Evaluation of spatial and temporal changes in illicit drug use in the Taipei metropolitan area via wastewater-based epidemiology.

Taiwan, identified as pivotal in the Asian drug trafficking chain, has been experiencing a surge in illicit drug-related issues. Wastewater-based epidemiology (WBE) has emerged as a promising approach for comprehensive evaluation of actual illicit drug usage. This study presents the first WBE investigation of illicit drug consumption in Taiwan based on the analysis of wastewater from four wastewater treatment plants (WWTPs) in the Taipei metropolitan area. Additionally, it demonstrates a high correlation between the amounts of illicit drugs seized and influent concentrations over an extended period of time. The reliability of solid-phase extraction and analysis via high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was validated for 16 illicit drugs (methamphetamine, ketamine, cocaine, codeine, methadone, morphine, meperidine, fentanyl, sufentanil, para-methoxyamphetamine (PMA), para-methoxymethamphetamine (PMMA), 3,4-methylenedioxymethamphetamine (MDMA), cathinone, methcathinone, mephedrone (MEPH), and 4-methylethcathinone (4-MEC)). Methamphetamine, ketamine, and 4-MEC were consistently detected in all wastewater samples, underscoring their prevalence in the Taipei metropolitan area. Biochemical oxygen demand (BOD) and ammonia nitrogen (ammonia N) were employed to reduce uncertainty in estimations of population size during back-calculation of illicit drug consumption. The results indicate that methamphetamine was the most consumed drug (175-740 mg day-1 1000 people-1), followed by ketamine (22-280 mg day-1 1000 people-1). In addition, urban-related WWTPs exhibited higher consumption of methamphetamine and ketamine than did the suburban-related WWTP, indicating distinct illicit drug usage patterns between suburban and urban regions. Moreover, an examination of temporal trends in wastewater from the Dihua WWTP revealed a persistent predominance of ketamine and methamphetamine, consistent with statistical data pertaining to seizure quantities and urine test results. The study provides encouraging insight into spatial and temporal variations in illicit drug usage in the Taipei metropolitan area, emphasizing the complementary role of WBE in understanding trends in illicit drug abuse.

Sunlight enhanced the formation of tribromomethane from benzotriazole degradation during the sunlight/free chlorine treatment in the presence of bromide.

The coexistence of free chlorine and bromide under sunlight irradiation (sunlight/FC with Br-) is unavoidable in outdoor seawater swimming pools, and the formation of brominated disinfection byproducts could act more harmful than chlorinated disinfection byproducts. In this study, benzotriazole was selected as a model compound to investigate the degradation rate and the subsequent formation of disinfection byproducts via sunlight/FC with Br- process. The rate constants for the degradation of benzotriazole under pseudo first order conditions in sunlight/FC with Br- and sunlight/FC are 2.3 ± 0.07 × 10-1 min-1 and 6.0 ± 0.7 × 10-2 min-1, respectively. The enhanced degradation of benzotriazole can be ascribed to the generation of HO•, bromine species, and reactive halogen species (RHS) during sunlight/FC with Br-. Despite the fact that sunlight/FC with Br- process enhanced benzotriazole degradation, the reaction results in increasing tribromomethane (TBM) formation. A high concentration (37.8 µg/L) of TBM was detected in the sunlight/FC with Br-, which was due to the reaction of RHS. The degradation of benzotriazole was notably influenced by the pH value (pH 4 - 11), the concentration of bromide (0 - 2 mM), and free chlorine (1 - 6 mg/L). Furthermore, the concentration of TBM increased when the free chlorine concentrations increased, implying the formation potential of harmful TBM in chlorinated seawater swimming pools.

Reactive chlorine species in the enhanced degradation of UV stabilizers during the sunlight/free chlorine process.

