Fundamental Limits of the Spatial Control of Heterogeneous Nucleation on Biphilic Surfaces.

Condensation of water vapor on nonwetting surfaces, termed dropwise condensation, leads to rapid droplet removal and significantly improves heat transfer compared to wetting surfaces. However, the spatial distribution of heterogeneous nucleation sites during dropwise condensation is random. Furthermore, the low surface energy of the nonwetting substrate reduces the nucleation rate as predicted by classical nucleation theory. To achieve higher nucleation rates, biphilic surfaces having low nucleation energy barriers that rely on spatial heterogeneity of surface chemistry have been developed. Here, we use a robust method to create biphilic surfaces on flat and micropillar samples having various dimensions (pillar lengths: 10-15 µm, pillar heights: 0-15 µm) by utilizing lift-off microfabrication. Our fabrication approach leads to hydrophilic pillar tops and hydrophobic pillar sides and surrounding basal areas. To study water vapor condensation on the biphilic surfaces, we utilized optical microscopy in a controlled temperature and humidity environment. Interestingly, our studies show that while the majority of nucleation (≈100%) occurred only on the hydrophilic areas (pillar tops) for small pillar center-to-center spacing (pitch), the spatial control of heterogeneous nucleation broke down when the pitch increased. For larger pitches, we observed the nucleation of water droplets on the hydrophobic base in conjunction with hydrophilic pillar tops. Using theoretical models of vapor diffusion coupled with heat transfer and three-dimensional (3D) numerical simulations, we show that nucleation initiation on hydrophilic pillar tops leads to the formation of dry zones, preventing nucleation on hydrophobic regions. However, with increasing pitch, part of the hydrophobic region no longer feels the presence of the vapor depletion zone, resulting in subsequent nucleation at defect sites on the hydrophobic regions at the base. Our study offers insights into the fundamental limitations of biphilic condensation and offers avenues for their further improvement for applications such as boiling, icing, evaporation, and condensation.

Removal characteristics of 53 micropollutants during ozonation, chlorination, and UV/H2O2 processes used in drinking water treatment plant.

The removal of 53 emerging micropollutants (MPs), including 10 per- and polyfluorinated substances (PFASs), 25 pharmaceuticals and personal care products (PPCPs), 7 pesticides, 5 endocrine disrupters (EDCs), 3 nitrosamines, and 3 taste and odor compounds (T&Os), by chlorination, ozonation, and UV/H2O2 treatment was examined in deionized water and surface waters used as the raw waters in drinking water treatment plants (DWTPs) in South Korea. The UV/H2O2 treatment was effective in the removal of most MPs, whereas chlorination was selectively effective for 19 MPs, including EDCs (>70 %). MPs containing aromatic ring with electron-donating functional group, or primary and secondary amines were effectively removed by chlorination immediately upon reaction initiation. The removal of MPs by ozonation was generally lower than that of the other two processes at a low ozone dose (1 mg L-1), but higher than chlorination at a high ozone dose (3 mg L-1), particularly for 16 MPs, including T&Os. Compared in deionized water, the removals of MPs in the raw water samples were lower in all three processes. The regression models predicting the rate constants (kobs) of 53 MPs showed good agreement between modeled and measured value for UV/H2O2 treatment (R2 = 0.948) and chlorination (R2 = 0.973), despite using only dissolved organic carbon (DOC) and oxidant concentration as variables, whereas the ozonation model showed a variation (R2 = 0.943). Our results can provide the resources for determining which oxidative process is suitable for treating specific MPs present in the raw waters of DWTPs.

Non-target screening of volatile organic compounds in spray-type consumer products and their potential health risks.

