Occurrence, removal, and prioritization of organic micropollutants in four full-scale wastewater treatment plants in Korea.

This study investigated the occurrence, removal rate, and potential risks of 43 organic micropollutants (OMPs) in four municipal wastewater treatment plants (WWTPs) in Korea. Results from two-year intensive monitoring confirmed the presence of various OMPs in the influents, including pharmaceuticals such as acetaminophen (pain relief), caffeine (stimulants), cimetidine (H2-blockers), ibuprofen (non-steroidal anti-inflammatory drugs- NSAIDs), metformin (antidiabetics), and naproxen (NSAIDs) with median concentrations of >1 µg/L. Some pharmaceuticals (carbamazepine-anticonvulsants, diclofenac-NSAIDs, propranolol-ß-blockers), corrosion inhibitors (1H-benzotriazole-BTR, 4-methyl-1H-benzotriazole-4-TTR), and perfluorinated compounds (PFCs) were negligibly removed during WWTP treatment. The OMP concentrations in the influents and effluents were mostly lower in August than those of other months (p-value <0.05) possibly due to wastewater dilution by high precipitation or enhanced biodegradation under high-temperature conditions. The anaerobic-anoxic-oxic process (A2O) with a membrane bioreactor exhibited higher OMP removal than other processes, such as A2O with sedimentation or the conventional activated sludge process (p-value <0.05). Pesticides (DEET and atrazine), corrosion inhibitors (4-TTR and BTR), and metformin were selected as priority OMPs in toxicity-driven prioritization, whereas PFCs were determined as priority OMPs given their persistence and bioaccumulation properties. Overall, our results contribute to an important database on the occurrence, removal, and potential risks of OMPs in Korean WWTPs.

Perfect circular polarization of elastic waves in solid media.

Elastic waves involving mechanical particle motions of solid media can couple volumetric and shear deformations, making their manipulation more difficult than electromagnetic waves. Thereby, circularly polarized waves in the elastic regime have been little explored, unlike their counterparts in the electromagnetic regime, where their practical usage has been evidenced in various applications. Here, we explore generating perfect circular polarization of elastic waves in an isotropic solid medium. We devise a novel strategy for converting a linearly polarized wave into a circularly polarized wave by employing an anisotropic medium, which induces a so-far-unexplored coupled resonance phenomenon; it describes the simultaneous occurrence of the Fabry-Pérot resonance in one diagonal plane and the quarter-wave resonance in another diagonal plane orthogonal to the former with an exact 90° out-of-phase relation. We establish a theory explaining the involved physics and validate it numerically and experimentally. As a potential application of elastic circular polarization, we present simulation results demonstrating that a circularly polarized elastic wave can detect an arbitrarily oriented crack undetectable by a linearly polarized elastic wave.

Ultrasonic barrier-through imaging by Fabry-Perot resonance-tailoring panel.

Imaging technologies that provide detailed information on intricate shapes and states of an object play critical roles in nanoscale dynamics, bio-organ and cell studies, medical diagnostics, and underwater detection. However, ultrasonic imaging of an object hidden by a nearly impenetrable metal barrier remains intractable. Here, we present the experimental results of ultrasonic imaging of an object in water behind a metal barrier of a high impedance mismatch. In comparison to direct ultrasonic images, our method yields sufficient object information on the shapes and locations with minimal errors. While our imaging principle is based on the Fabry-Perot (FP) resonance, our strategy for reducing attenuation in our experiments focuses on customising the resonance at any desired frequency. To tailor the resonance frequency, we placed an elaborately engineered panel of a specific material and thickness, called the FP resonance-tailoring panel (RTP), and installed the panel in front of a barrier at a controlled distance. Since our RTP-based imaging technique is readily compatible with conventional ultrasound devices, it can realise underwater barrier-through imaging and communication and enhance skull-through ultrasonic brain imaging.

Integrating biological ion exchange with biological activated carbon treatment for drinking water: A novel approach for NOM removal, trihalomethane formation potential, and biological stability.

