Molecular insights into the bonding mechanisms between selenium and dissolved organic matter.

Natural organic matter (NOM) plays a critical role in the mobilization and bioavailability of metals and metalloids in the aquatic environment. Selenium (Se), an environmental contaminant of aquatic systems, has drawn increasing attention over the years. While Se is a vital micronutrient to human beings, animals and plants, excess Se intake may pose serious long-term risks. However, the interaction between Se and dissolved organic matter (DOM) remains relatively unexplored, especially the reaction mechanisms and interactions of specific NOM components of certain molecular weight and the corresponding functional group change. Herein, we report an investigation on the interactions between Se and DOM by focusing on the mass distribution profile change of operationally defined molecular weight fractions of humic acid (HA) and fulvic acid (FA). The results showed that across all molecular weights studied, HA fractions were more prone to enhanced aggregation upon introduction of Se into the system. For FA, the presence of Se species results in aggregation, dissociation, and redox reactions with the first two being the major mechanisms. Total organic carbon analysis (TOC), UV-vis spectroscopy (UV-vis), and Orbitrap MS data showed that [10, 30] kDa MW fraction had the largest aromatic decrease (CRAM-like, lignin-like and tannin-like) upon addition of SeO2 via dissociation as the dominant mechanism. Fourier transform infrared spectroscopy (FT-IR) revealed that Se based bridging or chelation of functional groups from individual DOM components through hydrogen bonding in the form of SeO⋯H and possibly Se⋯H and/or attractive electrostatic interactions lead to aggregated DOM1⋯Se⋯DOM2. It was concluded from two-dimensional correlation analyses of excitation emission matrix (EEM) and FT-IR that the preferred Se-binding follows lipid âž” peptide âž” tannin âž” aromatic functionalities. These results provide new understanding of Se interactions with various NOM components in aquatic environments and provide insight for Se assessing health risk and/or treatment of Se contaminated water.

Detail study on the interaction between perfluorooctanoic acid (PFOA) with human hemoglobin (Hb).

Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are often referred to as legacy perfluoroalkyl substances (PFAS). Human exposure to PFAS leads to severe negative health impacts including cancers, infertility, and dysfunction in the kidneys. Steady-state absorbance, fluorescence, and circular dichroism (CD) methods were used to study the interactions between PFOA and Hb. The results demonstrate the presence of multiple PFOA binding sites on the Hb protein. The detailed analysis of the ferric hemoglobin protein (met Hb) absorbance data as a function of PFOA concentration indicates the presence of at least two binding sites with equilibrium dissociation constants of 0.8 ± (0.2) × 10-6 M and 63 ± (15) × 10-5 M. A competitive binding study with 1,8-ANS showed PFOA can bind to the same binding site as 1,8-ANS on the Hb protein. The titration curve for PFOA binding to Hb in its CO bound form (CO-Hb) yields a single equilibrium dissociation constant of 139 ± (20) × 10-6 M. PFOA binding at low concentrations occurs at the high-affinity sites leading to the destabilization of the protein structure as reflected by changes in the CD spectrum. PFOA interactions with Hb also interfere with the kinetics of CO association to this protein. The rate for CO association to Hb increases at low PFOA concentrations, whereas at elevated PFOA concentrations, the ligand association is biphasic as a new kinetic process with a different rate constant was observed. Overall, this study provides a detailed explanation of PFOA-induced structural and conformational changes to the Hb protein based on the spectroscopy data.

Bisindolyl Maleimides and Indolylmaleimide Derivatives-A Review of Their Synthesis and Bioactivity.

The evolution of bisindolyl maleimides and indolyl maleimide derivatives and their unique biological activities have stimulated great interest in medicinal chemistry programs. Bisindolylmaleimide (BIM)-type compounds arise from natural sources such as arcyriarubin and are biosynthetically related to indolocarbazoles. BIMs are commonly the immediate synthetic precursors of indolocarbazoles, lacking a central bond between the two aromatic units and making them more flexible and drug-like. Synthetic endeavours within this class of compounds are broad and have led to the development of both remarkably potent and selective protein kinase inhibitors. Clinical BIM examples include ruboxistaurin and enzastaurin, which are highly active inhibitors of protein kinase C-ß. While BIMs are widely recognised as protein kinase inhibitors, other modes of activity have been reported, including the inhibition of calcium signalling and antimicrobial activity. Critically, structural differences can be used to exploit new bioactivity and therefore it is imperative to discover new chemical entities to address new targets. BIMs can be highly functionalised or chemically manipulated, which provides the opportunity to generate new derivatives with unique biological profiles. This review will collate new synthetic approaches to BIM-type compounds and their associated bioactivities with a focus on clinical applications.