Benzotriazole (BT) and 5-methyl-1H-benzotriazole (5-MeBT) are the most commonly used UV stabilizers and recalcitrant contaminants that are widely distributed in aquatic environments. The novelty of this study was to investigate the role of RCSs in the enhanced degradation of BT and 5-MeBT during the sunlight/free chlorine process. The results showed that sunlight/free chlorine could enhance the degradation of BT and 5-MeBT compared with that obtained with sunlight irradiation and chlorination alone, and this process was well described by pseudo-first-order kinetics. The degradation rate constants of BT and 5-MeBT during sunlight/free chlorine treatment at pH 7 were 0.094 ± 0.001 min-1 and 0.134 ± 0.002 min-1, respectively. The degradation rates further increased with increases in the chlorine dosage and under alkaline conditions (3.818 ± 0.243 min-1 for BT and 7.754 ± 0.716 min-1 for 5-MeBT at pH 9). The enhanced removal obtained during the sunlight/free chlorine process could be attributed to the generation of HO• and reactive chlorine species (RCSs), such as Cl• and ClO•. Under alkaline conditions, RCSs were the dominant reactive species, and their contribution increased from 21.2% to 98.7% with increases in the pH from 7 to 9; this phenomenon was due to changes in free chlorine and BT speciation. Radical scavenging tests further verified that BT was mainly decomposed by ClO•, and ClO• showed high reactivity toward deprotonated BT through second-order rate constant estimation. A byproduct analysis demonstrated that BT underwent hydroxylation and chlorine substitution, and a high yield of 1-chlorobenzotriazole (1-ClBT) formation was observed. Even though the sunlight/free chlorine process resulted in a low level of mineralization, no Microtox® toxicity was detected in the treated solutions. Briefly, the significant contribution of ClO• to BT removal under alkaline conditions implies that sunlight/free chlorine could be utilized in a broader range of treatment conditions.

Characterization and Prediction of Physical Properties of Luanta Fir Wood with Vacuum Hydrothermal Treatment.

This study used the luanta fir (Cunninghamia konishii Hayata) wood, one of the most used wood construction and building materials in Taiwan, as specimens to examine the impact of different conditions of vacuum hydrothermal (VH) treatment on the physical properties of this wood. A prediction model for these properties was created using a nondestructive spectroscopy technique. The test results revealed that the mass loss, moisture exclusion efficiency, anti-swelling efficiency, color difference, and surface contact angle of the VH-treated wood all increased under increasing heat treatment temperature and time. Moreover, the use of near-infrared (NIR) spectroscopy in creating the prediction model for the physical properties of the VH-treated luanta fir wood revealed that the ratios of performance to deviation (RPD) for mass loss, equilibrium moisture content, and color difference were all above 2.5, indicating a high prediction accuracy. These results suggested that an NIR spectrometer can serve as a useful instrument for the accurate prediction of the physical properties or for controlling the quality of VH-treated wood.

Enhanced MnO2 oxidation of methotrexate through self-sensitized photolysis.

MnO2, which is ubiquitous in soil and sediment in natural water environments, may play an important role in the photolysis of contaminants by sunlight, but the interactions between MnO2 and contaminants in aqueous environments under sunlight irradiation have not been investigated. In this study, the simultaneous presence of sunlight and MnO2 significantly enhanced the degradation efficiency of methotrexate (MTX). Accordingly, we hypothesized that the overall enhancement of this synergistic reaction is due to the additional production of Mn(III) via MTX self-sensitized photolysis. The pseudo-first-order kinetic model for the photoreaction of MTX with MnO2 (Light/MTX+MnO2) during the initial reaction kinetics (0-2 h) revealed a rate constant of 0.43 h1 ([MTX] = 20 µM, [MnO2] = 200 µM, and pH = 7), which is faster than that obtained with sunlight alone (0.14 h1) or MnO2 alone; Mn(II) and Mn(III) were formed at concentrations of 24.3 ± 1.0 µM and 14.8 ± 1.4 µM, respectively. Dissolved Mn(III) species were identified as the main oxidant species responsible for the degradation of MTX. Two reaction pathways for the production of Mn(III) through Light/MTX+MnO2 were proposed; MTX acts as a photosensitizer to produce 3MTX* responsible for the reduction of MnO2 to Mn(III), whereas O2• participates in the oxidation of Mn(Ⅱ) to Mn(Ⅲ). Byproduct analysis demonstrated that the Mn(III) generated in the Light/MTX+MnO2 system enhances C－N bond cleavage, ketonization, and hydrolysis pathways in the MTX transformation.