Ion exchange resins (IEX) are used in drinking water utilities to remove natural organic matter (NOM) from surface water; however, the disposal of used brine can be a major drawback. Recently, biological ion exchange (BIEX) has been proposed as an alternative to biological activated carbon (BAC) for removing natural organic matter (NOM). The present study is, to the best of our knowledge, the first attempt to use a hybrid BIEX and BAC (BIEX+BAC) system for drinking water treatment. The removal of NOM, assimilable organic carbon, and trihalomethane formation potential was investigated by operating four columns comprising IEX, BIEX, BAC, and BIEX+BAC with 18,000 bed volumes. The BIEX+BAC system was the most effective at removing dissolved organic carbon (59.9%). Based on fluorescence excitation-emission matrix spectroscopy, the BIEX+BAC column showed the maximum removal rates in all peak regions of T1, T2, and A. Using liquid chromatography-organic carbon detection, resin-containing columns were found to effectively remove humic substances, which are the principal precursors of trihalomethanes. The lowest potential for trihalomethane formation was observed in BIEX+BAC. BIEX+BAC also had the highest assimilable organic carbon removal efficiency (61.2%) followed by BIEX (52.3%), BAC (49.5%), and IEX (47.1%). The BIEX+BAC hybrid was found to be the most effective method for removing NOM fractions and reducing the formation of disinfection byproducts.

Efficiency of ozonation and O3/H2O2 as enhanced wastewater treatment processes for micropollutant abatement and disinfection with minimized byproduct formation.

Ozonation, a viable option for improving wastewater effluent quality, requires process optimization to ensure the organic micropollutants (OMPs) elimination and disinfection under minimized byproduct formation. This study assessed and compared the efficiencies of ozonation (O3) and ozone with hydrogen peroxide (O3/H2O2) for 70 OMPs elimination, inactivation of three bacteria and three viruses, and formation of bromate and biodegradable organics during the bench-scale O3 and O3/H2O2 treatment of municipal wastewater effluent. 39 OMPs were fully eliminated, and 22 OMPs were considerably eliminated (54 ± 14%) at an ozone dosage of 0.5 gO3/gDOC for their high reactivity to ozone or •OH. The chemical kinetics approach accurately predicted the OMP elimination levels based on the rate constants and exposures of ozone and •OH, where the quantum chemical calculation and group contribution method successfully predicted the ozone and •OH rate constants, respectively. Microbial inactivation levels increased with increasing ozone dosage up to ∼3.1 (bacteria) and ∼2.6 (virus) log10 reductions at 0.7 gO3/gDOC. O3/H2O2 minimized bromate formation but significantly decreased bacteria/virus inactivation, whereas its impact on OMP elimination was insignificant. Ozonation produced biodegradable organics that were removed by a post-biodegradation treatment, achieving up to 24% DOM mineralization. These results can be useful for optimizing O3 and O3/H2O2 processes for enhanced wastewater treatment.

In vitro bioanalytical assessment of the occurrence and removal of bioactive chemicals in municipal wastewater treatment plants in Korea.

Effluents of wastewater treatment plants (WWTPs) contain various organic micropollutants, some of which can exert negative effects on the quality of receiving waters or drinking water sources. This study monitored two full-scale WWTPs in Korea for the occurrence and removal of bioactive chemicals for a one-year period using a battery of in vitro bioassays as a complementary approach to chemical analysis. Bioassays covering different endpoints were employed, such as hormone receptor activation (AR and ERα), xenobiotic metabolism (PAH and PXR), oxidative stress response (Nrf2), and cytotoxicity. The WWTP influents showed AR, ERα, and PAH activities at ng/L - µg/L and PXR and Nrf2 activities at µg/L - mg/L as bioanalytical equivalent concentrations of a reference compound for each bioassay. These bioactivities decreased along with the WWTP treatment train, with significant removals achieved by the secondary biological treatment processes. Cytotoxicity was observed only for some municipal wastewater (M-WWTP) influents but was below the limit of quantification for most cases. The influent and effluent bioactivities observed in this study were mostly comparable to those reported in other WWTPs in the literature. Comparison of the bioactivities with the effect-based trigger (EBT) values indicates that the impact of WWTP effluents on receiving water quality was low for most endpoints. For Nrf2, however, further investigation is required to evaluate the observed high bioactivities compared with the current EBT. The observed ERα activity could partly be explained by the presence of some steroid estrogens. Overall, our results contribute to an important database for the concentrations and removal efficiencies of bioactive chemicals in WWTPs and demonstrate bioassays as a useful tool for urban water quality monitoring.

