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The photochemical transformation of pharmaceutical and personal care products (PPCPs) in wastewater effluents is an emerging concern for environmental scientists. In the current study, the photodegradation of 29 PPCPs was examined in effluents under simulated solar irradiation. Direct photodegradation, triplet state effluent organic matter (3EfOM*)-mediated and hydroxyl radical (HO•)-mediated degradation are three major pathways in the removal process. With the photodegradation of trace levels of PPCPs, the excitation-emission matrix (EEM) fluorescence intensities of the effluents were also gradually reduced. Therefore, fluorescence peaks have been identified, for the first time, as appropriate surrogates to assess the photodegradation of PPCPs. The humic-like fluorescence peak is linked to direct photolysis-labile PPCPs, such as naproxen, ronidazole, diclofenac, ornidazole, tinidazole, chloramphenicol, flumequine, ciprofloxacin, methadone, and dimetridazole. The tyrosine-like EEM peak is associated with HO•/CO3•--labile PPCPs, such as trimethoprim, ibuprofen, gemfibrozil, atenolol, carbamazepine, and cephalexin. The tryptophan-like peak is associated with 3EfOM*-labile PPCPs, such as clenbuterol, metoprolol, venlafaxine, bisphenol A, propranolol, ractopamine, salbutamol, roxithromycin, clarithromycin, azithromycin, famotidine, terbutaline, and erythromycin. The reduction in EEM fluorescence correlates well with the removal of PPCPs, allowing a model to be constructed. The solar-driven removal of EEM fluorescence was applied to predict the attenuation of 11 PPCPs in five field samples. A close correlation between the predicted results and the experimental results suggests that fluorescence may be a suitable surrogate for monitoring the solar-driven photodegradation of PPCPs in effluents. [ABSTRACT FROM AUTHOR]

Pharmaceutical and personal care products (PPCPs) are a group of emerging contaminants that have frequently been detected in aqueous environments. Phototransformation driven by solar irradiation is one of the most important natural processes for the elimination of PPCPs. In this study, primidone (PMD) was chosen as a model "photorefractory" compound. A series of experiments were conducted to assess if reactive intermediates (RIs), such as hydroxyl radical (HO), singlet oxygen (1O 2), and triplet states of dissolved organic matter (3DOM⁎), inhibited or enhanced the photochemical transformation of PMD under simulated solar irradiation. The results indicate that HO plays a key role in the photodegradation of PMD and that dissolved oxygen can affect the degradation rate of PMD by promoting HO formation. Our results demonstrated that PMD can not only react with free HO (HO -free) but also react with lower-energy hydroxylation agents (HO -like). The contributions of HO -free and HO -like to PMD degradation in various dissolved organic matter (DOM) solutions were estimated by a methane-quenching experiment. The results indicated that the HO -like species were important in the photodegradation of "photorefractory" compounds. The bimolecular reaction rate constant of the reaction of free HO with PMD was measured as (5.21 ± 0.02) × 109 M−1 s−1 by using electron pulse radiolysis. Furthermore, PMD was used as a probe to estimate the steady-state concentration of HO -free in various DOM solutions. Using the multivariate statistical strategies of orthogonal projection to latent structures discriminant analysis (OPLS-DA) and hierarchical clustering, 28 photochemical transformation products (TPs) of PMD were successfully identified from the DOM matrix. Unlabelled Image • Photochemical transformation of Primidone was investigated. • The contributions of free hydroxyl radical and lower-energy hydroxylation species were examined. • A method was proposed for the first time to estimate the steady state concentration of free hydroxyl radical. • 28 photochemical products of PMD were identified from the water matrix. • The photochemical degradation mechanisms of PMD were proposed. [ABSTRACT FROM AUTHOR]

The photolysis of acetaminophen, a widely used pharmaceutical, in simulated natural organic matter solutions was investigated. The triplet states of natural organic matter ( 3 NOM*) were found to play the dominant role in its photodegradation, while the contributions from hydroxyl radicals and singlet oxygen were negligible. Dissolved oxygen (DO) plays a dual role. From anaerobic to microaerobic (0.5 mg/L DO) conditions, the degradation rate of acetaminophen increased by 4–fold. That suggests the involvement of DO in reactions with the degradation intermediates. With increasing oxygen levels to saturated conditions (26 mg/L DO), the degradation rate became slower, mainly due to DO's quenching effect on 3 NOM*. Superoxide radical (O 2 - ) did not react with acetaminophen directly, but possibly quenched the intermediates to reverse the degradation process. The main photochemical pathways were shown to involve phenoxyl radical and N-radical cations, finally yielding hydroxylated derivatives, dimers and nitrosophenol. A reaction mechanism involving 3 NOM*, oxygen and O 2 - is proposed. [ABSTRACT FROM AUTHOR]