Widespread use of spray-type consumer products can raise significant concerns regarding their effects on indoor air quality and human health. In this study, we conducted non-target screening using gas chromatography-mass spectrometry (GC-MS) to analyze VOCs in 48 different spray-type consumer products. Using this approach, we tentatively identified a total of 254 VOCs from the spray-type products. Notably, more VOCs were detected in propellant-type products which are mostly solvent-based than in trigger-type ones which are mostly water-based. The VOCs identified encompass various chemical classes including alkanes, cycloalkanes, monoterpenoids, carboxylic acid derivatives, and carbonyl compounds, some of which arouse concerns due to their potential health effects. Alkanes and cycloalkanes are frequently detected in propellant-type products, whereas perfumed monoterpenoids are ubiquitous across all product categories. Among the identified VOCs, 12 compounds were classified into high-risk groups according to detection frequency and signal-to-noise (S/N) ratio, and their concentrations were confirmed using reference standards. Among the identified VOCs, D-limonene was the most frequently detected compound (freq. 21/48), with the highest concentration of 1.80 mg/g. The risk assessment was performed to evaluate the potential health risks associated with exposure to these VOCs. The non-carcinogenic and carcinogenic risks associated with the assessed VOC compounds were relatively low. However, it is important not to overlook the risk faced by occupational exposure to these VOCs, and the risk from simultaneous exposure to various VOCs contained in the products. This study serves as a valuable resource for the identification of unknown compounds in the consumer products, facilitating the evaluation of potential health risks to consumers.

Temporal and spatial distribution of microplastic in the sediment of the Han River, South Korea.

Sediments are sinks for microplastics (MPs) in freshwater environments. It is, therefore, necessary to investigate the occurrence and fate of accumulated MPs in the sediments, which pose a risk to aquatic organisms. We conducted the first comprehensive investigation of MPs in riverine sediment in South Korea to examine the temporal and spatial distribution of MPs in the sediment at the two main branches and downstream of the Han River. The average abundance of MPs over all sites was 0.494 ± 0.280 particles/g. Spatially, the MP abundance at three sites in the North Han River (0.546 ± 0.217 particles/g) was higher than those in the South Han River (0.383 ± 0.145 particles/g) and downstream of the Han River (0.417 ± 0.114 particles/g). The abundances of MPs before dams at two upstream sites were significantly higher than that at other sites because of the slow river flow velocity attributed to the artificial structure. The abundance of MPs after the mosoon season (October, 0.600 ± 0.357 particles/g) was higher than that before the mosoon season (April, 0.389 ± 0.099 particles/g). The most common polymer types observed were polyethylene (>38%) and polypropylene (>24%). Irrespective of the location and season, greater than 93% of MPs identified were fragments, and the remaining were fibers. The concentrations of TOC, TN, and TP in the sediment were positively correlated with MP abundance. MP abundance was also positively correlated with clay and silt fractions of the sediment; however, it was negatively correlated with sand fraction. This study provides a basis for the management of MP pollution by offering findings related to critical factors influencing MP abundance in sediment.

Analysis of semi-volatile organic compounds in indoor dust and organic thin films by house type in South Korea.

In this study, semi-volatile organic compounds (SVOCs) in samples of indoor dust and organic thin films obtained from 100 residential houses in South Korea, were examined, based on both target analysis using gas chromatography-mass spectrometry (GC-MS) and non-target analysis by gas chromatography-quadrupole time-of flight mass spectrometry (GC-QTOF-MS) screening. In the targeted approach, phthalates and polycyclic aromatic hydrocarbons (PAHs) were analyzed in dust and organic film samples, to find that both these classes of SVOCs were detected in dust and organic film samples, with the median concentrations of eight phthalates (Σ8 phthalate) and 16 PAHs (Σ16 PAH) being 1015.93 µg/g and 1824.97 ng/g in the dust samples, and 75.79 µg/m2 and 2252.78 ng/m2 in the organic film samples, respectively. Among the phthalates, in all house types. bis(2-ethylhexyl) phthalate (DEHP) was detected at the highest concentration, followed by dibutyl phthalate (DBP) and diisobuthyl phthalate (DiBP), with DEHP levels found to be highest in dwelling houses. DEHP levels were found to be significantly associated with building age and renovation status. Lower levels of DEHP were detected in houses less than 10 years old or that had undergone renovation in the previous 10 years. Among the assessed PAHs, a significant correlation was detected between benzo(a)pyrene in dust and building age (p < 0.05). These findings imply that the inhabitants of older houses are at a greater risk of exposure to SVOCs originating from indoor dust and organic films. Non-target screening of selected dust and organic film samples using GC-QTOF-MS data revealed the presence of numerous SVOC compounds, including triphenylphosphine oxide, (Z)-9-octadecenamide, and cyclosiloxanes, along with certain organophosphate flame retardants including tris(1-chloro-2-propyl) phosphate (TCPP) and tris(1,3-dichloroisopropyl) phosphate (TDCPP), and plasticizers. These compounds identified in the non-target screening are of emerging concern, and their presence in dust and organic films needs to be estimated.