Photoaged polystyrene microplastics serve as photosensitizers that enhance cimetidine photolysis in an aqueous environment.

Microplastics (MPs) have received much attention in recent years because of their continuous photoaging process in aquatic environments. However, little research has been conducted on the photochemistry of aged microplastics and the associated effects on coexisting pharmaceuticals. This study investigated the photodegradation of cimetidine via aged polystyrene microplastics (PS-MPs) with different aging times (0-7 d) under simulated sunlight irradiation (700 W/m2). PS-MPs with 5 d of aging time resulted in much faster cimetidine degradation (>99%) after 2 h of irradiation than pristine PS-MPs (<8%). The enhanced photodegradation of cimetidine by aged PS-MPs was related to the increase in chromophoric oxygenated groups (CO, C-O) followed by redshifted absorbance through the photoaging process, which induced the formation of the environmentally persistent free radicals (EPFRs) OH, 1O2 and 3PS*. However, only 1O2 and 3PS* contributed to enhanced cimetidine photodegradation, with 1O2 playing a more important role in our case. This work also demonstrated that other compounds that are susceptible to indirect photolysis, such as codeine and morphine, are likewise significantly degraded under irradiation in the presence of aged PS-MPs. Although previous studies have reported how MPs can increase the persistence of contaminants, this study demonstrates that MPs can serve as photosensitizers and alter the fate of coexisting pharmaceuticals in aquatic environments.

Characterization and Prediction of Mechanical and Chemical Properties of Luanta Fir Wood with Vacuum Hydrothermal Treatment.

Since the chemical composition of wood is closely related to its mechanical properties, chemical analysis techniques such as near-infrared (NIR) spectroscopy provide a reasonable non-destructive method for predicting wood strength. In this study, we used NIR spectra with principal component analysis (PCA) to reveal that vacuum hydrothermal (VH) treatment causes degradation of hemicellulose as well as the amorphous region of cellulose, resulting in lower hydroxyl and acetyl group content. These processes increase the crystallinity of the luanta fir wood (Cunninghamia konishii Hayata), which, in turn, effectively increases its compressive strength (σc,max), hardness, and modulus of elasticity (MOE). The PCA results also revealed that the primary factors affecting these properties are the hemicellulose content, hydroxyl groups in the cellulose amorphous region, the wood moisture content, and the relative lignin content. Moreover, the ratios of performance deviation (RPDs) for the σc,max, shear strength (σs,max), hardness, and modulus of rupture (MOR) models were 1.49, 1.24, 1.13, and 2.39, indicating that these models can be used for wood grading (1.0 < RPD < 2.5). Accordingly, NIR can serve as a useful tool for predicting the mechanical properties of VH-treated wood.

Intracellular organic matter from Chlorella vulgaris enhances the photodegradation of acetaminophen.

Algae is able to accelerate the photodegradation rate of contaminants under sunlight irradiation, and this process can be attributed to algal substances, namely, intracellular organic matter (IOM) and extracellular organic matter (EOM). This study aimed to investigate the efficiencies and mechanisms of the photodegradation of three pharmaceuticals - acetaminophen (ACE), codeine (COD) and cephradine (CFD) - in the presence of Chlorella vulgaris and its algal substances. The result shows that a much higher photodegradation rate of acetaminophen was obtained in the presence of IOM (kobs = 0.250 hr-1) than in the presence of EOM (kobs = 0.060 hr-1). The photodegradation mechanisms of acetaminophen were demonstrated and verified by scavenger experiments and probe tests. The major reactive species for acetaminophen photodegradation was triplet-state IOM (3IOM∗), which contributed 93.52% of the photodegradation, while ⋅OH was the secondary contributor (5.60%), with 1O2 contributing the least (0.88%). Chlorella vulgaris also effectively enhanced the photodegradation of codeine and cephradine. However, the photodegradation behaviors of codeine and cephradine in the presence of algal substances were different from those of acetaminophen, indicating that the photodegradation mechanisms might depend on the type of compound. This study not only demonstrates the effectiveness of algal substances in the photodegradation of acetaminophen, codeine and cephradine under sunlight irradiation but also provides a comprehensive study on the photodegradation mechanisms of acetaminophen in the presence of algal substances.

