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.

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.

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.

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.

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.

ß-Cyclodextrin Reverses Binding of Perfluorooctanoic Acid to Human Serum Albumin.

Perfluorooctanoic acid (PFOA), a persistent organic pollutant known to cause adverse health effects, strongly binds to human serum albumin (HSA). ß-Cyclodextrin (ß-CD), a nontoxic cyclic sugar, strongly complexes PFOA in a host-guest complex and has been proposed for environmental remediation of PFOA. The interactions between HSA, PFOA, and ß-CD were investigated in order to determine if ß-CD can reverse the binding of PFOA to HSA, with potential therapeutic applications toward exposure to PFOA. 19F Nuclear magnetic resonance (NMR), circular dichroism, and fluorescence spectroscopies were used to study these interactions. Multiple PFOA binding sites to HSA, one with strong affinity and others with low affinity, are evident from changes in the fluorescence emission spectra of HSA and the fluorescence lifetimes of the single Trp residue in HSA with increasing PFOA concentration. Structural changes in the protein are also evident from changes in the circular dichroism spectra of HSA upon titration of PFOA. Addition of ß-CD to PFOA and HSA reversed these changes, indicating that formation of the ß-CD:PFOA host-guest complex is favored even in the presence of HSA. Equimolar ß-CD to PFOA (1:1 ß-CD:PFOA ratio) causes dissociation of the weakly bound PFOA from HSA, whereas excess ß-CD relative to PFOA (5:1 ß-CD:PFOA ratio) leads to the complete disassociation of the strongly bound PFOA molecule from HSA. The 19F NMR studies further suggest that the 2:1 ß-CD:PFOA complex inhibits PFOA binding to HSA. These data demonstrate that ß-CD has potential to be used in therapeutic applications for PFOA in human blood.

ß-Cyclodextrin Attenuates Perfluorooctanoic Acid Toxicity in the Zebrafish Embryo Model.

Perfluorooctanoic acid (PFOA) has been linked to negative health outcomes including cancer, thyroid disease, infertility, and developmental delays. ß-Cyclodextrin (ß-CD), a cyclic sugar, has been previously shown to form strong host-guest complexes with PFOA, and is proposed as a means of environmental remediation with respect to this widespread contaminant. In the present study, ß-CD was directly examined with regards to possible attenuation of the toxicity of PFOA specifically employing the zebrafish (Danio rerio) embryo model. Zebrafish embryos were exposed to various concentrations of PFOA without ß-CD, and with equimolar (1:1) and excess (2:1) molar ratios of ß-CD to PFOA, and assessed for lethality and developmental toxicity through seven days post-fertilization (dpf). Rapid onset of lethality with limited morphological abnormalities was observed at relatively low concentrations of PFOA (LC50 ≈ 50 ppm), along with effects on morphometric and neurobehavioral parameters in surviving embryos. A highly significant difference (p < 0.0001) was observed between the 2:1 treatment, and both 1:1 and PFOA only treatments, with respect to lethal concentration and apparent neurobehavioral effects, suggesting an effectively reduced toxicity of the fully complexed PFOA. In contrast, however, neither ß-CD treatment reduced developmental toxicity with respect to the morphometric endpoint (i.e., interocular distance). Whereas LC50 of PFOA alone did not change over 7 dpf, the 1:1 and 2:1 values decreased slightly over time, suggesting either delayed or alternative toxic effects on later developmental stages at presumptively lowered levels. This study, therefore, indicates ß-CD may be an effective agent to reduce toxicity of and mitigate environmental health concerns associated with PFOA, but that further study is required to elucidate the mechanism of complexation as it relates to the attenuation of toxicity.

19F NMR Characterization of the Encapsulation of Emerging Perfluoroethercarboxylic Acids by Cyclodextrins.

Legacy perfluoroalkyl substances (PFASs) are known environmental pollutants with serious adverse health effects. Perfluoroethercarboxylic acids (PFECAs), emerging PFASs now being substituted for legacy PFASs, have recently been detected in the environment. Cyclodextrins (CDs) have been proposed as agents for the remediation of problematic pollutants, including legacy PFASs. The current study uses 19F NMR spectroscopy to measure the complexation of mono-, di-, and triether PFECAs by CDs for eventual environmental applications. Eight PFECAs were characterized by 19F and 13C NMR. The change in chemical shift of individual fluorines upon complexation of CDs at various stoichiometric ratios was used to determine the host-guest association constants. All studied PFECAs were most strongly encapsulated by ß-CD, with association constants from 102-105 M-1 depending on chain length and number of ether functionalities. 19F-1H heteronuclear Overhauser effect spectroscopy (HOESY) NMR experiments were performed for the ß-CD complexes of two branched monoethers, PFPrOPrA ("GenX") and PFDMMOBA, to elucidate the structural details of the complexes, determine the specific orientation, and position of ß-CD along the PFAS chain, and assess the roles of hydrogen-bonding and PFECA branching on the host-guest interactions. The results give new understanding into the fundamental nature of the host-guest complex between cyclodextrins and perfluorinated surfactants.

Effective removal of phosphate from aqueous solution using humic acid coated magnetite nanoparticles.

