Ohio Coronavirus Wastewater Monitoring Network: Implementation of Statewide Monitoring for Protecting Public Health.

CONTEXT: Prior to the COVID-19 pandemic, wastewater influent monitoring for tracking disease burden in sewered communities was not performed in Ohio, and this field was only on the periphery of the state academic research community. PROGRAM: Because of the urgency of the pandemic and extensive state-level support for this new technology to detect levels of community infection to aid in public health response, the Ohio Water Resources Center established relationships and support of various stakeholders. This enabled Ohio to develop a statewide wastewater SARS-CoV-2 (severe acute respiratory syndrome coronavirus 2) monitoring network in 2 months starting in July 2020. IMPLEMENTATION: The current Ohio Coronavirus Wastewater Monitoring Network (OCWMN) monitors more than 70 unique locations twice per week, and publicly available data are updated weekly on the public dashboard. EVALUATION: This article describes the process and decisions that were made during network initiation, the network progression, and data applications, which can inform ongoing and future pandemic response and wastewater monitoring. DISCUSSION: Overall, the OCWMN established wastewater monitoring infrastructure and provided a useful tool for public health professionals responding to the pandemic.

Kinetics and Mechanism of Ultrasonic Defluorination of Fluorotelomer Sulfonates.

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-]/[SO42-], over time. Initially, [F-]/[SO42-]4:2 FtS and [F-]/[SO42-]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 %SO42- release was drastically diminished. Therefore, thermolysis is the primary degradation pathway of FTSAs; •OH supplements SO42- 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.

Using solid-phase microextraction during ultrasound reveals higher aqueous PAHs release from contaminated sediment.

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.

In Situ EPR Spin Trapping and Competition Kinetics Demonstrate Temperature-Dependent Mechanisms of Synergistic Radical Production by Ultrasonically Activated Persulfate.

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.

Combined ultrasound-ozone treatment for reutilization of primary effluent-a preliminary study.

The present work is a preliminary study on the potential of low-frequency ultrasound irradiation coupled with O3 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-O3 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.

Effect of sediment particle size on polycyclic aromatic hydrocarbon bioaccessibility and degradation by ultrasound.

The effect of particle size on sonochemical desorption, degradation and change in bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) on contaminated sediments was investigated. Batch experiments were performed with the whole sediment (WS < 850 µm), a large size range fraction (150 µm < LSR < 850 µm), and a small size range fraction (SSR < 150 µm) of the whole sediment. PAH degradation followed pseudo first-order kinetics; PAHs on LSR sediments underwent more rapid degradation than on SSR and WS sediments (νPAH,LSR > νPAH,WS > νPAH,SSR). In addition, a higher sediment slurry concentration resulted in slower degradation of PAHs. Results are consistent with the more rapid particle size reduction of the LSR. More rapid particle size reduction and faster PAH degradation for the LSR fraction combined with analysis of particle velocities in both size ranges indicates that microjets as opposed to particle-particle collisions due to shockwaves are effective in rapid particle size reduction and PAH degradation. Moreover, the bioaccessible fraction (FPAH,fast,t) of sorbed PAHs in both particle size fractions was found to increase with sonication time but was more rapid with the LSR. Likewise, the more tightly bound PAHs, those in the slow desorbing fraction (FPAH,slow,t) of PAHs, decreased faster with sonication of LSR particles compared to SSR particles, consistent with the trend of particle size reduction. Results of this study suggest that ultrasonic treatment is more effective for larger size particle sediments, although sonication is also viable for small sediment sizes.

Synergistic, aqueous PAH degradation by ultrasonically-activated persulfate depends on bulk temperature and physicochemical parameters.

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.

Evidence of Air Dispersion: HFPO-DA and PFOA in Ohio and West Virginia Surface Water and Soil near a Fluoropolymer Production Facility.

Perfluorooctanoic acid (PFOA) was used as a fluoropolymer manufacturing aid at a fluoropolymer production facility in Parkersburg, WV from 1951 to 2013. The manufacturer introduced a replacement surfactant hexafluoropropylene oxide dimer acid (HFPO-DA) that has been in use at this site since 2013. Historical releases of PFOA and related epidemiological work in this area has been primarily focused on communities downstream. To provide an update on the ongoing impacts from this plant, 94 surface water samples and 13 soil samples were collected mainly upstream and downwind of this facility. PFOA was detected in every surface water sample with concentrations exceeding 1000 ng/L at 13 sample sites within an 8 km radius of the plant. HFPO-DA was also found to be widespread with the highest levels (>100 ng/L) found in surface water up to 6.4 km north of the plant. One sample site, 28 km north of the plant, had PFOA at 143 ng/L and HFPO-DA at 42 ng/L. Sites adjacent to landfills containing fluorochemical waste had PFOA concentrations ranging up to >1000 ng/L. These data indicate that downwind atmospheric transport of both compounds has occurred and that the boundaries of the impact zone have yet to be fully delineated.

