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.     

Characterization of polycyclic aromatic hydrocarbons (PAHs) on lime spray dryer (LSD) ash using different extraction methods

In this study, traditional Soxhlet, automatic Soxhlet and ultrasonic extraction techniques were employed to determine the speciation and concentration of polycyclic aromatic hydrocarbons (PAHs) on lime spray dryer (LSD) ash samples collected from the baghouse of a spreader stoker boiler. To test the efficiencies of different extraction methods, LSD ash samples were doped with a mixture of 16 US EPA specified PAHs to measure the matrix spike recoveries. The results showed that the spike recoveries of PAHs were different using these three extraction methods with dichloromethane (DCM) as the solvent. Traditional Soxhlet extraction achieved slightly higher recoveries than automatic Soxhlet and ultrasonic extraction. Different solvents including toluene, DCM:acetone (1:1 V/V) and hexane:acetone (1:1 V/V) were further examined to optimize the recovery using ultrasonic extraction. Toluene achieved the highest spike recoveries of PAHs at a spike level of 10 microg kg(-1). When the spike level was increased to 50 microg kg(-1), the spike recoveries of PAHs also correspondingly increased. Although the type and concentration of PAHs detected on LSD ash samples by different extraction methods varied, the concentration of each detected PAH was consistently low, at microg kg(-1) levels.     

Sonolytic reactions of phenanthrene in organic extraction solutions

Ultrasonic extraction is a common method used to extract semi-volatile and nonvolatile organic compounds such as polycyclic aromatic hydrocarbons (PAHs) from solid matrices. However, ultrasonic energy has been suspected to lead to undesired reactions of the solute and thus affect qualitative and quantitative results. In this paper, sonolytic reactions of phenanthrene in common organic extraction solutions were examined using a 20 kHz ultrasonic probe under conditions commonly used for ultrasonic extraction. Extraction parameters including phenanthrene concentration, solvent type, pulse length, and sonication time were investigated. Hexane:acetone (1:1 V/V) resulted in less phenanthrene degradation than dichloromethane (DCM):acetone (1:1 V/V). Initial solute concentration, length of sonication time, and solvent type affected the degradation of phenanthrene. Reaction byproducts including methylphenanthrene and methylnaphthalene detected after sonication indicate that phenanthrene reacts by both direct pyrolysis and reaction with methyl or ethyl radicals formed from solvent pyrolysis.     

Removal of mercury from sediment by ultrasound combined with biomass (transgenic Chlamydomonas reinhardtii)

As one of the most pervasive environmental problems, Hg pollution in sediment is particularly difficult to remediate because it cannot be decomposed. The application of ultrasound combined with biomass (transgenic Chlamydomonas reinhardtii (C. reinhardtii), a green alga) for the removal of Hg from model and contaminated sediments (Al₂O₃, α-HgS, and PACS-2 marine sediment) was investigated in this study. Ultrasound was found to enhance Hg release from Al₂O₃, α-HgS, and PACS-2 marine sediment into the aqueous phase compared to mechanical shaking. A transgenic C. reinhardtii (2AMT-2) expressing a plasmamembrane-anchored metallothionein polymer effectively recovered Hg(II) released into the aqueous phase by sonication over a broad pH range from 2.0 to 9.0. The results showed that this combined technique of ultrasound and alga biomass (2AMT-2) engineered for enhanced metal recovery was effective to remove Hg from solids and sediments, especially from Al₂O₃ and α-HgS with no natural organic matter. The results of this study are discussed with respect to the development of in situ remediation techniques for Hg-contaminated sediments.     

Photosensitized degradation of caffeine: role of fulvic acids and nitrate

The photolysis of caffeine was studied in solutions of fulvic acid isolated from Suwannee River, GA (SRFA) and Old Woman Creek Natural Estuarine Research Reserve, OH (OWCFA) with different chemical amendments (nitrate and iron). Caffeine degrades slowly by direct photolysis (>170 h in artificial sunlight), but we observed enhanced photodegradation in waters containing the fulvic acids. At higher initial concentrations (10 μM) the indirect photolysis of caffeine occurs predominantly through reaction with the hydroxyl radical (OH) generated by irradiated fulvic acids. Both rate constant estimates based upon measured OH steady-state concentrations and quenching studies using isopropanol corroborate the importance of this pathway. Further, OH generated by irradiated nitrate at concentrations present in wastewater effluent plays an important role as a photosensitizer even in the presence of fulvic acids, while the photo-Fenton pathway does not at neutral or higher pH. At lower initial concentrations (0.1 μM) caffeine photolysis reactions proceed even more quickly in fulvic acid solutions and are influenced by both short- and long-lived reactive species. Studies conducted under suboxic conditions suggest that an oxygen dependent long-lived radical e.g., peroxyl radicals plays an important role in the degradation of caffeine at lower initial concentration.