Elimination efficiency of synthetic musks during the treatment of drinking water with ozonation and UV-based advanced oxidation processes.

This study investigated the reaction kinetics and elimination efficiency of eleven synthetic musks during ozonation and UV254nm-based, advanced oxidation processes. The synthetic musks containing olefin moieties with electron-donating alkyl substituents such as octahydro tetramethyl naphthalenyl ethanone (OTNE) and ambrettolide (AMBT) showed high reactivity toward ozone (k ≥ 3.7 × 105 M-1 s-1) and free available chlorine (FAC) (k = 9.2 - 88 M-1 s-1), while all other synthetic musks were less ozone reactive (k = 0.3 - 560 M-1 s-1) and FAC-refractory. All synthetic musks showed high •OH reactivity (k > 5 × 109 M-1 s-1), except musk ketone (MK) (k = 2.3 × 109 M-1 s-1). In concordance with the kinetic information, OTNE and AMBT were efficiently eliminated (>97%) in simulated ozone treatments of drinking water at a specific ozone dose of 0.5 gO3/gDOC. The elimination levels of the other synthetic musks were below 50% at 0.5 gO3/gDOC. The fluence-based UV photolysis rate constant of the synthetic musks was determined to be (0.2 - 2.7) × 10-3 cm2/mJ. The elimination levels of synthetic musks during UV alone treatment ranged from 7 to 81% at a UV fluence of 500 mJ/cm2. The addition of 10 mg/L H2O2 (UV/H2O2) significantly enhanced the elimination of most synthetic musks (achieving >90% elimination at 500 mJ/cm2), indicating that the •OH reaction was mainly responsible for their elimination. The addition of 10 mg/L FAC (UV/FAC) also significantly enhanced the elimination of olefinic and aromatic synthetic musks (>90%), for which the reaction with ClO• was mainly responsible. For MK and two alkyl synthetic musks, their elimination during UV/FAC treatment was still limited (28 - 64%) and was mainly achieved by UV photolysis or reaction with •OH. In summary, this study substantiates the chemical kinetics approach as a helpful tool for predicting or interpreting the elimination of micropollutants during oxidative water treatment.

Reaction kinetics and degradation efficiency of halogenated methylparabens during ozonation and UV/H2O2 treatment of drinking water and wastewater effluent.

This study investigated the reaction kinetics and degradation efficiency of methylparaben and its halogenated products (Cl-, Br-, Cl,Cl-, Br,Cl-, and Br,Br-methylparabens) during ozonation and UV254/H2O2 treatment. Second-order rate constants for reactions of the parabens with ozone and •OH were [Formula: see text] = 107 - 108 M-1 s-1 and [Formula: see text] = (2.3 - 4.3)× 109 M-1 s-1 at pH 7. Species-specific [Formula: see text] values of the protonated and deprotonated parabens were closely related to phenol ring substituent effects via quantitative structure-activity relationships with other substituted phenols. The UV photolysis rate of the parabens [kUV = (2.4 - 7.2)× 10-4 cm2 mJ-1] depended on the halogenation state of the paraben and solution pH, from which species-specific quantum yields were also determined. In simulated treatments of drinking water and wastewater effluent, the parabens were efficiently eliminated during ozonation, requiring a specific ozone dose of > 0.26 gO3/gDOC for > 97% degradation. During UV/H2O2 treatment with 10 mg L-1 H2O2, the degradation levels were > 90% at a UV fluence of 2000 mJ cm-2, except for Cl,Cl-methylparaben. Kinetic models based on the obtained reaction kinetic parameters could successfully predict the degradation levels of the parabens. Overall, ozonation and UV/H2O2 were effective in controlling parabens and their halogenated products during advanced water treatment.

Mechanistic and Kinetic Understanding of the UV254 Photolysis of Chlorine and Bromine Species in Water and Formation of Oxyhalides.