Ferrate(VI) mediated degradation of the potent cyanotoxin, cylindrospermopsin: Kinetics, products, and toxicity.

The presence of cylindrospermopsin (CYN), a potent cyanotoxin, in drinking water sources poses a tremendous risk to humans and the environment. Detailed kinetic studies herein demonstrate ferrate(VI) (FeVIO42-, Fe(VI)) mediated oxidation of CYN and the model compound 6-hydroxymethyl uracil (6-HOMU) lead to their effective degradation under neutral and alkaline solution pH. A transformation product analysis indicated oxidation of the uracil ring, which has functionality critical to the toxicity of CYN. The oxidative cleavage of the C5=C6 double bond resulted in fragmentation of the uracil ring. Amide hydrolysis is a contributing pathway leading to the fragmentation of the uracil ring. Under extended treatment, hydrolysis, and extensive oxidation lead to complete destruction of the uracil ring skeleton, resulting in the generation of a variety of products including nontoxic cylindrospermopsic acid. The ELISA biological activity of the CYN product mixtures produced during Fe(VI) treatment parallels the concentration of CYN. These results suggest the products do not possess ELISA biological activity at the concentrations produced during treatment. The Fe(VI) mediated degradation was also effective in the presence of humic acid and unaffected by the presence of common inorganic ions under our experimental conditions. The Fe(VI) remediation of CYN and uracil based toxins appears a promising drinking water treatment process.

Computational Study of the Gas-Phase Thermal Degradation of Perfluoroalkyl Carboxylic Acids.

Perfluoroalkyl carboxylic acids (PFCAs) are persistent and ubiquitous pollutants. Environmental remediation is often achieved by absorption on matrices followed by high-temperature thermal treatment to desorb and decompose the PFCAs. Detailed product studies of the thermal degradation of PFCAs have been hampered by the complex nature of product mixtures and associated analytical challenges. On the basis of high-level computational studies, we propose reaction pathways and mechanisms for the high-temperature mineralization of a series of linear PFCAs with a backbone length from C-4 to C-8. The favored initial reaction pathways are nonselective C-C bond homolytic cleavages (with bond dissociation energies of ∼75-90 kcal/mol), resulting in carbon-centered radicals which can undergo ß-scissions (Ea ≈ 30-40 kcal/mol) which can be preceded by F atom shifts (Ea ≈ 30-45 kcal/mol). In competing barrierless processes, the carbon-centered radicals can lose •F, resulting in the formation of volatile perfluoroalkenes (ΔH ≈ 50-80 kcal/mol). A variety of competing fragmentation processes yield shorter chain perfluorinated PFCAs, isomeric alkenes, alkenoic acids, alkyl, and alkyloic acid radicals. The results provide the energetics for primary, secondary, and tertiary reaction products and insight into the fundamental understanding of the pyrolytic pathways of PFCAs leading to their mineralization.

UV/Sodium percarbonate for bisphenol A treatment in water: Impact of water quality parameters on the formation of reactive radicals.

