Photochemical fate of ß-blocker pindolol in riverine and its downstream coastal waters.

Pindolol (PIN) is a commonly used ß-blocker drug and has been frequently detected in various natural waters. Comprehensive understanding of its environmental photochemical transformation is necessary to assess its environmental risk. In this study, the photodegradation kinetics and mechanisms of PIN in both freshwater and coastal water were investigated for the first time. The photodegradation experiments were carried out by steady-state photochemical experiment under simulated sunlight irradiation. The results showed that the photodegradation rate of PIN in the freshwater of the Pearl River estuary was significantly faster than that in its downstream coastal water. In river water, PIN can undergo both direct photolysis and indirect photolysis induced by riverine dissolved organic matter (DOM) mainly through excited triplet-state of DOM and singlet oxygen, while direct photolysis dominated its degradation in coastal water. The promotion effect was found to be much greater for Suwannee River Natural Organic Matter (SRNOM) than that of the sampled riverine DOM, due to its high steady-state concentrations of reactive species. Interestingly, coastal DOM in northern and southern China were found to have similar promotion effects on PIN photodegradation for the first time, but both less than that of riverine DOM. A total of seven degradation products of PIN resulting from hydroxylation, hydrogen abstraction and cleavage of ether bond were identified. Biological toxicity of one products were found to be higher than that of PIN. These results are of significance for knowing the persistence and ecological risk of PIN in natural waters.

Photo-production of excited triplet-state of dissolved organic matters in inland freshwater and coastal seawater.

The excited triplet-state of dissolved organic matter (3DOM*) is a major reactive intermediate in sunlit waters. Its quantum yield is important in understanding the fate of organic micropollutants. The degradation efficiency of its chemical probe, 2,4,6-trimeythlphenol (fTMP), is generally used as a proxy of the quantum yield. However, fTMP has been described and modelled only for freshwater systems. Therefore, this study quantified fTMP in inland freshwater and coastal seawater sampled in Japan by conducting steady-state photochemical experiments. Optical properties of water were then used to model fTMP. Results indicated that the inland freshwater DOM originated mainly from terrestrial sources, while the coastal seawater DOM were microbial-dominated. On average, inland freshwater exhibited lower fTMP (61.2 M-1) than coastal seawater (79.7 M-1) and the coastal seawater exhibited significant variations in the proportion of high-energy 3DOM* (> 250 kJ/mol). In addition, E2:E3 (ratio of absorbance at 254 to 365 nm) was positively correlated with fTMP of inland freshwater, coastal seawater, and the overall dataset. Catchment conditions such as forest coverage also influenced the production of 3DOM* and high-energy 3DOM* in inland freshwater. Furthermore, the developed models estimated fTMP based on the optical properties of both freshwater and seawater, providing valuable insights about 3DOM* photochemistry in the aquatic environment.

Insights into the mechanisms of natural organic matter on the photodegradation of indomethacin under natural sunlight and simulated light irradiation.

Indomethacin (INDO) is an antipyretic and analgesic pharmaceutical that has been widely detected in the aquatic environment. Photodegradation is an essential pathway for removal of INDO in sunlit surface water, however the effect of dissolved organic matter (DOM) on its photodegradation and the ecotoxicity of photodegradation products are largely unknown. In this study, the effect of DOM on the photodegradation of INDO under both natural and simulated light irradiation was studied. The results showed that indirect photolysis is the main photodegradation pathway of INDO in presence of DOM where 3DOM* plays the most important promoting role. Compared to commercial DOM (SRNOM and SRFA), DOM extracted from local-lake water (SLDOM) promoted the photodegradation to the highest extent. Although the steady-state concentrations of 3DOM* of SRNOM and SRFA were higher than SLDOM, their inhibition effect surpassed SLDOM namely higher light screening effect and phenolic antioxidant concentrations. The photodegradation pathway in pure water is different from that in DOM system where the decarboxylation of acetic acid chain and the oxidative fracture of indole ring are the main degradation pathways. Density Functional Theory (DFT) calculation further supports the proposed degradation pathways of INDO. ECOSAR calculation showed that the toxicity of INDO photodegradation products to aquatic organisms may maintain or even exceed its parent compound. Therefore, comprehensive understanding of the impact of DOM on the photodegradation of INDO is of crucial significance for evaluating its ecological risk in the natural environment.