Advanced microplastic monitoring using Raman spectroscopy with a combination of nanostructure-based substrates.

Micro(nano)plastic (MNP) pollutants have not only impacted human health directly, but are also associated with numerous chemical contaminants that increase toxicity in the natural environment. Most recent research about increasing plastic pollutants in natural environments have focused on the toxic effects of MNPs in water, the atmosphere, and soil. The methodologies of MNP identification have been extensively developed for actual applications, but they still require further study, including on-site detection. This review article provides a comprehensive update on the facile detection of MNPs by Raman spectroscopy, which aims at early diagnosis of potential risks and human health impacts. In particular, Raman imaging and nanostructure-enhanced Raman scattering have emerged as effective analytical technologies for identifying MNPs in an environment. Here, the authors give an update on the latest advances in plasmonic nanostructured materials-assisted SERS substrates utilized for the detection of MNP particles present in environmental samples. Moreover, this work describes different plasmonic materials-including pure noble metal nanostructured materials and hybrid nanomaterials-that have been used to fabricate and develop SERS platforms to obtain the identifying MNP particles at low concentrations. Plasmonic nanostructure-enhanced materials consisting of pure noble metals and hybrid nanomaterials can significantly enhance the surface-enhanced Raman scattering (SERS) spectra signals of pollutant analytes due to their localized hot spots. This concise topical review also provides updates on recent developments and trends in MNP detection by means of SERS using a variety of unique materials, along with three-dimensional (3D) SERS substrates, nanopipettes, and microfluidic chips. A novel material-assisted spectral Raman technique and its effective application are also introduced for selective monitoring and trace detection of MNPs in indoor and outdoor environments.

Occurrence and characteristics of microplastics in fish of the Han River, South Korea: Factors affecting microplastic abundance in fish.

This study examined the abundance of microplastics (MPs) in 106 fish from 22 species inhabiting three sites of the Han River, South Korea. In total, 1753 MPs from 106 fish samples were identified with an average abundance of 15.60 ± 13.45 MPs per individual fish (MPs indiv-1) in the North Han River, 16.35 ± 12.32 MPs indiv-1 in the South Han River, and 20.14 ± 10.01 MPs indiv-1 in downstream of the Han River, indicating that the fish in the downstream of the Han River was the most contaminated by MPs. The dominant size of MPs detected in fish ranged between 0.1 and 0.2 mm, and the most common polymer types found in fish were polypropylene (PP) (≥40%) and polyethylene (PE) (≥23%), followed by polytetrafluoroethylene (PTFE) (≥16%) at all sampling locations. A significant correlation was observed between the log-transformed number of MPs with log-transformed fish length (p < 0.01) and with log-transformed fish weight (p < 0.01). The Kruskal-Wallis test disclosed a significant difference in the number of MPs among the feeding habits (p < 0.01), indicating that omnivorous and insectivorous fish contained more MPs than carnivorous and herbivorous fish. In addition, fish habitat result showed that pelagic fish contained a higher level of MPs than demersal fish, but no significant differences in the number of MPs among fish habitats were observed (p > 0.05).