This study investigated the UV254 photolysis of free available chlorine and bromine species in water. The intrinsic quantum yields for •OH and X• (X = Cl or Br) generation were determined by model fitting of formaldehyde formation using a tert-butanol assay to be 0.61/0.45 for HOCl/OCl- and 0.32/0.43 for HOBr/OBr-. The steady-state •OH concentration in UV/HOX was higher than that in UV/OX- by a factor of 23.3 and 7.8 for Cl and Br, respectively. This was attributed to the different •OH consumption rate by HOCl versus OCl-, while for HOBr/OBr-, both the •OH formation and consumption rates were implied. This was supported by a k of 1.4 × 108 M-1 s-1 for the •OH reaction with HOCl, which was >14 times less than the k for •OH reactions with OCl-, HOBr, and OBr-. Formation of ClO3- and BrO3- was found to be significant with apparent quantum yields of 0.12-0.23. A detailed mechanistic study on the formation of XO3- including a new pathway involving XO• is presented, which has important implications as the level of XO3- can exceed the regulation (BrO3-) or guideline (ClO3-) values during UV/halogen oxidant water treatment. Our new kinetic models well simulate the experimental results for the halogen oxidant decomposition, probe compound degradation, and formation of ClO3- and BrO3-.

Enhanced Thermoelectric Conversion Efficiency of CVD Graphene with Reduced Grain Sizes.

The grain size of CVD (Chemical Vapor Deposition) graphene was controlled by changing the precursor gas flow rates, operation temperature, and chamber pressure. Graphene of average grain sizes of 4.1 µm, 2.2 µm, and 0.5 µm was synthesized in high quality and full coverage. The possibility to tailor the thermoelectric conversion characteristics of graphene has been exhibited by examining the grain size effect on the three elementary thermal and electrical properties of σ, S, and k. Electrical conductivity (σ) and Seebeck coefficients (S) were measured in a vacuum for supported graphene on SiO2/Si FET (Field Effect Transistor) substrates so that the charge carrier density could be changed by applying a gate voltage (VG). Mobility (µ) values of 529, 459, and 314 cm²/V·s for holes and 1042, 745, and 490 cm²/V·s for electrons for the three grain sizes of 4.1 µm, 2.2 µm, and 0.5 µm, respectively, were obtained from the slopes of the measured σ vs. VG graphs. The power factor (PF), the electrical portion of the thermoelectric figure of merit (ZT), decreased by about one half as the grain size was decreased, while the thermal conductivity (k) decreased by one quarter for the same grain decrease. Finally, the resulting ZT increased more than two times when the grain size was reduced from 4.1 µm to 0.5 µm.

In-Plane Thermal Conductivity of Polycrystalline Chemical Vapor Deposition Graphene with Controlled Grain Sizes.

Manipulation of the chemical vapor deposition graphene synthesis conditions, such as operating P, T, heating/cooling time intervals, and precursor gas concentration ratios (CH4/H2), allowed for synthesis of polycrystalline single-layered graphene with controlled grain sizes. The graphene samples were then suspended on 8 µm diameter patterned holes on a silicon-nitride (Si3N4) substrate, and the in-plane thermal conductivities k(T) for 320 K < T < 510 K were measured to be 2660-1230, 1890-1020, and 680-340 W/m·K for average grain sizes of 4.1, 2.2, and 0.5 µm, respectively, using an opto-thermal Raman technique. Fitting of these data by a simple linear chain model of polycrystalline thermal transport determined k = 5500-1980 W/m·K for single-crystal graphene for the same temperature range above; thus, significant reduction of k was achieved when the grain size was decreased from infinite down to 0.5 µm. Furthermore, detailed elaborations were performed to assess the measurement reliability of k by addressing the hole-edge boundary condition, and the air-convection/radiation losses from the graphene surface.

Experiments of wave cancellation with elastic phononic crystal.

The objective of this work is to experimentally demonstrate that two incident beams of ultrasonic waves can be cancelled by using an elastic phononic crystal (PC) prism. Although PCs are known to be used for wave cancellation, there appears no experimental demonstration especially for elastic waves. Here, we use an elastic PC prism embedded in an aluminum plate, which can split an input incident beam into multiple output beams. Two signals of different incident angles are reversely sent to the prism for the wave cancellation experiment. For successful wave cancellation experiments, the magnitudes and phase difference of the input sources were carefully tuned. The experimental results were found to agree well with the predictions from numerical simulations.