Apparent quantum yield for photo-production of singlet oxygen in reservoirs and its relation to the water matrix.

Man-made reservoirs are important for human daily lives and offer different functions, however they are contaminated due to anthropogenic activities. Dissolved organic matter (DOM) from each reservoir is unique in composition, which further determines its photo-reactivity. Thus, this study aimed to investigate the photo-reactivity of reservoir DOM in terms of the quantum yield for photo-production of singlet oxygen (Ф1O2). We sampled surface water of 50 reservoirs in Japan and determined their Ф1O2 using simulated sunlight together with bulk water analysis. Their Ф1O2 ranged from 1.46 × 10-2 to 6.21 × 10-2 (mean, 2.55 × 10-2), which was identical to those of lakes and rivers reported in the literature, but lower than those of wetland water and wastewater. High-energy triplet-state of DOM accounted for 59.4% of the 1O2 production in the reservoir water on average. Among the bulk water properties, the spectral slope of wavelength from 350 to 400 nm (S350-400) was statistically detected as the most important predictor for Ф1O2. Furthermore, the multiple linear regression model employed S350-400 and the biological index as predictors with no intercorrelations and reasonable accuracy (r2 = 0.86), while the random forest model showed a better accuracy (r2 = 0.90). Overall, these major findings are beneficial for understanding the photo-reactivity of reservoir waters.

Photodegradation of organic micropollutants in aquatic environment: Importance, factors and processes.

Photochemical reactions widely occur in the aquatic environment and play fundamental roles in aquatic ecosystems. In particular, solar-induced photodegradation is efficient for many organic micropollutants (OMPs), especially those that cannot undergo hydrolysis or biodegradation, and thus can mitigate chemical pollution. Recent reports indicate that photodegradation may play a more important role than biodegradation in many OMP transformations in the aquatic environment. Photodegradation can be influenced by the water matrix such as pH, inorganic ions, and dissolved organic matter (DOM). The effect of the water matrix such as DOM on photodegradation is complex, and new insights concerning the disparate effects of DOM have recently been reported. In addition, the photodegradation process is also influenced by physical factors such as latitude, water depth, and temporal variations in sunlight as these factors determine the light conditions. However, it remains challenging to gain an overview of the importance of photodegradation in the aquatic environment because the reactions involved are diverse and complex. Therefore, this review provides a concise summary of the importance of photodegradation and the major processes related to the photodegradation of OMPs, with particular attention given to recent progress on the major reactions of DOM. In addition, major knowledge gaps in this field of environmental photochemistry are highlighted.

Basic influent sewage quality reflects sewershed characteristics in Tokyo city.

Sewage comprises multifarious information on sewershed characteristics. For instance, influent sewage quality parameters (ISQPs) (e.g., total nitrogen (TN)) are being monitored regularly at all treatment plants. However, the relationship between ISQPs and sewershed characteristics is rarely investigated. Therefore, this study statistically investigated relationships between ISQPs and sewershed characteristics, covering demographic, social, and economic properties in Tokyo city as an example of a megacity. To this end, we collected ISQPs and sewershed characteristic data from 2015 to 2020 in 10 sewersheds in Tokyo city. By principal component analysis, spatial variability of ISQPs was aggregated into two principal components (89.8% contribution in total), indicating organics/nutrients and inorganic salts, respectively. Concentrations of organics/nutrients were significantly correlated with the population in sewersheds (daytime population density, family size, age distribution, etc.). Inorganic salts are significantly correlated with land cover ratios. Finally, a multiple regression model was developed for estimating the concentration of TN based on sewershed characteristics (R2=0.97). Scenario analysis using the regression model revealed that possible population movements in response to the coronavirus pandemic would substantially reduce the concentration of TN. These results indicate close relationships between ISQPs and sewershed characteristics and the potential applicability of big data of ISQPs to estimate sewershed characteristics and vice versa.