Reported herein is an investigation of the impact of water quality parameters on the formation of carbonate radical anion (CO3•-) and hydroxyl radical (HO•) in UV/sodium percarbonate (UV/SPC) system versus in UV/hydrogen peroxide (UV/H2O2) system for bisphenol A (BPA) degradation in water. Pathways of CO3•- oxidation of BPA were proposed in this study based on the evolution of direct transformation products of BPA. Observed in this study, the degradation of BPA in the UV/SPC system was slower than that in the UV/H2O2 system in the secondary effluents collected from a local wastewater treatment plant due to the significant impact of coexisting constituents in the matrices on the former system. Single water quality parameter (e.g., solution pH, common anion, or natural organic matter) affected radical formations and BPA degradation in the UV/SPC system in a way similar to that in the UV/H2O2 system. Namely, the rise of solution pH decreased the steady state concentration of HO• resulting in a decrease in the observed pseudo first-order rate constant of BPA (kobs). Chloride anion and sulfate anion played a negligible role over the examined concentrations; nitrate anion slightly suppressed the reaction at the concentration of 20 mM; bicarbonate anion decreased the steady state concentrations of both CO3•- and HO• exerting significant inhibition on BPA degradation. Different extents of HO• scavenging were observed for different types of natural organic matter in the order of fulvic acid > mixed NOM > humic acid. However, the impact was generally less pronounced on BPA degradation in the UV/SPC system than that in the UV/H2O2 system due to the existence of CO3•-. The results of this study provide new insights into the mechanism of CO3•- based oxidation and new scientific information regarding the impact of water quality parameters on BPA degradation in the sytems of UV/SPC and UV/H2O2 from the aspect of reactive radical formation, which have reference value for UV/SPC application in wastewater treatment.

Making waves: Defining advanced reduction technologies from the perspective of water treatment.

Studies related to advanced reduction technologies (ARTs) have grown exponentially since the term was first coined in 2013. Despite recent interests in ARTs, the conditions and requirements for these processes have yet to be defined and clarifed. In comparision to well defined advanced oxidation technologies/processes (AOTs/AOPs) which involve the generation of hydroxyl radical as the common characteristic, ARTs function by electron donation from a variety of reducing agents and activators. Based on an extensive literature review, we propose that ARTs be defined as processes employing strong chemical reductants with E° ≤ -2.3 V vs. normal hydrogen electrode at 25 ºC. While extensive studies have revealed critical fundamental details of AOTs/AOPs mediated processes, there are still significant gaps in elucidation of the mechanistic details of reductive degradation/transformation of highly toxic compounds by ARTs. A significant number of pollutants and toxins resistant to AOTs/AOPs treatment are effectively degraded by ARTs. A great leap is needed on understanding ARTs to fully utilize their potential to efficiently remediate recalcitrant compounds of different sources and structures.

Application of dimensional analysis in sorption modeling of the styryl pyridinium cationic dyes on reusable iron based humic acid coated magnetic nanoparticles.

Cationic dyes exist in various industrial wastewaters and removal prior to discharge is necessary due to their carcinogenic behavior which poses a serious threat to human health. Iron based humic acid coated magnetic nanoparticles (HA-MNPs) were evaluated for the removal of 2-[4-(dimethylamino) styryl]-1-methylpyridinium iodide (2-ASP) as a model compound for cationic styryl pyridinium dyes from aqueous media. HA-MNPs were prepared by co-precipitation and characterized. The adsorption of 2-ASP, measured by fluorescence, demonstrates HA-MNPs are efficient for the 2-ASP removal with a maximum adsorption capacity of ~8 mg/g. Kinetic behavior and equilibrium studies showed the adsorption process fits with pseudo 2nd order and Langmuir isotherm models. The adsorption is relatively fast with ~70% of the adsorption complete within 30 min. The overall removal increases by increasing solution pH. The observed increase in adsorption can be assigned to an enhanced electrostatic attraction between the positively charged 2-ASP and the increase in the negative charge on the HA-MNPs surface as a function of increasing solution pH. Effective and repetitive regeneration of the HA-MNPs was achieved using NaOH treatment of saturated sorbent. Regeneration of HA-MNPs showed that removal efficiency remains consistently high after five consecutive cycles. Dimensional analysis suggested that initial concentration/sorbent dose ratio should be considered for accurate sorption modeling confirmed by experimental data. Then generalized empirical models for isothermal study and removal efficiency prediction were accurately deduced. This finding will help researchers in sorption studies to design their experiments more efficiently and to develop improved empirical models in removal prediction.

Elucidation of specific binding sites and extraction of toxic Gen X from HSA employing cyclodextrin.