Occurrence, Potential Sources, and Risk Assessment of Volatile Organic Compounds in the Han River Basin, South Korea.

Increasing public awareness about the aesthetics and safety of water sources has shifted researchers' attention to the adverse effects of volatile organic compounds (VOCs) on humans and aquatic organisms. A total of 17 VOCs, including 10 volatile halogenated hydrocarbons and seven volatile non-halogenated hydrocarbons, were investigated at 36 sites of the Han River Basin, which is the largest and most important drinking water source for residents of the Seoul metropolitan area and Gyeonggi province in South Korea. The VOC concentrations ranged from below detection limits to 1.813 µg L-1. The most frequently detected VOC was 1,2-dichloropropane, with a detection frequency of 80.56%, as it is used as a soil fumigant, chemical intermediate, and industrial solvent. In terms of geographical trends, the sampling sites that were under the influence of sewage and industrial wastewater treatment plants were more polluted with VOCs than other areas. This observation was also supported by the results of the principal component analysis. In the present study, the detected concentrations of VOCs were much lower than that of the predicted no-effect concentrations, suggesting low ecological risk in the Han River. However, a lack of available ecotoxicity data and limited comparable studies warrants further studies on these compounds.

Spectroscopic analysis of microplastic contaminants in an urban wastewater treatment plant from Seoul, South Korea.

In this study, a systematic multi-spectroscopic analysis of microplastics (MPs) sampled from a metropolitan area of Seoul was undertaken to elevate understanding of the role of wastewater treatment plants (WWTPs) in eliminating suspended contaminants including MPs before releasing the effluent water into the environment. We analyzed pollutants in influent and effluent samples from a WWTP in Seoul, South Korea. Spectroscopic and microscopic methods were used to analyze MPs. Fourier-transform infrared (FT-IR) spectroscopy in the wavenumber region between 4000 and 715 cm-1 was employed to estimate the abundance of MPs in wastewater. Stereomicroscope images and Nile red staining were used to facilely identify MPs in both influents and effluents to compare the results with those of FT-IR data. Hyperspectral imaging could identify MPs in the influent sample with the reflection method at 400-900 nm. Our preliminary results indicate that the most observed MPs after the wastewater were filtered by a 45 µm stainless steel mesh filter were polyethylene (PE) and polypropylene (PP). The total number of the prevalent MPs in influent samples decreased significantly. Nanostructure particles could be found by field-emission scanning electron microscopy (FE-SEM). Our combined multi-spectroscopic study should be helpful to provide a guideline for the rapid spectroscopic analysis of freshwater in the Han River, Seoul, South Korea.

Nanostructured Raman substrates for the sensitive detection of submicrometer-sized plastic pollutants in water.

We prepared novel Raman substrates for the sensitive detection of submicron-sized plastic spheres in water. Anisotropic nanostar dimer-embedded nanopore substrates were prepared for the efficient identification of submicron-sized plastic spheres by providing internal hot spots of electromagnetic field enhancements at the tips of nanoparticles. Silver-coated gold nanostars (AuNSs@Ag) were inserted into anodized aluminum oxide (AAO) nanopores for enhanced microplastic (MP) detection. We found that surface-enhanced Raman scattering (SERS) substrates of AuNSs@Ag@AAO yielded stronger signals at the same weight percentages for polystyrene MP particles with diameters as small as 0.4 µm, whereas such behaviors could not be observed for larger MPs (diameters of 0.8 µm, 2.3 µm, and 4.8 µm). The detection limit of the submicrometer-sized 0.4 µm in our Raman measurements were estimated to be 0.005% (∼0.05 mg/g =50 ppm) along with a fast detection time of only a few min without any sample pretreatments. Our nano-sized dimensional matching substrates may provide a useful tool for the application of SERS substrates for submicrometer MP pollutants in water.