Degradation of methadone by the sunlight/FC process: Kinetics, radical species participation and influence of the water matrix.

Free chlorine sunlight photolysis (sunlight/FC) markedly enhances the degradation rate of methadone, a synthetic opioid used medically, over that obtained using sunlight alone. The pseudo-first-order rate constants of methadone degradation under acidic conditions ([methadone] = 0.2 µM, [free chlorine] = 4 µM, and pH = 4) for sunlight/FC and sunlight photolysis are 7.0 ±â€¯1.1 × 10-2 min-1 and 1.4 ±â€¯0.2 × 10-2 min-1, respectively. The improved methadone degradation can be attributed to the production of HO and reactive chlorine species (RCS) during sunlight/FC photolysis. HO and RCS predominantly accounted for degradation during sunlight/FC photolysis under acidic and neutral conditions, while direct photolysis was the major contributor towards methadone degradation in alkaline conditions. The initial pH (pH 4-11) and free chlorine concentration (1-6 µM) significantly influenced the overall degradation efficiency of methadone. The presence of HCO3-, Cl- and dissolved organic matters, which may competitively react with HO and RCS, retard the degradation of methadone in synthetic wastewater. Consequently, a 50% lower methadone degradation rate was observed when deionized (DI) water was replaced with tap water. These results emphasize the need to consider different water matrices when applying sunlight/FC photolysis for water treatment.

Flavones Isolated from Scutellariae radix Suppress Propionibacterium Acnes-Induced Cytokine Production In Vitro and In Vivo.

Scutellariae radix, the root of Scutellaria baicalensis, has long been applied in traditional formulations and modern herbal medications. Propionibacterium acnes (P. acnes) in follicles can trigger inflammation and lead to the symptom of inflammatory acnes vulgaris. This study was aimed at evaluating the effect of Scutellariae radix extract and purified components isolated from it on inflammation induced by P. acnes in vitro and in vivo. The results showed the ethyl acetate (EA) soluble fraction from the partition of crude ethanolic extract from Scutellariae radix inhibited P. acnes-induced interleukin IL-8 and IL-1ß production in human monocytic THP-1 cells. Seven flavones were isolated from the EA fraction by repeated chromatographies, and identified as 5,7-dihydroxy-6-methoxyflavone (FL1, oroxylin), 5,7-dihydroxy-8-methoxyflavone (FL2, wogonin), 5-hydroxy-7,8-dimethoxyflavone (FL3, 7-O-methylwogonin), 5,6'-dihydroxy-6,7,8,2'-tetramethoxy flavone (FL4, skullcapflavone II), 5,7,4'-trihydroxy-8-methoxyflavone (FL5), 5,2',6'-trihydroxy-7,8-dimethoxyflavone (FL6, viscidulin II), and 5,7,2',5'-tetrahydroxy-8,6'-dimethoxyflavone (FL7, ganhuangenin). They all significantly suppressed P. acnes-induced IL-8 and IL-1ß production in THP-1 cells, and FL2 exerted the strongest effect with half maximal inhibition (IC50) values of 8.7 and 4.9 µM, respectively. Concomitant intradermal injection of each of the seven flavones (20 µg) with P. acnes effectively attenuated P. acnes-induced ear swelling, and decreased the production of IL-6 and tumor necrosis factor-α in ear homogenates. Our results suggested that all the seven flavones can be potential therapeutic agents against P. acnes-induced skin inflammation.