The presence of per and poly-fluoroalkyl substances (PFAS), commonly referred to as forever chemicals, in aquatic systems is a serious global health problem. While the remediation of PFAS from aqueous media has been extensively investigated, their interactions with and removal from biological systems have received far less attention. We report herein structural alterations to human serum albumin (HSA) upon addition of perfluoro(2-methyl-3-oxahexanoic) acid (Gen X) monitored by changes to the fluorescence and circular dichroism (CD) spectra of HSA. The equilibrium association constant for Gen X binding to HSA is 7( ± 1) × 103 M-1 determined from changes in HSA fluorescence emission data during titration. Site-specific HSA binding fluorophores, 8-anilinonaphthalene-1-sulfonic acid (1,8-ANS), warfarin and dansyl-L-proline were used to investigate the specific binding sites of Gen X on HSA. A competitive displacement study yields association constants for Gen X to HSA at the 1,8-ANS, warfarin, and dansyl-L-proline binding sites to be 6.25 ( ± 0.5) × 104 M-1, 1.1 × 106 M-1, and 2.5( ± 0.2) × 109 M-1 respectively. Addition of ß-cyclodextrin (ß-CD) and heptakis(6-deoxy-6-amino)-ß-cyclodextrin heptahydrochloride to the HSA:Gen X complex leads to the effective extraction of Gen X from the complex with the return of HSA in its native form. Gen X also leads to displacement of site-specific binding fluorophores bound to HSA, while subsequent addition of ß-CD extracts Gen X from HSA with the return of the characteristic fluorescence of the HSA bound site-specific agent. These results illustrate the strong and specific binding sites of Gen X on HSA and demonstrate the principles for the potential application of ß-CD for the remediation of PFAS from biological systems.

Determination and Environmental Implications of Aqueous-Phase Rate Constants in Radical Reactions.

Interests in the kinetics of radical-induced reactions in aqueous solution have grown remarkably due to their water engineering significance (e.g., advanced oxidation processes). Although compilations of the rate constants (k) for various radicals have been documented, surprisingly a systematic review has yet to be reported on the development of reliable methods for determining k values. A knowledge gap exists to critically evaluate and screen the various methods to measure them. In this review, we summarize the direct and indirect methods under steady-state and non-steady-state conditions, followed by critical evaluations on their advantages and disadvantages. The radicals of ·OH, [Formula: see text] , [Formula: see text] , and Cl· were chosen based on their significant aquatic environmental relevance. MS excel spreadsheets that demonstrate the determination processes were provided allowing one to reproduce the data and/or to analyze the unprocessed raw data as a "template". We formulated a standard operation procedure for the k determination, although there is simply no "versatile" method fitting for all radical reactions. Finally, existing challenges and future research focus are discussed. This is the first review covering methodological approaches and considerations, aiming to provide a holistic and fundamental basis to choose an appropriate method for determining the k values for bimolecular reactions between target compounds and radicals in the aqueous phase.

Selective oxidation of H1-antihistamines by unactivated peroxymonosulfate (PMS): Influence of inorganic anions and organic compounds.

The rapid and selective peroxymonosulfate (PMS) induced transformation of H1-antihistamines cetirizine (CET) and diphenhydramine (DPH) can be influenced by the presence of common organic and inorganic water constituents. Presence of HCO3- and/or CO32-, which often exhibit powerful inhibition on the advanced oxidation processes (AOPs), can enhance the PMS mediated transformation of CET/DPH. The observed promotion is demonstrated by the changed solution pH through detailed kinetic studies. The impact of halide ions is remarkable, with I- inhibiting the process through consumption of PMS, while Cl- increases slightly the transformation kinetics through the formation and subsequent reactions of HOCl. The CET/DPH degradation in the Br-/PMS system is influenced by the generation of reactive species such as HOBr which leads to different reaction pathways as compared to PMS alone. The results demonstrated the performance of PMS can be tailored through varying the experimental parameters. In addition, the presence of model organic constituents found in water, e.g., humic acid, phenol, pyridine or sorbate, has a minimal effect on the PMS mediated oxidation processes, highlighting the strong application potential of PMS in water treatment.

Rapid transformation of H1-antihistamines cetirizine (CET) and diphenhydramine (DPH) by direct peroxymonosulfate (PMS) oxidation.