Dropwise condensation on solid hydrophilic surfaces.

Droplet nucleation and condensation are ubiquitous phenomena in nature and industry. Over the past century, research has shown dropwise condensation heat transfer on nonwetting surfaces to be an order of magnitude higher than filmwise condensation heat transfer on wetting substrates. However, the necessity for nonwetting to achieve dropwise condensation is unclear. This article reports stable dropwise condensation on a smooth, solid, hydrophilic surface (θa = 38°) having low contact angle hysteresis (<3°). We show that the distribution of nano- to micro- to macroscale droplet sizes (about 100 nm to 1 mm) for coalescing droplets agrees well with the classical distribution on hydrophobic surfaces and elucidate that the wettability-governed dropwise-to-filmwise transition is mediated by the departing droplet Bond number. Our findings demonstrate that achieving stable dropwise condensation is not governed by surface intrinsic wettability, as assumed for the past eight decades, but rather, it is dictated by contact angle hysteresis.

Greenhouse gas emissions from advanced oxidation processes in the degradation of bisphenol A: a comparative study of the H2O2/UV, TiO2 /UV, and ozonation processes.

To estimate greenhouse gas (GHG) emissions and degradation rate constants (kobs) from H2O2/UV-C, TiO2/UV-C, and ozonation processes in the degradation of bisphenol A (BPA), the laboratory scale experiments were conducted. In the H2O2/UV-C process, the fastest degradation rate constant (kobs = 0.353 min-1) was observed at 4 mM of H2O2, while the minimum GHG emission was achieved at 3 mM of H2O2. In the TiO2/UV-C process, the fastest rate constant (kobs = 0.126 min-1) was achieved at 2000 mg/L of TiO2, while the minimum GHG emission was observed at 400 mg/L of TiO2. In the ozonation process, GHG emissions were minimal at 5 mg/L of O3, but the degradation rate constant kept on increasing as the O3 concentration increased. There were three major types of GHG emissions in the advanced oxidation processes (AOPs). In the ozonation process, most of the GHG emissions were generated by electricity consumption. TiO2/UV-C process accounted for a significant portion of the GHGs generated by the use of chemicals. Finally, the H2O2/UV-C process produced similar GHG emissions from both chemical inputs and electricity consumption. The carbon footprint calculation revealed that for the treatment of 1 m3 of water contaminated with 0.04 mM BPA, the H2O2/UV-C process had the smallest carbon footprint (0.565 kg CO2 eq/m3), followed by the TiO2/UV-C process (3.445 kg CO2 eq/m3) and the ozonation process (3.897 kg CO2 eq/m3). Our results imply that the increase in removal rate constant might not be the optimal parameter for reducing GHG emissions during the application of these processes. Graphical abstract .

Concentration and distribution of per- and polyfluoroalkyl substances (PFAS) in the Asan Lake area of South Korea.

Seasonal and spatial variations in per- and polyfluoroalkyl substances (PFAS) concentrations in different environmental media in the Asan Lake area of South Korea were investigated by measuring liquid chromatography-tandem mass spectrometry (LC-MS/MS). The mean concentrations of Σ16 PFAS in the different media were in the ranges of 20.7-98.2 pg/m3 in air, 17.7-467 ng/L in water, 0.04-15.0 ng/g dry weight (dw) in sediments, and not detected (n.d.)-12.9 ng/g dw in soils, and the mean concentrations of Σ19 PFAS in fish ranged from n.d. to 197 ng/g wet weight. The most frequently detected PFAS were perfluorooctanoic acid (PFOA) in air and soils, perfluoropentanoic acid (PFPeA) in water, and perfluorooctane sulfonate (PFOS) in sediment and fish. Long-chain PFAS species dominated over short-chain PFAS in most media samples except for the water phase. Sediment-water partition coefficients (log Kd) and bioaccumulation factors (log BAF) of PFAS were calculated using measured concentrations in water, sediments, and fish. Log Kd of PFAS tended to increase with increasing CF2 units of PFAS, and perfluorodecanoic acid (PFDA) and PFOS showed the highest log BAF value (> 3.0) in all fish species. These results indicate that longer-chain PFAS, especially PFOS, can be effectively accumulated in biota such as fish.

