Ultrasound (US) was shown to activate persulfate (PS) providing an alternative activation method to base or heat as an in situ chemical oxidation (ISCO) method. The kinetics and mechanism of ...ultrasonic activation of PS were examined in aqueous solution using an in situ electron paramagnetic resonance (EPR) spin trapping technique and radical trapping with probe compounds. Using the spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), hydroxyl radical (•OH) and sulfate radical anion (SO4 •–) were measured from ultrasonic activation of persulfate (US-PS). The yield of •OH was up to 1 order of magnitude greater than that of SO4 •–. The comparatively high •OH yield was attributed to the hydrolysis of SO4 •– in the warm interfacial region of cavitation bubbles formed from US. Using steady-state approximations, the dissociation rate of PS in cavitating bubble systems was determined to be 3 orders of magnitude greater than control experiments without sonication at ambient temperature. From calculations of the interfacial volume surrounding cavitation bubbles and using the Arrhenius equation, an effective mean temperature of 340 K at the bubble–water interface was estimated. Comparative studies using the probe compounds tert-butyl alcohol and nitrobenzene verified the bubble–water interface as the location for PS activation by high temperature with •OH contributing a minor role in activating PS to SO4 •–. The mechanisms unveiled in this study provide a basis for optimizing US-PS as an ISCO technology.
•Coupling COMSOL simulations with acoustic pressure maps informs sono-reactor design.•Simulations show high acoustic pressures along the neck of a multi-stepped horn.•Hydrophone measurements indicate ...cavitation along horn neck and verify simulations.•Conical bottom reactor maximizes cavitational volume compared to typical reactors.
Scaled-up and economically viable sonochemical systems are critical for increased use of ultrasound in environmental and chemical processing applications. In this study, computational simulations and acoustic pressure maps were used to design a larger-scale sono-reactor containing a multi-stepped ultrasonic horn. Simulations in COMSOL Multiphysics showed ultrasonic waves emitted from the horn neck and tip, generating multiple regions of high acoustic pressure. The volume of these regions surrounding the horn neck were larger compared with those below the horn tip. The simulated acoustic field was verified by acoustic pressure contour maps generated from hydrophone measurements in a plexiglass box filled with water. These acoustic pressure contour maps revealed an asymmetric and discrete distribution of acoustic pressure due to acoustic cavitation, wave interaction, and water movement by ultrasonic irradiation. The acoustic pressure contour maps were consistent with simulation results in terms of the effective scale of cavitation zones (∼10cm and <5cm above and below horn tip, respectively). With the mapped acoustic field and identified cavitation location, a cylindrically-shaped sono-reactor with a conical bottom was designed to evaluate the treatment capacity (∼5L) for the multi-stepped horn using COMSOL simulations. In this study, verification of simulation results with experiments demonstrates that coupling of COMSOL simulations with hydrophone measurements is a simple, effective and reliable scientific method to evaluate reactor designs of ultrasonic systems.
Blooms of toxic cyanobacteria in water supply systems are a global issue affecting water supplies on every major continent except Antarctica. The occurrence of toxic cyanobacteria in freshwater is ...increasing in both frequency and distribution. The protection of water supplies has therefore become increasingly more challenging. To reduce the risk from toxic cyanobacterial blooms in drinking water, a multi-barrier approach is needed, consisting of prevention, source control, treatment optimization, and monitoring. In this paper, current research on some of the critical elements of this multi-barrier approach are reviewed and synthesized, with an emphasis on the effectiveness of water treatment technologies for removing cyanobacteria and related toxic compounds. This paper synthesizes and updates a number of previous review articles on various aspects of this multi-barrier approach in order to provide a holistic resource for researchers, water managers and engineers, as well as water treatment plant operators.
Ultrasound coupled with activated persulfate can synergistically degrade aqueous organic contaminants. Here, in situ electron paramagnetic resonance spin trapping was used to compare radicals ...produced by ultrasonically activated persulfate (US-PS) and its individual technologies, ultrasound alone (US) and heat-activated persulfate (PS), with respect to temperature. Radicals were trapped using 5,5-dimethyl-1-pyrroline-N-oxide, DMPO, to form detectable nitroxide adducts. Using initial rates of radical adduct formation, and compared to US and PS, US-PS at 40 and 50 °C resulted in the largest synergistic production of radicals. Radicals generated from US were reasonably consistent from 40 to 70 °C, indicating that temperature had little effect on cavitational bubble collapse over this range. However, synergy indexes calculated from initial rates showed that ultrasonic activation of persulfate at the bubble interface changes with temperature. From these results, we speculate that higher temperatures enhance persulfate uptake into cavitation bubbles via nanodroplet injection. DMPO-OH was the predominant adduct detected for all conditions. However, competition modeling and spin trapping in the presence of nitrobenzene and atrazine probes showed that SO4 •– predominated. Therefore, the DMPO-OH signal is derived from SO4 •– trapping with subsequent DMPO-SO4 – hydrolysis to DMPO-OH. Spin trapping is effective in quantifying total radical adduct formation but limited in measuring primary radical speciation in this case.