Fast Photomineralization of Dissolved Organic Matter in Acid Mine Drainage Impacted Waters.

Acid mine drainage (AMD) formed from pyrite (iron disulfide) weathering contributes to ecosystem degradation in impacted waters. Solar irradiation has been shown to be an important factor in the biogeochemical cycling of iron in AMD-impacted waters, but its impact on dissolved organic matter (DOM) is unknown. With a typical AMD-impacted water (pH 2.7-3) collected from the Perry State Forest watershed in Ohio, we observed highly efficient (>80%) photochemical mineralization of DOM within hours in a solar simulator resembling twice summer sunlight at 40°N. We confirmed that the mineralization was initially induced by •OH formed from FeOH2+ photodissociation and was inhibited 2-fold by dissolved oxygen removal, suggesting the importance of both the photochemical reaction and oxygen involvement. Size exclusion chromatography and Fourier transform ion cyclotron resonance mass spectrometry elucidated that any remaining organic matter was comprised of smaller and highly aliphatic compounds. The quantitative and qualitative changes in DOM are likely to constitute an important component in regional carbon cycling and nutrient release and to influence downstream aquatic ecosystems in AMD-affected watersheds.

Photochemical acetochlor degradation induced by hydroxyl radical in Fe-amended wetland waters: Impact of pH and dissolved organic matter.

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 [Fe]T ≈ 6 µM and plateaued at high [Fe]T. At the highly acidic pH of acid mine drainage (AMD) waters, AC degradation was enhanced by two-orders-of magnitude with increasing [Fe]T and no plateau was observed under the conditions tested ([Fe]T ≤ 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.

Kinetics and Mechanism of Ultrasonic Activation of Persulfate: An in Situ EPR Spin Trapping Study.

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.

Isoproturon Reappearance after Photosensitized Degradation in the Presence of Triplet Ketones or Fulvic Acids.

Isoproturon (IPU) is a phenylurea herbicide used to control broad-leaf grasses on grain fields. Photosensitized transformation induced by excited triplet states of dissolved organic matter (3DOM*) has been identified as an important degradation pathway for IPU in sunlit waters, but the reappearance of IPU in the absence of light is observed after the initial photolysis. In this study, we elucidate the kinetics of this photodegradation and dark-reappearance cycling of IPU in the presence of DOM proxies (aromatic ketones and reference fulvic acids). Using mass spectrometry and nuclear magnetic resonance spectroscopic techniques, a semi-stable intermediate (IPUint) was found to be responsible for IPU reversion and was identified as a hydroperoxyl derivative of IPU. IPUint is photogenerated from incorporation of diatomic oxygen to IPU and is subjected to thermolysis whose rate depends on temperature, pH, the presence of DOM, and inorganic ions. These results are important to understand the overall aquatic fate of IPU and structurally similar compounds under diurnal conditions.

Combining COMSOL modeling with acoustic pressure maps to design sono-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 (∼ 10 cm and <5 cm 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 (∼ 5 L) 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.

Toxic cyanobacteria and drinking water: Impacts, detection, and treatment.

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.

Designing and characterizing a multi-stepped ultrasonic horn for enhanced sonochemical performance.

The commonly used ultrasonic horn generates localized cavitation below its converging tip resulting in a dense bubble cloud near the tip and limiting diffusion of reactive components into the bubble cloud or reactive radicals out of the bubble cloud. To improve contact between reactive components, a novel ultrasonic horn design was developed based on the principles of the dynamic wave equation. The horn, driven at 20 kHz, has a multi-stepped design with a cone-shaped tip increasing the energy-emitting surface areas and creating multiple reactive zones. Through different physical and chemical experiments, performance of the horn was compared to a typical horn driven at 20 kHz. Hydrophone measurements showed high acoustic pressure areas around the horn neck and tip. Sonochemiluminescence experiments verified multiple cavitation zones consistent with hydrophone readings. Calorimetry and dosimetry results demonstrated a higher energy efficiency (31.3%) and a larger hydroxyl radical formation rate constant (0.36 µM min(-1)) compared to typical horns. In addition, the new horn degraded naphthalene faster than the typical horn tested. The characterization results demonstrate that the multi-stepped horn configuration has the potential to improve the performance of ultrasound as an advanced oxidation technology by increasing the cavitation zone in the solution.

Increasing the bioaccessibility of polycyclic aromatic hydrocarbons in sediment using ultrasound.

