Shuwen Yan

Degradation of diclofenac by advanced oxidation and reduction processes: kinetic studies, degradation pathways and toxicity assessments.

Many pharmaceutical compounds and metabolites are found in surface and ground waters suggesting their ineffective removal by conventional wastewater treatment technologies. Advanced oxidation/reduction processes (AO/RPs), which utilize free radical reactions to directly degrade chemical contaminants, are alternatives to traditional water treatment. This study reports the absolute rate constants for reaction of diclofenac sodium and model compound (2, 6-dichloraniline) with the two major AO/RP radicals: the hydroxyl radical (•OH) and hydrated electron (e(aq)(-)). The bimolecular reaction rate constants (M(-1) s(-1)) for diclofenac for •OH was (9.29 ± 0.11) × 10(9), and for e(-)(aq) was (1.53 ± 0.03) ×10(9). To provide a better understanding of the decomposition of the intermediate radicals produced by hydroxyl radical reactions, transient absorption spectra are observed from 1 - 250 μs. In addition, preliminary degradation mechanisms and major products were elucidated using (60)Co γ-irradiation and LC-MS. The toxicity of products was evaluated using luminescent bacteria. These data are required for both evaluating the potential use of AO/RPs for the destruction of these compounds and for studies of their fate and transport in surface waters where radical chemistry may be important in assessing their lifetime.

Photochemically Induced Formation of Reactive Oxygen Species (ROS) from Effluent Organic Matter

The formation of reactive oxygen species (ROS) from effluent organic matter (EfOM) was investigated under simulated solar irradiation. In this study, EfOM was isolated into three different fractions based on hydrophobicity. The productivity of ROS in EfOM was measured and compared with that of natural organic matter (NOM) isolates, including Suwannee River humic acid/fulvic acid (SRHA/FA) and Pony Lake fulvic acid (PLFA). The hydrophilic (HPI) component had a greater quantum yield of 1O2 than those of the hydrophobic (HPO) and transphilic (TPI) fractions because the HPI contained peptides and proteins. Regarding O2•-, the phenolic moieties acted as electron donating species after photochemical excitation and therefore electron transfer to oxygen. A positive correlation was found between the phenolic concentrations and the steady state O2•-concentrations. H2O2 accumulated during the irradiation process from superoxide as precursor. Potentially, due to the presence of proteins or other organic species in the HPI fraction, the decay rates of H2O2 in the dark for both the effluent wastewater and the HPI fraction were significantly faster than the rates observed in the standard NOM isolates, the HPO and TPI fractions. Autochthonous NOM showed a higher •OH productivity than terrestrial NOM. The [•OH]ss was lowest in the HPI fraction due to the lack of humic fraction and existence of soluble microbial products (SMPs), which easily reacted with •OH. Overall, the HPO and TPI fractions were the major sources of superoxide, H2O2 and •OH under simulated solar irradiation. The HPI fraction dominated the production of 1O2 and acted as a sink for H2O2 and •OH.

Hydroxyl Radical Oxidation of Cylindrospermopsin (Cyanobacterial Toxin) and Its Role in the Photochemical Transformation

Cylindrospermopsin (CYN), an alkaloid guanidinium sulfated toxin, is produced by a number of cyanobacteria regularly found in lakes, rivers, and reservoirs. Steady-state and time-resolved radiolysis methods were used to determine reaction pathways and kinetic parameters for the reactions of hydroxyl radical with CYN. The absolute bimolecular reaction rate constant for the reaction of hydroxyl radical with CYN is (5.08 ± 0.16) × 10(9) M(-1) s(-1). Comparison of the overall reaction rate of CYN with hydroxyl radical with the individual reaction rate for addition to the uracil ring in CYN indicate the majority of the hydroxyl radicals (84%) react at the uracil functionality of CYN. Product analyses using liquid chromatography-mass spectrometry indicate the major products from the reaction of hydroxyl radical with CYN involve attack of hydroxyl radical at the uracil ring and hydrogen abstraction from the hydroxy-methine bridge linking the uracil ring to the tricyclic guanidine functionality. The role of hydroxyl radical initiated pathways in the natural organic matter (NOM) photosensitized transformation of CYN were evaluated. Scavenger and trapping experiments indicate that hydroxyl radical mediated transformations account for approximately ~70% of CYN destruction in surface waters under solar irradiation in the presence of NOM. The absence of solvent isotope effect indicates singlet oxygen does not play a significant role in the NOM sensitized transformation of CYN. The primary degradation pathways for HO• mediated and NOM photosensitized destruction of CYN involve destruction of the uracil ring. The fundamental kinetic parameters determined from these studies are critical for the accurate evaluation of hydroxyl-radical based technologies for the remediation of this problematic cyanotoxin in drinking water and important in the assessment of the environmental oxidative transformation of uracil based compounds.