With growing interest in advanced oxidation processes (AOPs), the number of research studies on peroxymonosulfate (PMS) mediated pollutant degradation has increased significantly due to its high radical generation potential upon activation. However, rare studies have focused on the non-radical based PMS reactions. In this study, degradation of model H1-antihistamines cetirizine (CET) and diphenhydramine (DPH) by unactivated PMS was investigated. Addition of scavengers to the reaction mixture ruled out the involvement of hydroxyl radical (OH), sulfate radical (SO4-), singlet oxygen (1O2) and superoxide anion radical (O2-), indicating direct PMS oxidation as the predominant reaction path. Such a mechanism was further supported by the N-oxide products identified by mass spectrometry and nuclear magnetic resonance (NMR) analyses. Solution pH had a pronounced influence on the degradation kinetics regardless the presence or absence of transition metal Fe(II). The highest species dependent second order rate constants were kHSO5-/DPH0 of 175 ± 15.9 M-1 s-1 and kHSO5-/CET- of 36.6 ± 0.16 M-1 s-1. The addition of 100 µM Fe(II) promoted OH mediated degradation of H1-antihistamines and their N-oxide products. This study demonstrated selective transformation with the potential for extensive degradation employing both the direct and catalytic PMS oxidative processes.

Removal of As(III) from Water Using the Adsorptive and Photocatalytic Properties of Humic Acid-Coated Magnetite Nanoparticles.

The oxidation of highly toxic arsenite (As(III)) was studied using humic acid-coated magnetite nanoparticles (HA-MNP) as a photosensitizer. Detailed characterization of the HA-MNP was carried out before and after the photoinduced treatment of As(III) species. Upon irradiation of HA-MNP with 350 nm light, a portion of the As(III) species was oxidized to arsenate (As(V)) and was nearly quantitatively removed from the aqueous solution. The separation of As(III) from the aqueous solution is primarily driven by the strong adsorption of As(III) onto the HA-MNP. As(III) removals of 40-90% were achieved within 60 min depending on the amount of HA-MNP. The generation of reactive oxygen species (•OH and 1O2) and the triplet excited state of HA-MNP (3HA-MNP*) was monitored and quantified during HA-MNP photolysis. The results indicate 3HA-MNP* and/or singlet oxygen (1O2) depending on the reaction conditions are responsible for converting As(III) to less toxic As(V). The formation of 3HA-MNP* was quantified using the electron transfer probe 2,4,6-trimethylphenol (TMP). The formation rate of 3HA-MNP* was 8.0 ± 0.6 × 10-9 M s-1 at the TMP concentration of 50 µM and HA-MNP concentration of 1.0 g L-1. The easy preparation, capacity for triplet excited state and singlet oxygen production, and magnetic separation suggest HA-MNP has potential to be a photosensitizer for the remediation of arsenic (As) and other pollutants susceptible to advanced oxidation.

Circulating transcripts in maternal blood reflect a molecular signature of early-onset preeclampsia.

Circulating RNA (C-RNA) is continually released into the bloodstream from tissues throughout the body, offering an opportunity to noninvasively monitor all aspects of pregnancy health from conception to birth. We asked whether C-RNA analysis could robustly detect aberrations in patients diagnosed with preeclampsia (PE), a prevalent and potentially fatal pregnancy complication. As an initial examination, we sequenced the circulating transcriptome from 40 pregnancies at the time of severe, early-onset PE diagnosis and 73 gestational age-matched controls. Differential expression analysis identified 30 transcripts with gene ontology annotations and tissue expression patterns consistent with the placental dysfunction, impaired fetal development, and maternal immune and cardiovascular system dysregulation characteristic of PE. Furthermore, machine learning identified combinations of 49 C-RNA transcripts that classified an independent cohort of patients (early-onset PE, n = 12; control, n = 12) with 85 to 89% accuracy. C-RNA may thus hold promise for improving the diagnosis and identification of at-risk pregnancies.

Comparative toxicometabolomics of perfluorooctanoic acid (PFOA) and next-generation perfluoroalkyl substances.

