UV/persulfate processes for the removal of total organic carbon from coagulation-treated industrial wastewaters.

Sulfate radical-based oxidation processes were investigated to understand the relationship between persulfate (PS) consumption and total organic carbon (TOC) removal from industrial wastewater under various PS concentrations. First, the degradation and mineralization of Bisphenol A (BPA) (initial concentration: 11 mg/L) were investigated in ultraviolet (UV)/PS systems. Complete degradation was achieved within 30 min of UV irradiation, and 41%-72% TOC removal was achieved at PS concentrations of 200 and 400 mg/L. The consumed concentration of S2O82- and generated concentration of SO42- increased gradually to similar levels. The ratio of the PS consumption to TOC removal based on the mass concentration (mg/L) was 14.5 and 23.2 at 180 min for 200 and 400 mg/L of S2O82-, respectively. Three types of coagulation-treated industrial wastewater from metal-processing, food-processing, and adhesive-producing plants were obtained, and TOC removal was analyzed using the same UV/PS systems (initial TOC concentration: 100 mg/L). The TOC removal rates ranged from 16.9% to 94.4% after 180 min of UV irradiation at PS concentrations of 1,000, 2,000, 4,000, and 8,000 mg S2O82-/L. Despite the higher TOC removal at higher PS concentrations, the PS activation efficiency decreased significantly as the PS concentration increased. Only approximately 30%-40% activation efficiency was achieved at a PS concentration of 8,000 mg/L. In this study, the ratio of PS consumption to TOC removal ranged from 20.6 to 43.9.

Effect of liquid recirculation flow on sonochemical oxidation activity in a 28 kHz sonoreactor.

Sonochemical oxidation activity may be significantly enhanced by optimizing the geometric factors of a sonoreactor and implementing additional physical actions, such as mechanical mixing and gas sparging. This study investigates the effects of liquid recirculation flow on sonochemical oxidation reactions. This was carried out through experimental testing with a 28 kHz bath-type sonoreactor under various liquid heights and flow rates, ranging from 1λ to 4.0λ and 1.5-6.0 L/min, respectively. The potassium iodide (KI) dosimetry and sonochemiluminescence methods were used in the experiment. With an increase in the liquid height/volume, the pseudo zero-order kinetic constant and the mass of triiodide (I3-) ions fluctuated. The optimal liquid height was 2.0λ, 2.5λ, and 3.0λ, based on the appropriate formation of a cavitation active zone in the reactor. The introduction of a liquid recirculation flow led to a large reduction in sonochemical activity due to the shrinkage of the cavitation active zone. However, the sonochemical activity increased at higher flow rates through the capture of ultrasonic energy at the bottom zone. This increase was attributed to the formation of a strong and expanded active zone limited to the reactor bottom to the height of the recirculation flow. The results demonstrate that applying a high rate liquid flow adjacent to the transducer module may be beneficial for enhanced sonochemical activity.

Gas chromatography-triple quadrupole mass spectrometry as a cost-effective method for the determination of polychlorinated dibenzo-p-dioxins and furans in contaminated soils.

The aim of this study was to evaluate the performance of gas chromatography (GC)-triple quadrupole mass spectrometry (QqQ, MS/MS) as an alternative to the standard GC-high resolution mass spectrometry (GC-HR/MS) for soils contaminated with polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). GC-QqQ (MS/MS) using a dynamic multiple reaction monitoring (dMRM) mode was optimized for the quantitative analysis of 17 PCDD/Fs. A comparative study between GC-QqQ (MS/MS) and GC-HR/MS was carried out to validate the results of actual field soil samples. Although GC-HR/MS has excellent sensitivity and selectivity, the validation parameters obtained by GC-QqQ (MS/MS) also met the recommended criteria of the standard method. The results for total and I-TEQ (international toxic equivalent) value of the PCDD/F concentrations of over 86.0 pg/g and 4.3 pg I-TEQ/g, respectively, in actual field soil samples showed good agreement between the two methods, falling within ±25% relative difference. In consideration of the remediation goal (100 pg I-TEQ/g), GC-QqQ (MS/MS) can be an alternative cost-effective method for use in soil remediation research.

Ultrasound-assisted soil washing processes using organic solvents for the remediation of PCBs-contaminated soils.