Photochemical Transformation of Aminoglycoside Antibiotics in Simulated Natural Waters

Aminoglycoside antibiotics are widely used in human therapy and veterinary medicine. We report herein a detailed study on the natural-organic-matter- (NOM-) photosensitized degradation of aminoglycosides in aqueous media under simulated solar irradiation. It appears that the direct reaction of the excited states of NOM ((3)NOM*) with aminoglycosides is minor. The contributions of reactive oxygen species (ROSs) in the bulk solutions are also unimportant, as determined by an assessment based on steady-state concentrations and bimolecular reaction rate constants in a homogeneous reaction model. The inhibition of the photodegradation by isopropamide is rationalized through competitive sorption with aminoglycosides on the NOM surface, whereas the addition of isopropanol negligibly affects degradation because it quenches HO(•) in the bulk solution but not HO(•) localized on the NOM surface where aminoglycosides reside. Therefore, a sorption-enhanced phototransformation mechanism is proposed. The sorption of aminoglycosides on NOM follows a dual-mode model involving Langmuir and linear isotherms. The steady-state concentration of HO(•) on the surface of NOM was calculated as 10(-14) M, 2 orders of magnitude higher than that in the bulk solution. This fundamental information is important in the assessment of the fate and transport of aminoglycosides in aqueous environments.

Kinetic Study of Hydroxyl and Sulfate Radical-Mediated Oxidation of Pharmaceuticals in Wastewater Effluents

Advanced oxidation processes (AOPs), such as hydroxyl radical (HO•)- and sulfate radical (SO4•-)-mediated oxidation, are alternatives for the attenuation of pharmaceuticals and personal care products (PPCPs) in wastewater effluents. However, the kinetics of these reactions needs to be investigated. In this study, kinetic models for 15 PPCPs were built to predict the degradation of PPCPs in both HO•- and SO4•--mediated oxidation. In the UV/H2O2 process, a simplified kinetic model involving only steady state concentrations of HO• and its biomolecular reaction rate constants is suitable for predicting the removal of PPCPs, indicating the dominant role of HO• in the removal of PPCPs. In the UV/K2S2O8 process, the calculated steady state concentrations of CO3•- and bromine radicals (Br•, Br2•- and BrCl•-) were 600-fold and 1-2 orders of magnitude higher than the concentrations of SO4•-, respectively. The kinetic model, involving both SO4•- and CO3•- as reactive species, was more accurate for predicting the removal of the 9 PPCPs, except for salbutamol and nitroimidazoles. The steric and ionic effects of organic matter toward SO4•- could lead to overestimations of the removal efficiencies of the SO4•--mediated oxidation of nitroimidazoles in wastewater effluents.

Insights into the photo-induced formation of reactive intermediates from effluent organic matter: The role of chemical constituents

In the present study, the formation of triplet states of organic matters (3OM∗) from effluent organic matter (EfOM) under simulated solar irradiation was investigated. EfOM was separated into hydrophobic (HPO), transphilic (TPI), and hydrophilic (HPI) components. The quantum yield coefficients (ƒTMP) of 3OM∗ were measured for each component and compared to those of reference natural organic matter (NOM). NaBH4 reduction was performed on the EfOM, and the effect of aromatic ketones moieties on triplet formation was also determined. Furthermore, the apparent quantum yield of 1O2 (Φ1O2) and O2•- (ΦO2•-) was measured. Our results suggested that the HPI fraction acted as a sink for 3OM∗. A linear correlation was observed between ƒTMP and Φ1O2 for NOM/EfOM, except for NaBH4-reduced effluent and HPI components. Both ƒTMP and Φ1O2 were positively correlated with the contribution rates of NaBH4-reducible moieties (aromatic ketones) toward 3OM∗. Aromatic ketones were primarily responsible for the production of 3OM∗ from EfOM, whereas quinone moieties played a key role in the production of 3OM∗ in NOM-enriched solutions. Understanding the role of chemical constituents on the photo activity of EfOM/NOM is essential for providing useful insights on their photochemical effects in aquatic systems.