Occurrence and Fate of Micropollutants in Private Wastewater Treatment Facility (WTF) and Their Impact on Receiving Water.

This study investigated the occurrence and removals of micropollutants in the sewage treatment tank (STT) which is a typical private wastewater treatment facility used in the rural communities in Korea, and their impact on receiving water. STTs were selected in eight provinces to examine the regional difference in the composition of micropollutant occurrence. We measured ten selected micropollutants in influents and effluents of STTs, as well as upstream and downstream of its receiving surface water. The dominant micropollutants in the influent of the STTs were caffeine (13,346 ng/L), acetaminophen (11,331 ng/L), ibuprofen (1440 ng/L), and naproxen (1313 ng/L), in agreement with the amounts produced annually in Korea. In the effluent, caffeine (1912 ng/L), acetaminophen (1586 ng/L), naproxen (475 ng/L), and ibuprofen (389 ng/L) were detected in relatively high concentrations. The composition of micropollutants in STT influents showed little regional variation by provinces, suggesting that the consumption pattern of these micropollutants did not show regional variation. The removal efficiencies of the selected micropollutants at the STTs ranged from 12% (carbamazepine) to 88% (acetaminophen), lower than typical removal by sewage treatment plants (STPs). This result is probably due to the automatic operation systems and simple treatment processes in STTs compared with STPs. The concentrations of selected micropollutants upstream of the receiving water were generally lower compared with those observed downstream, indicating that effluent from STTs was the main source. The per capita discharge loads of STTs and annual emissions rates (kg/year) from private wastewater treatment facilities were estimated for the selected micropollutants.

Effect of nitrate, carbonate/bicarbonate, humic acid, and H2O2 on the kinetics and degradation mechanism of Bisphenol-A during UV photolysis.

In this study, the effects of natural water components (nitrate, carbonate/bicarbonate, and humic acid) on the kinetics and degradation mechanisms of bisphenol A (BPA) during UV-C photolysis and UV/H2O2 reaction were examined. The presence of NO3- (0.04-0.4 mM) and CO32-/HCO3- (0.4-4 mM) ions increased BPA degradation during UV photolysis. Humic acid less than 3 mg/L promoted BPA degradation, but greater than 3 mg/L of humic acid inhibited BPA degradation. During the UV/H2O2 reaction, all water matrix components acted as radical scavengers in the order of humic acid > CO32-/HCO3- > NO3-. All of the degradation reactions agreed with the pseudo-first-order kinetics. While eight byproducts (m/z = 122, 136, 139, 164, 181, 244, 273, 289) were identified in UV-C/NO3- photolysis reaction, four (m/z = 122, 136, 164, 244) and three byproducts (m/z = 122, 136, 164) were observed during UV-C/NO3-/CO32-/HCO3- and UV-C/CO32-/HCO3- reactions. Nitrogenated and hydrogenated byproducts were first observed during the UV-C/NO3- photolysis, but only hydrogenated byproducts as adducts were detected during the UV-C/NO3-/CO32-/HCO3- photolysis. Nitrogenated and hydrogenated byproducts were formed in the early stage of degradation by OH or NO2 radicals, and these byproducts were subsequently degraded into smaller compounds with further reaction during UV-C/NO3- and UV-C/NO3-/CO32-/HCO3- reactions. In contrast, BPA was directly degraded into smaller compounds by ß-scission of the isopropyl group by CO3-/HCO3 radicals during UV-C/CO32-/HCO3- reaction. Our results imply that the water components can change the degradation mechanism of BPA during UV photolysis.