Photodegradation of propranolol in surface waters: An important role of carbonate radical and enhancing toxicity phenomenon.

Antihypertensive propranolol (PRO) is frequently detected in surface waters and has adverse effects on aquatic organisms. In this study, its photochemical fate in surface water with the aspect of kinetics, products and toxicity were investigated employing steady-state photochemistry experiments and ecotoxicity tests. The results showed that photodegradation of PRO was enhanced in river water than that in phosphate buffer where dissolved organic matter (DOM), NO3-, and HCO3- played important roles. DOM accelerated the photodegradation mainly through generation of excited triplet-state DOM while NO3- played dual roles in the photodegradation. The reaction between excited triplet-state PRO and HCO3- can generate carbonate radical (CO3·-) to promote the photodegradation. The second-order reaction rate constant between PRO and CO3·- was determined to be (3.4 ± 0.8) × 108 M-1 s-1. Eight photodegradation products were identified in the studied river water sample. Finally, the toxicity evaluated by Vibrio fischeri increased after photodegradation and three photodegradation products were responsible for the increasing toxicity, which was concluded from the significant correlation between toxicity parameters and quantity of the photodegradation products.

Photodegradation of three antidepressants in natural waters: Important roles of dissolved organic matter and nitrate.

Antidepressants have become ubiquitous emerging organic pollutants. Therefore, it is essential to investigate photodegradation of the antidepressants in environment waters for their ecological risk assessment. However, photodegradation behavior of antidepressants varied from different structures and photodegradation mechanism was rarely known for most antidepressants. Herein, citalopram (CIT), paroxetine (PAR) and fluvoxamine (FLUVO) were employed to study the photodegradation behavior of antidepressants in lake water. Results show that direct photolysis of CIT decreased when pH increased from 6 to 9 while the pH effect was not obvious on direct photolysis of FLUVO and PAR. Photodegradation of CIT occurred from its triplet-state and can undergo self-photosensitization through reaction with the generated hydroxyl radical (·OH). In lake water, PAR and FLUVO are degraded mainly via direct photolysis, while CIT is transformed mainly via indirect photolysis. Dissolved organic matter (DOM) and NO3- was proved to be the main factors affecting antidepressants photodegradation in lake water. DOM and NO3- showed inhibition effect on photodegradation of FLUVO and PAR, while promoted CIT degradation. The promotion effect of CIT was mainly through reaction with ·OH and excited triplet-state of DOM while singlet oxygen played a minor role. Based on the photodegradation products identified by MS/MS, the photodegradation pathways were proposed for CIT and PAR, respectively. For FLUVO, one (Z)-isomer degradation product was also found. Understanding the photodegradation behavior of antidepressants is vital for providing data to do ecological risk assessment.

Photodegradation of acebutolol in natural waters: Important roles of carbonate radical and hydroxyl radical.

Acebutolol (ACE) has been widely used for the treatment of cardiovascular disorders, and its photochemical fate in natural waters is a matter of concern due to its ubiquitous occurrence and its toxicity to aquatic organisms. In this study, the photodegradation of ACE in river water and synthetic waters were investigated under simulated sunlight irradiation. The results demonstrated that ACE photodegradation rate in river water was 3.2 times higher than that in pure water. Then the influences of HCO3-, NO3- and DOM on ACE photolysis were investigated under their concentrations similar with the ones in river water. ACE photodegradation was significantly enhanced in the presence of HCO3- alone, and the scavenging experiments and the electron paramagnetic resonance experiments together proved that HCO3- could be oxidized by triplet-excited state of ACE to generate CO3•-, which subsequently played a key role in ACE degradation. The presence of both NO3- and DOM also increased the ACE photodegradation rates, and •OH and 3DOM* were found to be involved in the degradation. In addition, when DOM was added to a solution with HCO3-, the enhancement effect of HCO3- on ACE photodegradation was weakened due to the scavenging of CO3•- by DOM combined with the light screening effect of DOM.

Mechanism of bicarbonate enhancing the photodegradation of ß-blockers in natural waters.