Owing to environmental health concerns, a number of per- and polyfluoroalkyl substances (PFAS) have been phased-out, and increasingly replaced by various chemical analogs. Most prominent among these replacements are numerous perfluoroether carboxylic acids (PFECA). Toxicity, and environmental health concerns associated with these next-generation PFAS, however, remains largely unstudied. The zebrafish embryo was employed, in the present study, as a toxicological model system to investigate toxicity of a representative sample of PFECA, alongside perfluorooctanoic acid (PFOA) as one of the most widely used, and best studied, of the "legacy" PFAS. In addition, high-resolution magic angle spin (HRMAS) NMR was utilized for metabolic profiling of intact zebrafish embryos in order to characterize metabolic pathways associated with toxicity of PFAS. Acute embryotoxicity (i.e., lethality), along with impaired development, and variable effects on locomotory behavior, were observed for all PFAS in the zebrafish model. Median lethal concentration (LC50) was significantly correlated with alkyl chain-length, and toxic concentrations were quantitatively similar to those reported previously for PFAS. Metabolic profiling of zebrafish embryos exposed to selected PFAS, specifically including PFOA and two representative PFECA (i.e., GenX and PFO3TDA), enabled elaboration of an integrated model of the metabolic pathways associated with toxicity of these representative PFAS. Alterations of metabolic profiles suggested targeting of hepatocytes (i.e., hepatotoxicity), as well as apparent modulation of neural metabolites, and moreover, were consistent with a previously proposed role of mitochondrial disruption and peroxisome proliferator-activated receptor (PPAR) activation as reflected by dysfunctions of carbohydrate, lipid and amino acid metabolism, and consistent with a previously proposed contribution of PFAS to metabolic syndrome. Taken together, it was generally concluded that toxicity of PFECA is quantitatively and qualitatively similar to PFOA, and these analogs, likewise, represent potential concerns as environmental toxicants.

Fundamental Studies of the Singlet Oxygen Reactions with the Potent Marine Toxin Domoic Acid.

Domoic acid (DA), a potent marine toxin, is readily oxidized upon reaction with singlet oxygen (1O2). Detailed product studies revealed that the major singlet oxygenation reaction pathways were the [2 + 2] cycloaddition (60.2%) and ene reactions (39.8%) occurring at the Z double bond. Diene isomerization and [4 + 2] cycloaddition, common for conjugated diene systems, were not observed during the singlet oxygenation of DA. The bimolecular rate constant for the DA reaction with 1O2 determined by competition kinetics was 5.1 × 105 M-1 s-1. Based on the rate constant and steady-state concentrations of 1O2 in surface waters, the environmental half-life of DA due to singlet oxygen-induced transformations is between 5 and 63 days. The 1O2 reaction product mixture of DA did not exhibit significant biological activity based on ELISA studies, indicating that singlet oxygenation could be an important natural detoxification process. The characteristic oxidation products can provide valuable markers for the risk assessment of DA-contaminated natural waters.

Novel franklinite-like synthetic zinc-ferrite redox nanomaterial: synthesis, and evaluation for degradation of diclofenac in water.

The current study investigates a novel redox technology based on synthetic franklinite-like zinc-ferrite nanomaterial with magnetic properties and redox nature for potential use in water treatment. Physicochemical characterization revealed the nanoscale size and AB2O4 spinel configuration of the zinc-ferrite nanomaterial. The redox activity of nanoparticles was tested for degradation of diclofenac (DCF) pharmaceutical in water, without any added external oxidants and under dark experimental conditions. Results revealed ~90% degradation in DCF (10 µM) within 2 min of reaction using 0.17 g/L Zn1.0Fe2.0O4. Degradation of DCF was due to chemical reduction by surface electrons on zinc-ferrite and oxidation by oxygen-based radicals. Three byproducts from reduction route and eight from oxidation pathways were identified in the reaction system. Reaction pathways were suggested based on the identified byproducts. Results demonstrated the magnetic zinc-ferrite is a standalone technology that has a great promise for rapid degradation of organic contaminants, such as DCF in water.

Degradation and transformation of bisphenol A in UV/Sodium percarbonate: Dual role of carbonate radical anion.

