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.

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.

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.

Ultrasonic destruction of surfactants: application to industrial wastewaters.

This research focused on the use of sonication to destroy surfactants and surface tension properties in industrial wastewaters that affect traditional water treatment processes. We have investigated the sonochemical destruction of surfactants and a chelating agent to understand the release of metals from surfactants during sonication. In addition, the effects of physical properties of surfactants and the effect of ultrasonic frequency were investigated to gain an understanding of the factors affecting degradation. Sonochemical degradation of surfactants was observed to be more effective than nonsurfactant compounds. In addition, as the concentration is increased, the degradation rate constant does not decrease as significantly as with nonsurfactant compounds in the near-field acoustical processor reactor. The degradation of metal complexes is not as effective as in the absence of the metal. However, this is likely an artifact of the model complexing agent used. Surfactant metal complexes are expected to be faster, as they will accumulate at the hot bubble interface, significantly increasing ligand exchange kinetics and thus degradation of the complex.