The impact of HCO3- on the photodegradation of ß-blockers was investigated under simulated sunlight irradiation. The results show that in the presence of HCO3-, the photodegradation rates increase significantly for sotalol (SOT), whereas no effects on the degradation of carvedilol and arotinolol are observed. Using quenching experiments, electron paramagnetic resonance spectra and degradation product determination, we demonstrate that carbonate radical (CO3•-) is formed by direct oxidation of HCO3- by triplet-excited SOT (3SOT*) and plays a significant role in SOT photodegradation. Competition kinetics experiments show that the three ß-blockers all have high second-order rate constants (107-108 M-1 s-1) for the reaction with CO3•-. However, only 3SOT* has a higher reduction potential that can oxidize HCO3- to produce CO3•-. Thus, enhanced SOT removal rates in the presence of HCO3- were observed. In addition, the results show that seawater DOM could increase HCO3--induced photodegradation of SOT, whereas SRNOM mainly behaves as a CO3•- quencher and decreases the removal rate of SOT. The results underscore the role of HCO3- in limiting the persistence of organic pollutants like SOT in sunlit natural waters, and especially in marine and coastal waters.

Dichlorine radicals (Cl2•-) promote the photodegradation of propranolol in estuarine and coastal waters.

Propranolol (PRO) is frequently detected in estuarine and coastal waters, which has adverse effects on estuarine and coastal ecosystems. In this study, the effects of halide ions and DOM from estuarine and coastal waters on the photochemical transformation of PRO were investigated. The results demonstrated that the presence of Br- alone exhibited slight effect on photochemical transformation of PRO, while photodegradation rates of PRO increased with the addition of 0.1-0.54 M Cl-. The quenching experiments and the laser flash photolysis experiments together demonstrated the generation of Cl2•- in the photolytic systems. Cl2•- is possibly produced through the charge separation of exciplex of 3PRO* and Cl- rather than via direct oxidation of Cl-. Additional experiments indicated that addition of seawater DOM inhibited the halide ions-sensitized photodegradation rates of PRO, which may be due to the quenching of Cl2•- by phenolic substances in DOM molecules. Compared with pure water, three new photochemical intermediates were identified in the presence of DOM or Cl-. The direct photolysis of PRO mainly reacted by hydroxyl additions, hydroxyl elimination and de-propylation, whereas electron transfer coupled with H-abstraction by Cl2•- and 3DOM* was proposed as the primary role for PRO degradation in the presence of Cl- or DOM.

Photochemistry of dissolved organic matter extracted from coastal seawater: Excited triplet-states and contents of phenolic moieties.

Coastal seawater constitutes an important ecosystem receiving inputs of organic micropollutants (OMPs) such as sulfa antibiotics from land-based sources or mariculture activities. It is necessary to investigate photodegradation of OMPs in coastal seawaters for assessing their environmental fate and risks. However, effects of coastal seawater dissolved organic matter (S-DOM) on OMPs photodegradation are largely unknown, given that chemical compositions of S-DOM are different from those of freshwater DOM. Herein, photochemical characteristics of S-DOM extracted from Dalian coastal seawaters were investigated by simulating photochemical experiment adopting sulfachloropyridazine as a case. Results show that S-DOM accelerates the photodegradation mainly through excited triplet-state DOM (3DOM*) with an apparent rate constant (4.43 × 108 M-1 s-1) ten folds of that of freshwater DOM, which is mainly due to much lower phenol contents detected in the S-DOM (0.022 mg-Gallic acid mg-C-1). The S-DOM impacted by mariculture can photogenerate more high-energy 3DOM* than those less impacted by mariculture, further contributing to the high 3DOM* reactivity. The study shows that to accurately predict photolytic persistence of OMPs in field water bodies, it is of significance to determine the second-order reaction rate constants between 3DOM* and target OMPs using DOM extracted from relevant water bodies.

Disparate effects of DOM extracted from coastal seawaters and freshwaters on photodegradation of 2,4-Dihydroxybenzophenone.

