (acoustic energy) between 2.1 and 64 W. Residual activity was monitored using a spectrophotometric method and data analysis was performed using ANOVA. A significant enhancement of enzyme inactivation (p < 0.05) was observed at each frequency with an increase of sonication time and power. Inactivation of peroxidase by ultrasound followed first order kinetics and an increase of the rate constant with the power applied was observed for all the frequencies studied. Overall, low frequency (20 kHz) and low power are not effective on the enzyme inactivation and the level of residual activity remained high. The use of 378 and 583 kHz (48 W) is particularly effective for complete enzyme inactivation

Intensification of hydroxyl radical production in sonochemical reactors

The efficacy of sonochemical reactors in chemical processing applications has been well established in the laboratory scale of operation though at a given set of operating parameters and no efforts have been directed in terms of maximizing the free radical production. In the present work, the effect of different operating parameters viz. pH, power dissipation into the system, effect of additives such as air, haloalkanes, titanium dioxide, iron and oxygen on the extent of hydroxyl radical formation in a sonochemical reactor have been investigated using salicylic acid dosimetry. Possible mechanisms for oxidation of salicylic acid in the presence of different additives have also been established. It has been observed that acidic conditions under optimized power dissipation in the presence of iron powder and oxygen result in maximum liberation of hydroxyl radicals as quantified by the kinetic rate constant for production of 2,5- and 2,3-dihydroxybenzoic acid. The study has enabled the optimization of the conditions for maximum efficacy of sonochemical reactors where free radical attack is the controlling mechanism for the chemical processing applications

Industrial wastewater treatment using hydrodynamic cavitation and heterogeneous advanced Fenton processing

A combination of hydrodynamic cavitation and heterogeneous advanced Fenton process (AFP) based on the use of zero valent iron as the catalyst has been investigated for the treatment of real industrial wastewater. The effect of various operating parameters such as inlet pressure, temperature, and the presence of copper windings on the extent of mineralization as measured by total organic carbon (TOC) content have been studied with the aim of maximizing the extent of degradation. It has been observed that increased pressures, higher operating temperature and the absence of copper windings are more favourable for a rapid TOC mineralization. A new approach of latent remediation has also been investigated where hydrodynamic cavitation is only used as a pre-treatment with an aim of reducing the overall cost of pollutant degradation. It has been observed that approach of latent remediation works quite well with about 50–60% removal of TOC using only minimal initial treatment by hydrodynamic cavitation