Ultrasonic soil washing processes using organic solvents were investigated for the development of novel remediation technologies for persistent organic pollutants (POPs)- contaminated soils. Aluminum foil erosion was first tested to understand sonophysical activity in water, methanol (polar) and n-hexane (nonpolar) in a 28 kHz double-bath-type sonoreactor. Significant sonophysical damage on the aluminum foil was observed at the antinodes for all solvents, and the order of degree of sonophysical damage was as follows: water > methanol > n-hexane. Subsequently, conventional (mechanical mixing only) and ultrasonic soil washing (mechanical mixing and ultrasound) techniques were compared for the removal of polychlorinated biphenyls (PCBs) from soil. Two types of contaminated soils, fresh (Soil A, C0 = 2.5 mg/kg) and weathered (Soil B, C0 = 0.5 mg/kg), were used and the applied soil-to-liquid (S:L) ratio was 1:5 and 1:10 for methanol and n-hexane, respectively. The polar solvent significantly increased washing efficiencies compared to the nonpolar solvent, despite the nonpolar nature of the PCBs. Washing efficiency was significantly enhanced in ultrasonic soil washing compared to conventional washing, owing to macro- and micro-scale sonophysical actions. The highest washing efficiencies of 90% for Soil A and 70% for Soil B were observed in the ultrasonic washing processes using methanol. Additionally, a single operation of the ultrasonic washing process was superior to two sequential processes with conventional mixing in terms of washing efficiency, consumption of washing agents, treatment of washing leachate, and operation time. Finally, the removal of PCBs in an organic solvent (methanol) was investigated in photolytic and sonolytic processes for the post-treatment of soil washing leachate. A photolysis efficiency of 80% was obtained within 60 min of UV exposure for intensities of 1.0, 2.0, and 4.0 W/cm2. The primary mechanism of PCBs degradation is photolytic dechlorination. In contrast, no degradation was detected in the sonolytic process, as the excess organic solvent acted as a strong radical scavenger.

Ultrasound-assisted soil washing processes for the remediation of heavy metals contaminated soils: The mechanism of the ultrasonic desorption.

Ultrasound-assisted soil washing processes were investigated for the removal of heavy metals (Cu, Pb, and Zn) in real contaminated soils using HCl and EDTA. The ultrasound-assisted soil washing (US/Mixing) process was compared with the conventional soil washing (Mixing) process based on the mechanical mixing. High removal efficiency (44.8% for HCl and 43.2% for EDTA) for the metals was obtained for the most extreme conditions (HCl 1.0 M or EDTA 0.1 M and L:S = 10:1) in the Mixing process. With the aide of ultrasound, higher removal efficiency (57.9% for HCl and 50.0% for EDTA) was obtained in the same extreme conditions and similar or higher removal efficiency (e.g., 54.7% for HCl 0.5 M and L:S = 10:1 and 50.5% for EDTA 0.05 M and L:S = 5:1) was achieved even in less extreme conditions (lower HCl or EDTA concentration and L:S ratio). Therefore, it was revealed that the US/Mixing was advantageous over the conventional Mixing processes in terms of metal removal efficiency, consumption of chemicals, amount of generated washing leachate, and volume/size of washing reactor. In addition, the heavy metals removal was enhanced for the smaller soil particles in the US/Mixing process. It was due to more violent movement of smaller particles in slurry phase and more violent sonophysical effects. In order to understand the mechanism of ultrasonic desorption, the desorption test was conducted using the paint-coated beads with three sizes (1, 2, and 4 mm) for the free and attached conditions. It was found that no significant desorption/removal of paint from the beads was observed without the movement of beads in the water including floatation, collision, and scrubbing. Thus, it was suggested that the simultaneous application of the ultrasound and mechanical mixing could enhance the physical movement of the particles significantly and the very high removal/desorption could be attained.

Cavitational activity in heterogeneous systems containing fine particles.

Ultrasound has been increasingly used in various processes containing a variety of homogeneous and heterogeneous systems. For largescale applications, a high energy efficiency of the process is required. With this view, the calorimetric energy and cavitational activity measurements were carried out in heterogeneous systems consisting of both liquid and solid phases (fine particles) in a 28-kHz double-bath sonoreactor. Ultrasonic soil washing for the remediation of clay-sized soils (∼75 µm), contaminated with metals (Cu, Pb, and Zn), was used as a case study. As the liquid height/volume in the inner vessel increased under the same input electrical power, the inner vessel calorimetric energy also increased, whereas the total calorimetric energy between the inner vessel and the outer reactor remained approximately constant. No significant differences in calorimetric energies were observed for both with and without soil conditions. The chemical activity under similar experimental conditions was evaluated using sonochemiluminescence. Different sonochemiluminescence trends were observed depending up on the presence and size of beads. The highest total sonochemiluminescence intensity with a uniform spatial distribution was obtained from fine beads (#200, 75 µm) suspended in the vessel. Ultrasound application significantly enhanced the removal efficiency of heavy metals when combined with mechanical agitation. The enhanced removal efficiency of the combined processes was attributed to a significant removal of metals from the residual (F5) fraction. It has been concluded that ultrasound has enough extraction power to be comparable to methods that employ extremely powerful acids for washing fine particles.