Nanoscale-Agglomerate-Mediated Heterogeneous Nucleation.

Water vapor condensation on hydrophobic surfaces has received much attention due to its ability to rapidly shed water droplets and enhance heat transfer, anti-icing, water harvesting, energy harvesting, and self-cleaning performance. However, the mechanism of heterogeneous nucleation on hydrophobic surfaces remains poorly understood and is attributed to defects in the hydrophobic coating exposing the high surface energy substrate. Here, we observe the formation of high surface energy nanoscale agglomerates on hydrophobic coatings after condensation/evaporation cycles in ambient conditions. To investigate the deposition dynamics, we studied the nanoscale agglomerates as a function of condensation/evaporation cycles via optical and field emission scanning electron microscopy (FESEM), microgoniometric contact angle measurements, nucleation statistics, and energy dispersive X-ray spectroscopy (EDS). The FESEM and EDS results indicated that the nanoscale agglomerates stem from absorption of sulfuric acid based aerosol particles inside the droplet and adsorption of volatile organic compounds such as methanethiol (CH3SH), dimethyl disulfide (CH3SSCH), and dimethyl trisulfide (CH3SSSCH3) on the liquid-vapor interface during water vapor condensation, which act as preferential sites for heterogeneous nucleation after evaporation. The insights gained from this study elucidate fundamental aspects governing the behavior of both short- and long-term heterogeneous nucleation on hydrophobic surfaces, suggest previously unexplored microfabrication and air purification techniques, and present insights into the challenges facing the development of durable dropwise condensing surfaces.

Degradation mechanisms of Microcystin-LR during UV-B photolysis and UV/H2O2 processes: Byproducts and pathways.

The removal and degradation pathways of microcystin-LR (MC-LR, [M+H]+ = 995.6) in UV-B photolysis and UV-B/H2O2 processes were examined using liquid chromatography-tandem mass spectrometry. The UV/H2O2 process was more efficient than UV-B photolysis for MC-LR removal. Eight by-products were newly identified in the UV-B photolysis ([M+H]+ = 414.3, 417.3, 709.6, 428.9, 608.6, 847.5, 807.4, and 823.6), and eleven by-products were identified in the UV-B/H2O2 process ([M+H]+ = 707.4, 414.7, 429.3, 445.3, 608.6, 1052.0, 313.4, 823.6, 357.3, 245.2, and 805.7). Most of the MC-LR by-products had lower [M+H]+ values than the MC-LR itself during both processes, except for the [M+H]+ value of 1052.0 during UV-B photolysis. Based on identified by-products and peak area patterns, we proposed potential degradation pathways during the two processes. Bond cleavage and intramolecular electron rearrangement by electron pair in the nitrogen atom were the major reactions during UV-B photolysis and UV-B/H2O2 processes, and hydroxylation by OH radical and the adduct formation reaction between the produced by-products were identified as additional pathways during the UV-B/H2O2 process. Meanwhile, the degradation by-products identified from MC-LR during UV-B/H2O2 process can be further degraded by increasing H2O2 dose.

Desorption of micropollutant from spent carbon filters used for water purifier.

In this study, to examine the accumulated micropollutants in the spent carbon filter used in the water purifier, first, the method to desorb micropollutant from the activated carbon was developed and optimized. Then, using this optimized desorption conditions, we examined which micropollutants exist in spent carbon filters collected from houses in different regions in Korea where water purifiers were used. A total of 11 micropollutants (caffeine (CFF), acetaminophen (ACT), sulfamethazine (SMA), sulfamethoxazole (SMZ), metoprolol (MTP), carbamazepine (CBM), naproxen (NPX), bisphenol-A (BPA), ibuprofen (IBU), diclofenac (DCF), and triclocarban (TCB)) were analyzed using LC/MS-MS from the spent carbon filters. CFF, NPX, and DCF had the highest detection frequencies (>60%) in the carbon filters (n = 100), whereas SMA, SMZ, and MTP were only detected in the carbon filters, but not in the tap waters (n = 25), indicating that these micropollutants, which exist less than the detection limit in tap water, were accumulated in the carbon filters. The regional micropollutant detection patterns in the carbon filters showed higher levels of micropollutants, especially NPX, BPA, IBU, and DCF, in carbon filters collected in the Han River and Nakdong River basins where large cities exist. The levels of micropollutants in the carbon filter were generally lower in the regions where advanced oxidation processes (AOPs) were employed at nearby water treatment plants (WTPs), indicating that AOP process in WTP is quite effective in removing micropollutant. Our results suggest that desorption of micropollutant from the carbon filter used can be a tool to identify micropollutants present in tap water with trace amounts or below the detection limit.