Ozonation of Cylindrospermopsin (Cyanotoxin): Degradation Mechanisms and Cytotoxicity Assessments

Cylindrospermopsin (CYN) is a potent toxic alkaloid produced by a number of cyanobacteria frequently found in lakes and reservoirs used as drinking water sources. We report for the first time detailed pathways for the degradation of CYN by treatment with ozone. This was accomplished by use of ultra-high-performance liquid chromatography (UHPLC)-quadrupole time-of-flight mass spectrometry (QTOF MS), which revealed that CYN is readily degraded by ozone with at least 36 transformation products. Structural similarities among the major products indicated that the carbon-carbon double bond in the uracil ring of CYN was most susceptible to attack by ozone. Furthermore, the nitrogen functionality associated with the tricyclic guanidine moiety is also involved via a degradation pathway that has not been previously observed. To assess the potential toxicity of ozonation products of CYN, the cytotoxicity of CYN and the mixture of its ozonation products was measured in a human hepatoma cell line (HepG2). The IC50 for CYN at 24 and 48 h incubations was approximately 64.1 and 12.5 μM, respectively; however, the ozonation products of CYN did not exhibit measurable cytotoxicity to human cells. The results indicate ozone is an effective and practical method for CYN attenuation in water treatment without formation of overtly toxic transformation products.

Development of Fluorescence Surrogates to Predict the Photochemical Transformation of Pharmaceuticals in Wastewater Effluents

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.

Development of Novel Chemical Probes for Examining Triplet Natural Organic Matter under Solar Illumination

Excited triplet states of chromophoric dissolved organic matter (3CDOM*) are critical transient species in environmental photochemistry. In the present study, sorbic amine (2,4-hexadien-1-amine) and sorbic alcohol were employed as new probe molecules for triplet measurements and compared to the results measured from sorbic acid under identical conditions. Unlike sorbic acid, sorbic amine and sorbic alcohol were not directly photolyzed under solar irradiation. Photosensitized isomerization of the probes with the conjugated diene structure could yield four geometrical isomers. The separation and quantitative determination of the geometrical isomers were accomplished using HPLC and high-resolution NMR analyses. When photoirradiated Suwannee River natural organic matter (SRNOM) was employed as a source of 3CDOM*, significantly different photosensitized isomerization rates were observed for the diverse charged probes. The bimolecular reaction rate constants between 3SRNOM* and the probes were calculated as (0.42 ± 0.1) × 109 M-1 s-1 for sorbic acid, (1.1 ± 0.1) × 109 M-1 s-1 for sorbic alcohol, and (5.2 ± 0.4) × 109 M-1 s-1 for sorbic amine, respectively. The average apparent Φtriplet was (0.96 ± 0.03)% based on an irradiation range of 290 to 400 nm. We developed highly selective and efficient probes for triplet determination and elucidated the different reaction behaviors of these conjugated dienes containing different charged substituents within the photochemical energy transfer process.

Occurrence and estrogenic activity of steroid hormones in Chinese streams: A nationwide study based on a combination of chemical and biological tools

Steroid hormones (SHs) are continuously released into the aquatic environment through various pathways after being excreted by humans and animals, interfere with the normal function of the endocrine system and may affect the physiology and reproduction of exposed aquatic life. To conduct a nationwide investigation of the occurrence and biological effects of SHs in surface river/steam water in China, we quantitated 27 selected SHs in 217 surface water samples by solid-phase extraction (SPE) tandem LC-MS/MS and used a recombinant yeast estrogen assay to screen extracts of the water samples for estrogenic activities. SHs were commonly found in the surface water samples, and their levels were typically in the ng L-1 range. Estrone (E1) and estriol (E3) were normally present in several to dozens of times higher concentrations than estradiol (E2) and 17-a-Ethinylestradiol (EE2). The high concentrations (mean > 1 μg L-1) of SumSHs were primarily obtained in areas under extreme water stress, specifically the eastern coastal areas. Source apportionment based on the profiles of the target compounds indicated that 54.5% of the SHs in target samples came from freshly discharged untreated sewage. The estrogen equivalent (EEQ(bio)) values ranged from 0.01 to 40.27 ng L-1, and the calculated EEQ (EEQ(cal)) values were generally lower than the corresponding EEQ(bio) values for all samples. E2 was the main contributor to the estrogenicity among the three estrogens, with a contribution ratio of 82.8%. The risk quotient values of E2 were highest and ranged from 1.55 to 782.95, and 76.0% of the target surface samples displayed the greatest environmental risk. We concluded that the impacts of SHs on humans in Chinese surface waters should not be ignored and that certain actions should be taken to decrease the levels of SHs in source waters, especially measures targeting SHs in untreated wastewater from the vast rural areas.