Copper-Based Two-Dimensional Metal-Organic Frameworks for Fenton-like Photocatalytic Degradation of Methylene Blue under UV and Sunlight Irradiation.

To efficiently degrade organic pollutants, photocatalysts must be effective under both ultraviolet (UV) radiation and sunlight. We synthesized a series of new metal-organic frameworks by using mild hydrothermal conditions. These frameworks incorporate three distinct bipyridyl ligands: pyrazine (pyr), 4,4'-bipyridine (bpy), and 1,2-bis(4-pyridyl)ethane (bpe). The resulting compounds are denoted as [Cu(pyz)(H2O)2MF6], [Cu(bpy)2(H2O)2]·MF6, and [Cu(bpe)2(H2O)2]·MF6·H2O [M = Zr (1, 3, and 5) and Hf (2, 4, and 6)]. All six compounds exhibited a two-dimensional crystal structure comprising infinitely nonintersecting linear chains. Compound 3 achieved 100% degradation of methylene blue (MB) after 8 min under UV irradiation and 100 min under natural sunlight in the presence of H2O2 as the electron acceptor. For compound 5, 100% MB degradation was achieved after 120 min under sunlight and 10 min under UV light. Moreover, reactive radical tests revealed that the dominant species involved in photocatalytic degradation are hydroxyl (•OH), superoxide radicals (•O2-), and photogenerated holes (h+). The photodegradation process followed pseudo-first-order kinetics, with photodegradation rate constants of 0.362 min-1 (0.039 min-1) for 3 and 0.316 min-1 (0.033 min-1) for 5 under UV (sunlight) irradiation. The developed photocatalysts with excellent activity and good recyclability are promising green catalysts for degrading organic pollutants during environmental decontamination.

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.

Temporal-spatial variation and environmental risk assessment of pharmaceuticals in tributaries of the Han River watershed, South Korea.

Eight compounds from three categories of pharmaceuticals [5 antibiotics, 2 non-steroidal anti-inflammatory drugs, and 1 anti-epileptics] were monitored at 24 sites in the tributaries of the Han River watershed in South Korea, 2016. The seasonal occurrence, temporal-spatial variation, potential compound source(s), and a risk assessment of this watershed, which is the largest drinking water source in the country, were investigated. Clarithromycin was detected most frequently (72.2%) with the greatest median concentration (0.151 ± 0.072 µg L-1), followed by carbamazepine and sulfamethoxazole. The seasonality of the pharmaceuticals was observed, with higher concentrations and detection frequencies in spring than in summer and autumn; this was possibly caused by lower levels of microbial activities associated with lower water temperatures than other seasons. In terms of geographical variation, urban areas had higher pharmaceutical concentrations than rural areas, which was attributed to the former's high population density and largest wastewater treatment plants (WWTPs) regardless of season. The total concentration and detection frequency of WWTPs were 12.4 and 2.5 times higher in downstream sites than upstream sites, thereby conveying that WWTPs were the main source for the presence of pharmaceuticals in tributaries. According to the results produced from calculations of the risk quotient (RQ) of aquatic organisms, clarithromycin and sulfamethazine were identified as posing relatively high ecological risk (RQ > 1) during the spring that was identified for this study. This study can provide policymakers with scientific support for prioritizing pollutant management and collections of global data on emerging pollutants.

Pharmaceutical compounds in tributaries of the Han River watershed, South Korea.

The Han River watershed is the largest and most important source of drinking water for the residents of the Seoul metropolitan area and the Gyeonggi province in South Korea. The tributaries of the watershed are vulnerable to contamination by effluents from nearby wastewater treatment plants (WWTPs) and non-point sources. In this study, a one-year monitoring study was performed to investigate the occurrence of 13 pharmaceuticals in 24 tributaries of the Han River watershed in October 2015. From the 13 pharmaceuticals, 12 were found in at least one sample, with the exception of chlortetracycline, which was not detected. The three most frequently detected compounds were clarithromycin (95.8%), carbamazepine (66.7%), and lincomycin (62.5%). Compounds found in high concentrations included clarithromycin (5.2675 µg L-1), ibuprofen (1.9646 µg L-1), and carbamazepine (1.1009 µg L-1). The total concentration of 12 pharmaceuticals in the Seoul metropolitan area (0.7128 µg L-1) was higher than that in the Gyeonggi area (0.3177 µg L-1) possibly due to the large-scale WWTPs located upstream. However, in IHR-3, which is located at the very upstream of the tributary and is not impacted by a WWTP, pharmaceuticals were not detected. This can be explained by the fact that most pharmaceuticals derived from WWTPs are related to human activity. The risk quotients (RQs) for the target pharmaceuticals were calculated on the basis of their presence in tributaries, and all pharmaceuticals presented RQs < 0.01, indicating that potential environmental impacts should be low. These results will be useful to monitor and assess the potential environmental risks of pharmaceuticals in the surface water.

Hazard Classification of Household Chemical Products in Korea according to the Globally Harmonized System of Classification and labeling of Chemicals.

OBJECTIVES: This study was conducted to review the validity of the need for the application of the Globally Harmonized System of Classification and Labeling of Chemicals (GHS) to household chemical products in Korea. The study also aimed to assess the severity of health and environmental hazards of household chemical products using the GHS. METHODS: 135 products were classified as 'cleaning agents and polishing agents' and 98 products were classified as 'bleaches, disinfectants, and germicides.' The current status of carcinogenic classification of GHS and carcinogenicity was examined for 272 chemical substances contained in household chemical products by selecting the top 11 products for each of the product categories. In addition, the degree of toxicity was assessed through analysis of whether the standard of the Republic of Korea's regulations on household chemical products had been exceeded or not. RESULTS: According to GHS health and environmental hazards, "acute toxicity (oral)" was found to be the highest for two product groups, 'cleaning agents and polishing agents', and 'bleaches, disinfectants, and germicides' (result of classification of 233 household chemical products) at 37.8% and 52.0% respectively. In an analysis of carcinogenicity assuming a threshold of IARC 2B for the substances in household chemical products, we found 'cleaning agents and polishing agents' to contain 12 chemical substances and 'bleaches, disinfectants, and germicides' 11 chemical substances. CONCLUSION: Some of the household chemical products were found to have a high hazard level including acute toxicity and germ cell mutagenicity, carcinogenicity, and reproductive toxicity. Establishing a hazard information delivery system including the application of GHS to household chemical products in Korea is urgent as well.