Emission of greenhouse gases from waste incineration in Korea.

Greenhouse gas (GHG) emission factors previously reported from various waste incineration plants have shown significant variations according to country-specific, plant-specific, and operational conditions. The purpose of this study is to estimate GHG emissions and emission factors at nine incineration facilities in Korea by measuring the GHG concentrations in the flue gas samples. The selected incineration plants had different operation systems (i.e., stoker, fluidized bed, moving grate, rotary kiln, and kiln & stoker), and different nitrogen oxide (NOx) removal systems (i.e., selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR)) to treat municipal solid waste (MSW), commercial solid waste (CSW), and specified waste (SW). The total mean emission factors for A and B facilities for MSW incineration were found to be 134 ± 17 kg CO2 ton-1, 88 ± 36 g CH4 ton-1, and 69 ± 16 g N2O ton-1, while those for CSW incineration were 22.56 g CH4 ton-1 and 259.76 g N2O ton-1, and for SW incineration emission factors were 2959 kg CO2 ton-1, 43.44 g CH4 ton-1 and 401.21 g N2O ton-1, respectively. Total emissions calculated using annual incineration for MSW were 3587 ton CO2-eq yr-1 for A facility and 11,082 ton CO2-eq yr-1 for B facility, while those of IPCC default values were 13,167 ton CO2-eq yr-1 for A facility and 32,916 ton CO2-eq yr-1, indicating that the emissions of IPCC default values were estimated higher than those of the plant-specific emission factors. The emission of CSW for C facility was 1403 ton CO2-eq yr-1, while those of SW for D to I facilities was 28,830 ton CO2-eq yr-1. The sensitivity analysis using a Monte Carlo simulation for GHG emission factors in MSW showed that the GHG concentrations have a greater impact than the incineration amount and flow rate of flue gas. For MSW incineration plants using the same stoker type in operation, the estimated emissions and emission factors of CH4 showed the opposite trend with those of NO2 when the NOx removal system was used, whereas there was no difference in CO2 emissions.

Effects of molecular size fraction of DOM on photodegradation of aqueous methylmercury.

This study investigated the photodegradation kinetics of MeHg in the presence of various size fractions of dissolved organic matter (DOM) with MW < 3.5 kDa, 3.5 < MW < 10 kDa, and MW > 10 kDa. The DOM fraction with MW < 3.5 kDa was most effective in MeHg photodegradation. Increasing UV intensity resulted in the increase of photodegradation rate of the MeHg in all size of DOM fractions. Higher rates of MeHg degradation was observed at higher pH. For the portion of MW < 3.5 kDa, the photodegradation rate of MeHg increased with increasing DOM concentration, indicating that radicals such as singlet oxygen (1O2) radicals can be effectively produced by DOM. At higher portion of MW > 3.5 kDa, the inhibition of MeHg degradation was observed due to the effect of DOM photo-attenuation. Our result indicates that radical mediated reaction is the main mechanism of photodegradation of MeHg especially in the presence of MW < 3.5 kDa. Our results imply that the smaller molecular weight fraction (MW < 3.5 kDa) of DOM mainly increased the photodegradation rate of MeHg.