In this study, the effect of sonication on the distribution of polycyclic aromatic hydrocarbons (PAHs) in the bioaccessible and less bioaccessible fractions of three contaminated sediments (Little Scioto River, OH-LS; Gary, IN-GI; Eagle Harbor, WA-EH) was examined. After 60min sonication, the fractions of naphthalene, phenanthrene and pyrene remaining in the LS sediment were 0.76±0.18, 0.83±0.04 and 0.76±0.05, respectively, indicating ultrasonic degradation of PAHs in the sediment. In addition, there was a significant decrease in PAH concentration (i.e., up to 91.4%) in the less bioaccessible fractions for all three sediments with sonication. The bioaccessible fraction of phenanthrene and pyrene in LS and pyrene in EH increased by 12.9%, 48.3% and 27.8%, respectively, followed by a slight decrease due to degradation. The initial increase suggests that ultrasonic irradiation of sediment either transfers the PAHs from the less bioaccessible sites to the bioaccessible sites for treatment or transforms less bioaccessible sites into bioaccessible sites. A comparatively smaller reduction (i.e., 20.2%) in the less bioaccessible fraction in GI sediment is attributed to the larger fraction of black carbon in the organic carbon content of the sediment hindering the ability of ultrasound to switch the PAHs from the less to the more bioaccessible sites. Overall ultrasonic irradiation of contaminated sediments is a technique to enhance contaminant remediation by reducing the fraction of contaminants in less bioaccessible sites.

Kinetics and mechanism of sonochemical degradation of pharmaceuticals in municipal wastewater.

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 DW (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.

Contaminant-mediated photobleaching of wetland chromophoric dissolved organic matter.

Photolytic transformation of organic contaminants in wetlands can be mediated by chromophoric dissolved organic matter (CDOM), which in turn can lose its reactivity from photobleaching. We collected water from a small agricultural wetland (Ohio), Kawai Nui Marsh (Hawaii), the Everglades (Florida), and Okefenokee Swamp (Georgia) to assess the effect of photobleaching on the photofate of two herbicides, acetochlor and isoproturon. Analyte-spiked water samples were irradiated using a solar simulator and monitored for changes in CDOM light absorbance and dissolved oxygen. Photobleaching did not significantly impact the indirect photolysis rates of either herbicide over 24 hours of irradiation. Surprisingly, the opposite effect was observed with isoproturon, which accelerated DOM photobleaching. This phenomenon was more pronounced in higher-CDOM waters, and we believe that the redox pathway between triplet-state CDOM and isoproturon may be responsible for our observations. By contrast, acetochlor indirect photolysis was dependent on reaction with the hydroxyl radical and did not accelerate photobleaching of wetland water as much as isoproturon. Finally, herbicide indirect photolysis rate constants did not correlate strongly to any one chemical or optical property of the sampled waters.

Sonochemical degradation of ciprofloxacin and ibuprofen in the presence of matrix organic compounds.

Ciprofloxacin (CIPRO) and ibuprofen (IBU), a hydrophilic and a hydrophobic compound, respectively, were degraded by ultrasound at the frequencies of 20 and 620 kHz in aqueous solution containing matrix organic compounds. Compared to in its absence, in the presence of terephthalate (TA), a commonly used OH scavenger, CIPRO degradation was inhibited by a factor of 40-1500 depending on the frequency and initial concentration. However, the degradation rates of IBU were only reduced between 30% and 80% with TA present compared to in its absence. Similar to TA, the presence of Suwannee River Fulvic Acid (SRFA) inhibited CIPRO degradation to a greater extent than that of IBU but overall inhibition by SRFA was dramatically less than by TA. Although both TA and SRFA inhibited the degradation of CIPRO and IBU, the mechanisms of inhibition are different. TA reacts with OH in bulk solution and our evidence also indicates that it accumulates on or interacts with cavitation bubbles. On the other hand, SRFA stays in bulk solution, quenching OH and/or associating with the target compounds.

Using pulsed wave ultrasound to evaluate the suitability of hydroxyl radical scavengers in sonochemical systems.

Hydroxyl radical (()OH) scavengers are commonly used in sonochemistry to probe the site and nature of reaction in aqueous cavitational systems. Using pulsed wave (PW) ultrasound with comparative sonochemistry we evaluated the performance of ()OH scavengers (i.e., formic acid, carbonic acid, terephthalic acid/terephthalate, iodide, methanesulfonate, benzenesulfonate, and acetic acid/acetate) in a sonochemical system to determine which ()OH scavengers react only in bulk solution and which ()OH scavengers interact with cavitation bubbles. The ability of each scavenger to interact with cavitation bubbles was assessed by comparing the pulse enhancement (PE) of 10µM of a probe compound, carbamazepine (CBZ), in the presence and absence of a scavenger. Based on PE results, acetic acid/acetate appears to scavenge ()OH in bulk solution, and not interact with cavitation bubbles. Methanesulfonate acts as reaction promoter, increasing rather than inhibiting the degradation of CBZ. For formic acid, carbonic acid, terephthalic acid/terephthalate, benzenesulfonate, and iodide, the PE was significantly decreased compared to in the absence of the scavenger. These scavengers not only quench ()OH in bulk solution but also affect the cavity interface. The robustness of acetic acid/acetate as a bulk ()OH scavenger was validated for pH values between 3.5 and 8.9 and acetic acid/acetate concentrations from 0.5 to 0.1M.