Dissolved organic matter (DOM) plays an important role in degradation of organic pollutants by photochemically-produced reactive intermediates (RIs), such as excited triplet-states of DOM (3DOM*), singlet oxygen (1O2) and hydroxyl radical (·OH). However, it is not clear whether DOM extracted from coastal seawaters (CS-DOM) and DOM derived from freshwaters (FW-DOM) exhibit similar effects on photodegradation of organic micropollutants. Herein, 2,4-dihydroxybenzophenone (BP-1) was adopted as a model compound to probe the effects of different DOM on photodegradation kinetics of organic micropollutants. Results show that the CS-DOM promotes the photodegradation of BP-1 mainly via the pathway involving 3DOM*; while 3DOM*, 1O2 and ·OH are responsible for BP-1 photodegradation in the presence of the FW-DOM. Compared with the FW-DOM, the CS-DOM undergoes more photobleaching, and contains less aromatic C=C and C=O functional groups. Although 3DOM* formation quantum yields for the CS-DOM are relatively higher than those for the FW-DOM, the CS-DOM has lower rates of light absorption, leading to lower steady-state RI concentrations for the CS-DOM. BP-1 photodegradation in the presence of the CS-DOM is faster than in the presence of the FW-DOM, due to higher second-order reaction rate constants between BP-1 and CS-3DOM* and fewer antioxidants contained in the CS-DOM.

Acoustic wave propagation in bubbly flow with gas, vapor or their mixtures.

Presence of bubbles in liquids could significantly alter the acoustic waves in terms of wave speed and attenuation. In the present paper, acoustic wave propagation in bubbly flows with gas, vapor and gas/vapor mixtures is theoretically investigated in a wide range of parameters (including frequency, bubble radius, void fraction, and vapor mass fraction). Our finding reveals two types of wave propagation behavior depending on the vapor mass fraction. Furthermore, the minimum wave speed (required for the closure of cavitation modelling in the sonochemical reactor design) is analyzed and the influences of paramount parameters on it are quantitatively discussed.

Effects of mass transfer on damping mechanisms of vapor bubbles oscillating in liquids.

The damping mechanisms play an important role in the behavior of vapor bubbles. In the present paper, effects of mass transfer on the damping mechanisms of oscillating vapor bubbles in liquids are investigated within a wide range of parameter zone (e.g. in terms of frequency and bubble Péclet number). Results of the vapor bubbles are also compared with those of the gas bubbles. Our findings reveal that the damping mechanisms of vapor bubbles are significantly affected by the mass transfer especially in the regions with small and medium bubble Péclet number. Comparing with the gas bubbles, the contributions of the mass-transfer damping mechanism for the vapor bubble case are quite significant, being the dominant damping mechanism in a wide region.

[Enhancement of functional expression of wheat peroxidase WP1 in prokaryotic system by co-transforming with hemA and hemL of Esherichia coli].

Wheat grain peroxidase 1 (WP1) belonged to class III plant peroxidase with cofactor heme, which not only has antifungal activity, but also influences the processing quality of flour. In order to enhance functional expression of WP1 in prokaryotic system by increasing endogenous heme synthesis, we constructed a recombinant plasmid pACYC-A-L containing hemA and hemL of Esherichia coli. Then, we co-transformed it into host strain T7 Express with secretive expression vector (pMAL-p4x-WP1) or non-secretive expression vector (pET21a-MBP-WP1), respectively. The MBP-WP1 fusion protein was further purified by amylose affinity chromatography and its peroxidase activity was assayed using 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonate) (ABTS) as substrate. At 12 h after induction at 28 degree, the extracellular 5-aminolevulinic acid (5-ALA) production of T7 Express/pACYC-A-L was up to 146.73 mg/L, simultaneously the extracellular porphrins also increased dramatically. The peroxidase activity of functional MBP-WP1 obtained from T7 Express/ (pACYC-A-L + pMAL-p4x-WP1) was 14.6-folds of that purified from T7 Express/ pET21a-MBP-WP1. This study not only successfully enhanced functional expression of wheat peroxidase 1 in Esherichia coli, but also provided beneficial references for other important proteins with cofactor heme.