Iron (Fe) plays a critical role in the formation of hydroxyl radical (OH) which may participate in the indirect photodegradation of aquatic contaminants. While Fe photochemistry has been extensively ...studied, the efficacy of iron amendments for contaminant attenuation in sunlit natural waters has not been well researched. We studied the efficacy of this approach by monitoring OH induced acetochlor (AC) degradation and determining OH production rates with terephthalate (TPA) as a probe. Surface wetland waters as well as model fulvic acid (FA) solutions were amended with Fe(III) salt at different concentrations at pH values of 2.7, 5, and 7.6. We observed no significant enhancement in the AC degradation rate at circumneutral pH. At pH 5, AC degradation increased by more than 50% with an Fe addition up to an FeT ≈ 6 μM and plateaued at high FeT. At the highly acidic pH of acid mine drainage (AMD) waters, AC degradation was enhanced by two-orders-of magnitude with increasing FeT and no plateau was observed under the conditions tested (FeT ≤ 500 μM). While the Fe induced relative difference in OH production rates determined using TPA was useful in elucidating the reaction mechanism for different dissolved organic matter types at different pH values, the absolute value of OH production rates over-predicted the transformation of AC suggesting the existence of unknown side reactions and/or alternative reactive intermediates.
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•Fe-assisted enhancement in acetochlor (AC) degradation increased with decreasing pH.•AC decay rate plateaued at 2 and 6 μM FeT at pH 7.6 and 5, respectively.•AC decay rate increased with increasing FeT at all FeT tested at pH 2.7.•DOM promoted Fe-assisted photodegradation at pH ≥ 5 but inhibited it at pH 2.7.
•PAHsaq during US is higher than PAHsaq after US is ceased.•Analysis of PAHs after US treatment is ceased underestimates released PAHs.•PAHs resorb onto sediment within 10 min after US is turned ...off.•SPME fibers allow for measurement of PAHsaq during course of US treatment.
Ultrasound (US) releases polycyclic aromatic hydrocarbons (PAHs) from contaminated creosote sediments and degrades PAHs in aqueous solution. However, it is unclear how much PAHs release occurs during active US compared to after US is stopped. In this study, solid-phase microextraction (SPME) was used to determine aqueous PAH concentrations desorbed from Little Scioto River creosote contaminated sediment during exposure to 20 kHz ultrasound (US) at a power of 430 W L−1. First, SPME fiber-water partition coefficients,KSPME, were experimentally determined and shown to be comparable with previous studies. Next, PAH concentrations released into aqueous solution were determined by sequentially exposing fresh, conditioned SPME fibers in a reactor containing the contaminated sediment and DI for 10 min periods. Three consecutive 10 min periods each were measured during US and after US. Compared to mixing only, PAHs desorbed during ultrasound was significantly higher. In addition, for phenanthrene, anthracene, and fluoranthene, US showed significantly higher aqueous concentrations during US compared with after US. For these less soluble PAHs, desorption into the aqueous phase reaches and surpasses expected equilibrium aqueous concentrations. However, when US is ceased, PAHs appear to resorb onto sediment resulting in the lower concentrations measured in these PAH compounds after US that are similar to expected equilibrium aqueous concentrations. Typical analytical extraction methods for determining the effects of US require stopping treatment and may underestimate the potential US has for release of contaminants from sediment during US. Using SPME during US treatment reveals that the concentration of PAHs during US may surpass the expected equilibrium aqueous concentration of some PAHs congeners. To our knowledge, this higher concentration observed during US compared to after US has not been shown previously.
A series of six pharmaceuticals were degraded by continuous wave (CW) and pulsed wave (PW) ultrasound at 205 kHz using deionized water, wastewater effluent, and its isolated organic matter matrices. ...In deionized water, we observed that hydrophobicity is superior to diffusivity (D W) for predicting degradation kinetics. Enhancements in degradation kinetics by the PW mode were greatest for the highest D W (i.e., fluorouracil (5-FU)) and K OW (i.e., lovastatin (LOVS)) compounds, indicating that a pharmaceutical with either high diffusivity and low hydrophobicity or low diffusivity and high hydrophobicity benefits from additional time to populate the bubble–water interface during the silent cycle of PW ultrasound. Degradation of 5-FU and LOVS were inhibited by wastewater effluent to a greater extent than the other pharmaceuticals. In addition, a pulse enhancement (PE) for 5-FU and LOVS was not present in wastewater effluent. Irradiating 5-FU and LOVS in hydrophobic (HPO), transphilic (TPI), and hydrophilic (HPI) fractions of effluent organic matter (EfOM) showed that the TPI fraction reduced the PE the most, followed by the HPI and HPO fractions. The smaller size of the TPI over the HPO fraction and higher hydrophobicity of TPI over HPI implicate both size and hydrophobicity of EfOM in hindering degradation of pharmaceuticals.