Surface water contains a large amount of dissolved organic matter (DOM). Interactions between DOM and micropollutants have a significant impact on micropollutant degradation. In this study, algal extracellular polymeric substances (EPS) and natural organic matter (NOM) were selected as two DOM sources and oxytetracycline (OTC) as a representative micropollutant. EPS was mainly composed of tryptophan and protein-like organics, while NOM was mainly composed of fulvic acid-like, humic acid-like, and hydrophobic acid components. In addition, OTC degradation significantly decreased when bound with EPS and the C=O and C–H bonds of CH 2 or CH 3 groups may be involved in binding EPS and OTC, respectively, while –COOH may be involved in the binding of NOM and OTC. Furthermore, triplet intermediates were found to play a major role in OTC photodegradation in both EPS and NOM, with the contribution calculated as 49.96% and 44.61%, respectively. Steady-state concentrations of 3EPS* in EPS and 3NOM* in NOM were 3.59 × 10−14 mol L−1 and 5.54 × 10−15 mol L−1, respectively. These results provide new insights into the degradation of antibiotic-containing wastewater in the natural environment or engineering applications. [Display omitted] • C–H and C=O bonds in EPS participate in the binding interaction between EPS and OTC. • Both in EPS and NOM, triplet states contribute the most to OTC degradation, followed by OH. • EPS contains more protein-like matters that are more readily to generate triplet states under irradiation. [ABSTRACT FROM AUTHOR]

• The emerging Aerucyclamide A (ACA) was purified from the Microcystis aeruginos. • The hydroxyl radical accounted 72% for the photodegradation of ACA. • The thiazole and thiazoline moieties were the reaction sites in ACA. • The acute toxicity of ACA was a quarter of that of microcystin-LR (MC-LR). • The half-life of ACA is longer than MC-LR in aqueous environment. Aerucyclamide A (ACA) is an emerging cyanopeptide toxin produced by cyanobacteria, and its transformation pathway has rarely been reported. In the present study, ACA was purified from cyanobacterial extracts, and photodegradation processes were investigated in dissolved organic matter (DOM) solutions. Under simulated solar irradiation, the photodegradation of ACA was dominated by •OH oxidation, accounting for ~72% of the indirect photodegradation. The bimolecular reaction rate constant of ACA with •OH was (6.4 ± 0.2) × 109 M −1 s −1. Our results indicated that the major reactive sites of ACA toward •OH are thiazoline and thiazole moieties. Product analysis via high-resolution mass spectrometry suggested that hydrogen abstraction and gradual hydroxylation are the main photodegradation pathways. The acute toxicity assessment indicate that the products generated in photolysis process did not show any measurable toxicity to Thamnocephalus platyurus. Photodegradation experiments with various DOM-phycocyanin mixtures demonstrated that the half-life of ACA is much longer than that of microcystin-LR. [ABSTRACT FROM AUTHOR]

• The reaction rate constants of PPRIs with E2 were measured at various pH. • EfOM can act as a photosensitizer and an inhibitor in the phototransformation of E2. • Solar photodegradation can reduce the risk of endocrine disruption impacted by E2. Photodegradation of the natural steroid 17β-estradiol (E2), an endocrine-disrupting hormone that has been widely detected in aquatic environments, was investigated in wastewater effluents at various pH ranges under simulated solar irradiation. The rate of E2 degradation in the sewage effluents was stable at pH 6.0-7.0 but suddenly increased from pH 8.0-10.0. The second-order reaction rate constants of E2 with 3EfOM* and CO 3 •− were measured to increase 11.0-fold and 18.0-fold from pH 6.0 to 10.0, respectively. Two main reasons are proposed for this sharp increase. First, the change in the ionization state of E2 made it susceptible to oxidation by triplet-state effluent organic matter (3EfOM*) and carbonate radicals (CO 3 •−). Second, the steady-state concentration of CO 3 •− increased with increasing pH. Indirect photolysis was suggested to be the main degradation pathway in the sewage effluents, and 3EfOM* was proposed to play a major role at pH 8.0-9.0, while CO 3 •− played a significant role at pH 10.0. In this study, EfOM was shown for the first time to inhibit the oxidation of E2 initiated by 3EfOM* and CO 3 •−. Thus, we suggest that EfOM plays a dual role in the photodegradation of E2: EfOM can not only be activated as 3EfOM* to degrade E2 but also can inhibit the degradation of E2 by reducing the E2 oxidation intermediate back to E2. The estrogenic activity of the photodegradation products was also studied. The in vitro estrogenic activity of E2 solutions decreased approximately as fast as the E2 photodegradation occurred in the effluent water at various pH values, suggesting that solar photodegradation in sewage effluents reduces the risk of endocrine disruption in waters impacted by E2 and subject to continuing inputs. The results of this study are important for predicting the environmental fate of endocrine-disrupting chemicals and developing methods for their removal from aquatic environments. Image, graphical abstract [ABSTRACT FROM AUTHOR]