The bicarbonate and carbonate ions (HCO3- &CO32-) will consume hydroxyl radical (HO•) to generate carbonate radical anion (CO3•-) in hydroxyl radical based advanced oxidation processes (HO•-AOPs) resulting in reduced oxidation efficiencies of the systems. However, despite the HO• quenching effect of carbonate species, the contribution of CO3•- to the degradation of bisphenol A (BPA) was observed in UV/sodium percarbonate (UV/SPC). In order to study the performance of UV/SPC for BPA degradation and the role of CO3•- in this process, the degradation kinetics and mechanisms of BPA in UV/SPC and in UV/hydrogen peroxide (UV/H2O2) were compared at equivalent concentration of H2O2. In this study, the observed degradation rates of BPA by UV/SPC and by UV/H2O2 in Milli-Q water were similar. Variation of the BPA degradation rates in the presence of radical quenchers, tert-butanol and phenol, suggested that both CO3•- and HO• contributed to the degradation of BPA in UV/SPC. Second order rate constant of CO3•- towards BPA ( [Formula: see text]  = 2.23 × 108 M-1 s-1) and steady state concentrations of CO3•- ( [Formula: see text]  = 2.3 × 10-12 M) and HO• ( [Formula: see text]  = 1.82 × 10-14 M) in UV/SPC were determined with competition kinetics at 1 mM SPC and pH 8.5. The high [Formula: see text] observed in UV/SPC compensated for the smaller [Formula: see text] compared to [Formula: see text] and the consumption of HO• making the degradation rate of BPA in UV/SPC comparable to that in UV/H2O2. Detailed studies on identification of transformation products (TPs) of BPA in UV/SPC revealed that phenol ring and isopropylidene bridge were the main reactive sites of BPA. Degradation pathways were proposed accordingly. The results of kinetic and mechanistic studies provide better fundamental understanding of the degradation of BPA in UV/SPC and HCO3-&CO32- impact on BPA degradation by HO•-AOPs. This also demonstrates potential for CO3•- based water purification technologies.

UV and Visible Light-Driven Production of Hydroxyl Radicals by Reduced Forms of N, F, and P Codoped Titanium Dioxide.

The photocatalytic activities of reduced titanium dioxide (TiO2) materials have been investigated by measuring their ability to produce hydroxyl radicals under UV and visible light irradiation. Degussa P25 TiO2 was doped with nitrogen (N), fluorine (F), and/or phosphorus (P) and then subjected to surface modification employing a thermo-physicochemical process in the presence of reducing agent sodium borohydride (NaBH4). The reduced TiO2 materials were characterized by a number of X-ray, spectroscopic and imaging methods. Surface doping of TiO2 was employed to modulate the band gap energies into the visible wavelength region for better overlap with the solar spectrum. Hydroxyl radical generation, central to TiO2 photocatalytic water purification applications, was quantitated using coumarin as a trap under UV and visible light irradiation of the reduced TiO2 materials. At 350 nm irradiation, the yield of hydroxyl radicals generated by the reduced forms of TiO2 was nearly 90% of hydroxyl radicals generated by the Degussa P25 TiO2. Hydroxyl radical generation by these reduced forms of TiO2 was also observed under visible light irradiation (419 and 450 nm). These results demonstrated that simple surface modification of doped TiO2 can lead to visible light activity, which is important for more economical solar-driven applications of TiO2 photocatalysis.

Fundamental study of the ultrasonic induced degradation of the popular antihistamine, diphenhydramine (DPH).

Diphenhydramine (DPH) the active ingredient in Benadryl, has been detected in streams, rivers and other surface water sources. As a bioactive compound, DPH impacts human health even at low concentrations. Ultrasonic irradiation at 640 kHz leads to the rapid degradation of DPH in aqueous solution. Radical scavenging experiments and detailed product studies indicate the DPH degradation involves direct pyrolysis and degradation reactions mediated by the hydroxyl radicals produced during cavitation. The degradation can be modeled by pseudo-first order kinetics yielding rate constants k of 0.210, 0.130, 0.082, 0.050, 0.035, 0.023 min-1 at the initial concentrations of 2.8, 5.2, 13.9, 27.0, 61.0, 160.0 µmol L-1, respectively. The degradation process follows the Langmuir-Hinshelwood (heterogeneous) model with a partition coefficient, KL-H = 0.06 µmol·L-1and reactivity constant kr = 1.96 µmol min-1·L-1. A competition kinetic study conducted employing the hydroxyl radical trap, coumarin, illustrates that DPH was degraded primarily by hydroxyl radical mediated processes. Computational studies employing Gaussian 09 basis set provide fundamental insight into the partitioning of the reaction pathways and the degradation mechanisms. The study demonstrates the ultrasonic degradation of DPH is rapid, follows simple kinetic expressions and is accurately modeled using computational methods.