Ultrasound degrades “legacy” per- and polyfluoroalkyl substances (PFAS) via thermolysis at the interface of cavitation bubbles. However, compared to “legacy” PFAS, polyfluoroalkyl substances have a ...lesser affinity to the interface and may react with •OH. To understand the effect of size on degradation kinetics and mechanism of polyfluoroalkyl substances, this work compared ultrasonic treatment (f = 354 kHz) of n:2 fluorotelomer sulfonates (FTSAs) of varying chain lengths (n = 4, 6, 8). Of the congeners tested, 4:2 fluorotelomer sulfonate (FtS) degraded the fastest in individual solutions and in mixtures. Sonolytic rate constants correlated to diffusion coefficients of FTSAs, indicating that diffuse short-chain FTSAs outcompete long-chain FTSAs to adsorb and react at the bubble interface. Interestingly, 4:2 and 8:2 FtS had different evolutions of fluoride-to-sulfate ratios, F–/SO4 2–, over time. Initially, F–/SO4 2–4:2 FtS and F–/SO4 2–8:2 FtS were respectively higher and lower than theoretical ratios. This difference was attributed to the lower maximum surface excess of 8:2 FtS, hindering its ability to pack and, consequently, defluorinate at the interface. In the presence of an •OH scavenger, FTSAs had similar %F– release compared to no scavenger, whereas %SO4 2– release was drastically diminished. Therefore, thermolysis is the primary degradation pathway of FTSAs; •OH supplements SO4 2– formation. These results indicate that ultrasound directly cleaves C–F bonds within the fluoroalkyl chain. This work shows that ultrasound efficiently degrades FTSAs of various sizes and may potentially treat other classes of polyfluoroalkyl substances.
•Combined US and activated persulfate synergistically degrades PAHs from 20 to 50 °C.•At 20 °C, US-PS rate constants strongly correlate with diffusion coefficients.•Synergy Indexes are greatest for ...all PAHs between 20 and 40 °C.•US-PS becomes antagonistic at 60 °C due to radical-radical recombination.
Coupling ultrasound with other remediation technologies has potential to result in synergistic degradation of contaminants. In this work, we evaluated synergisms from adding high-power ultrasound (20 kHz; 250 W) to activated persulfate over a range of bulk temperatures (20–60 °C). We studied the aqueous degradation kinetics of three polycyclic aromatic hydrocarbons (PAHs: naphthalene, phenanthrene, and fluoranthene) treated by ultrasound-alone, heat-activated persulfate, and combined ultrasonically-activated persulfate (US-PS). At 20 °C, observed US-PS rate constants strongly correlated with Wilke-Chang diffusion coefficients. This correlation indicates PAH molecules diffuse to the bubble-water interface prior to reaction with sulfate radicals (SO4−) generated at the interface. At higher temperatures, observed US-PS rate constants appear to be a more complicated function of temperature and diffusion coefficients. Synergy indexes for PAHs with fast diffusion coefficients were greatest at 20 °C. Fluoranthene, the largest and most hydrophobic PAH, had a maximum synergy index at 30 °C; it benefited from additional thermal persulfate activation in bulk solution. Fluoranthene synergy indexes, however, decreased above 30 °C and became antagonistic at 60 °C. Electron paramagnetic resonance (EPR) spin trapping was used to quantify hydroxyl radical (OH) produced from acoustic cavitation in the absence of persulfate. These data showed consistent OH production from 20 to 60 °C, indicating PAH antagonisms at 60 °C were not due to lower bubble collapse temperatures. Instead, the results suggest that PAH antagonisms are caused by increased radical–radical recombination as bulk temperature increases. In effort to develop an efficient, combined remediation technology, this work suggests bulk temperatures between 20 and 40 °C maximize US-PS synergisms.
The present work is a preliminary study on the potential of low-frequency ultrasound irradiation coupled with O
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process for the disinfection of a primary effluent from a municipal wastewater ...treatment plant preserving nutrient levels (in particular nitrogen and phosphorous), for its possible reuse in civil, industrial, and agricultural sectors. The treated water could be reused, after appropriate dilution, contributing to the circular economy perspective and reducing the need for both chemical fertilizer addition and freshwater supply. The effect of different specific ultrasonic energies and ozone doses was assessed on a bench-top system, composed of an ultrasonic reactor and a semi-batch ozonation vessel. The results showed that the combined US-O
3
process produces a good removal efficiency regarding soluble Chemical Oxygen Demand, sCOD (ca. 60%), anionic surfactants (ca. 50%), and formaldehyde (ca. 50%), and an optimal abatement for Methylene Blue Active Substances (MBAS, > 90%). The process also reached high disinfection performances, obtaining 4 logs for
E. coli
and 5 log abatement for Total Coliforms. The high removal efficiency is matched by an outstanding retention of nutrients (total nitrogen and orthophosphate) highlighting a high potential value for agricultural reuse of the treated primary effluent, with possible significant saving of chemical fertilizers. It was concluded that low-frequency ultrasound pre-treatment, combined with ozonation, could be a useful process for primary effluent recovery for several purposes. Further studies are expected to be planned and executed to evaluate system scale-up feasibility.
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