Effective removal of excess phosphate from water is critical to counteract eutrophication and restore water quality. In this study, low cost, environmentally friendly humic acid coated magnetite nanoparticles (HA-MNP) were synthesized and applied for the remediation of phosphate from aqueous media. The HA-MNPs, characterized by FTIR, TEM and HAADF-STEM showed the extensive coating of humic acid on the magnetite surface. The magnetic nanoparticles with diameters of 7-12 nm could be easily separated from the reaction mixture by using a simple hand held magnet. Adsorption studies demonstrate the fast and effective separation of phosphate with maximum adsorption capacity of 28.9 mg/g at pH 6.6. The adsorption behavior follows the Freundlich isotherm suggesting the formation of non-uniform multilayers of phosphate on the heterogeneous surface of HA-MNP. The adsorption kinetic fits the pseudo-second order model well with rate constants of 0.206 ± 0.003, 0.073 ± 0.002 and 0.061 ± 0.003 g mg-1min-1 for phosphate (P) concentrations of 2, 5 and 10 mg/L respectively. The removal of phosphate was found higher at acidic and neutral pH compared to basic conditions. The nanoparticles exhibit good selectivity and adsorption efficiency for phosphate in presence of co-existing ions such as Cl-, SO42-and NO3- with some inhibition effect by CO32-. The effect of temperature on the adsorption reveals that the process is endothermic and spontaneous. HA-MNPs are promising, simple, environmentally friendly materials for the removal of phosphate from aqueous media.

Oxidative remediation of 4-methylcyclohexanemethanol (MCHM) and propylene glycol phenyl ether (PPh). Evidence of contaminant repair reaction pathways.

A large spill of 4-methylcyclohexanemethanol (MCHM) and propylene glycol phenyl ether (PPh) into the Elk River near Charleston, West Virginia on January 9, 2014 led to serious water contamination and public concerns about appropriate remediation. To assess the feasibility of advanced oxidation processes (AOPs) for remediation of waters contaminated with these compounds, we induced hydroxyl radical (HO˙) reactions using time-resolved and steady-state radiolysis methods. Detailed product analyses showed initial HO˙ attack was at the benzene ring of PPh, and occurred through H-atom abstraction reactions for MCHM. Pulse radiolysis and steady state radiolysis experiments conducted using pure compound solutions, mixtures of the compounds and real water solvents allowed us to obtain mechanistic insights of hydroxyl radical attack and establish the fate of the compounds using AOP remediation technologies. These results demonstrate that hydroxyl radical induced oxidization of PPh can lead to "repair-type" reactions, which regenerates this contaminant. The study further highlights the importance of such counterproductive reactions for the quantitative estimate of the required amount of oxidant in any large-scale treatment approaches.

Detailed NMR investigation of cyclodextrin-perfluorinated surfactant interactions in aqueous media.

Perfluorochemicals (PFCs) are contaminants of serious concern because of their toxicological properties, widespread presence in drinking water sources, and incredible stability in the environment. To assess the potential application of α-, ß-, and γ-cyclodextrins for PFC remediation, we investigated their complexation with linear fluorinated carboxylic acids, sulfonates, and a sulfonamide with carbon backbones ranging from C4-C9. 19F Nuclear Magnetic Resonance (NMR) spectroscopy studies demonstrated ß-CD formed the strongest complexes with these PFCs. The polar head group had a modest influence, but for PFCs with backbones longer than six carbons, strong association constants are observed for 1:1 (K1:1∼105M-1) and 2:1 (K2:1∼103M-1) ß-CD:PFC complexes. Excess ß-CD can be used to complex 99.5% of the longer chain PFCs. Competition studies with adamantane-carboxylic acid and phenol confirmed the nature and persistence of the ß-CD:PFC complex. Detailed analyses of the individual NMR chemical shifts and Job plots indicate the favored positions of the ß-CD along the PFC chain. Solution pH, ionic strength, and the presence of humic acid have modest influence on the ß-CD:PFC complexes. The strong encapsulation of PFCs by ß-CD under a variety of water quality conditions demonstrates the tremendous potential of CD-based materials for the environmental remediation of PFCs.

Irradiation of ultrasound to 5-methylbenzotriazole in aqueous phase: Degradation kinetics and mechanisms.

Ultrasonic irradiation (640 kHz) leads to the effective degradation of 5-methyl-benzotriazole (5-MBT) in O2 saturated aqueous solution. Up to 97% of 5-MBT is eliminated within 2h of treatment. Upon extended treatment of 6h, UV absorbance of the n→π(∗) and π→π(∗) transitions associated with aromatic and conjugated systems are completely removed, indicating complete destruction of the aromatic system in 5-MBT. The decomposition of 5-MBT follows pseudo-first order kinetics and the observed decomposition rate dropped significantly in the presence of tertiary butyl alcohol. Detailed product studies were performed employing a negative mode ESI LC-MS. Twenty eight intermediate products were detected during ultrasonic mediated degradation of 5-MBT. Reaction pathways are proposed based on the structures of products assigned to observed 28 masses from LC-MS and commonly accepted degradation pathways observed by thermal and hydroxyl radical mediated pathways often associated with ultrasonic treatment.

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.

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.