Mechanism Of Photochemical Degradation Research Articles

Treatment of Pharmaceutical Industry Wastewater by PhotoelectroFenton Oxidation

The use of Photoelectro-Fenton oxidation to treat real pharmaceutical effluent is an attractiveoption for the elimination of complex and persistent organic contaminants. This advanced oxidation processcombines the electrochemical generation of highly reactive hydroxyl radicals (OH•) with the photochemicaldegradation of by-products, resulting in the efficient removal of pharmaceutical compounds fromwastewater. In the Photoelectro-Fenton process, an appropriate anode material, such as BDD or DSA, isused to generate OH•radicals through the electrochemical oxidation of Fe2+ ions. The addition of a smallamount of Fe2+ and H2O2 facilitates the Fenton reaction, leading to the production of additional OH•radicalsin the solution. The presence of these OH•radicals ensures the effective oxidation of pharmaceuticalpollutants, which are often resistant to conventional wastewater treatment methods. The use of UV orsunlight irradiation further enhances the Photoelectro-Fenton process by promoting thephotodecomposition of intermediate by-products formed during the oxidation process. This simultaneouselectrochemical and photochemical degradation mechanism provides synergistic effects, resulting inenhanced degradation and mineralization of pharmaceutical compounds. Studies have demonstrated thesuccessful application of Photoelectro-Fenton oxidation for the treatment of real pharmaceuticalwastewater, showing significant removal efficiencies for a wide range of pharmaceutical compounds,including antibiotics, analgesics, and hormones. Additionally, the process has been shown to effectivelydegrade recalcitrant by-products and reduce the overall toxicity of the wastewater. However, it is importantto consider factors such as optimal pH, Fe2+ and H2O2 dosages, irradiation intensity, and reaction time toachieve optimal treatment efficiency. Furthermore, the cost-effectiveness and scalability of thePhotoelectro-Fenton process need to be evaluated for its potential implementation in large-scale wastewatertreatment facilities.

Photochemical degradation mechanisms and ecotoxicity of propranolol in natural water under simulated and natural sunlight irradiation

The widespread use of propranolol (PRO) has led to its detection in all types of natural water bodies, and it is hazardous to both aquatic organisms and humans. In this study, the photochemical transformation of PRO in the natural environment was investigated using both simulated and outdoor light experiments. The photodegradation of PRO was found to be faster in Pearl river water and the dissolved organic matter (DOM) solutions than that in pure water under sunlight irradiation. Quenching experiments show that the excited triplet states DOM (3DOM*) played a major role while ·OH and 1O2 played minor roles in PRO degradation. The secondary reaction rate constants of 3DOM* with PRO were determined to be (4.32 ∼ 6.38) × 108 M−1 s−1. DOM with high steady-state concentrations of the generated reactive species has higher photochemical reactivity for PRO photodegradation. Total of seven products were identified in in pure water, Pearl River water and three DOM solutions. The degradation of PRO can be mainly through hydroxyl addition, dehydration, naphthalene removal and isopropyl removal reactions. The reaction sites predicted by frontier electronic density calculations can further infer degradation pathways. The ecotoxicity of degradation products was found to be decreased relative to PRO through Ecological Structure Activity Relationship (ECOSAR) program.

Photochemical degradation of short-chain chlorinated paraffins in aqueous solution by hydrated electrons and hydroxyl radicals.

Short-chain chlorinated paraffins (SCCPs) are a complex mixture of polychlorinated alkanes (C10-C13, chlorine content 40-70%), and have been categorized as persistent organic pollutants. However, there are knowledge gaps about their environmental degradation, particularly the effectiveness and mechanism of photochemical degradation in surface waters. Photochemically-produced hydrated electrons (e-(aq)) have been shown to degrade highly chlorinated compounds in environmentally-relevant conditions more effectively than hydroxyl radicals (·OH), which can degrade a wide range of organic pollutants. This study aimed to evaluate the potential for e-(aq) and ·OH to degrade SCCPs. To this end, the degradation of SCCP model compounds was investigated under laboratory conditions that photochemically produced e-(aq) or ·OH. Resulting SCCP degradation rate constants for e-(aq) were on the same order of magnitude as well-known chlorinated pesticides. Experiments in the presence of ·OH yielded similar or higher second-order rate constants. Trends in e-(aq) and ·OH degradation rate constants of the investigated SCCPs were consistent with those of other chlorinated compounds, with higher chlorine content producing in higher rate constants for e-(aq) and lower for ·OH. Above a chlorine:carbon ratio of approximately 0.6, the e-(aq) second-order rate constants were higher than rate constants for ·OH reactions. Results of this study furthermore suggest that SCCPs are likely susceptible to degradation in sunlit surface waters, facilitated by dissolved organic matter as a source of photochemically produced e-(aq) and ·OH.

Kinetics and reaction mechanism of photochemical degradation of diclofenac by UV-activated peroxymonosulfate.

Diclofenac (DCF) is a common non-steroidal anti-inflammatory drug, which is frequently detected in different environmental media such as surface water, groundwater, domestic sewage, and sediment. In this study, UV-activated peroxymonosulfate (PMS) was used to degrade DCF by generating active radicals (i.e., SO4˙− and HO˙) with strong oxidizing properties. The effects of PMS dosage, pH, initial DCF concentration and common water constituents on the removal of DCF as well as its degradation mechanism in UV/PMS system were investigated. Compared to UV alone and PMS alone systems, DCF was removed more efficiently in the UV/PMS system at pH 7.0 due to the contribution of SO4˙− and HO˙, and its degradation followed the pseudo-first order kinetic model. As the dosage of PMS or solution pH increased, the degradation efficiency of DCF was gradually enhanced. The highest DCF degradation was obtained at pH 11.0 in this study, because the molar absorption coefficient of PMS increased with increasing pH at 254 nm resulting in generation of more reactive radicals at high pH. Removal efficiency of DCF was decreased significantly with the increase in its initial concentration due to the insufficient concentration of radicals. The presence of HCO3− and NO3− could promote the degradation of DCF because of the role of carbonate radicals and extra HO˙ formed, respectively, while NOM inhibited DCF degradation due to its competition with DCF for reactive radicals. No obvious influence on DCF degradation was observed in the UV/PMS system with the addition of Cl− and SO42−. The degradation of DCF by UV/PMS in real waters was slightly suppressed compared with its removal in ultrapure water. Seven transformation products were detected using UPLC-QTOF/MS, and the potential degradation mechanism of DCF was thus proposed showing six reaction pathways including hydroxylation, decarboxylation, dechlorination–cyclization, formylation, dehydrogenation and dechlorination–hydrogenation.

Degradation of perfluorooctanoic acid adsorbed on Fe-zeolites with molecular oxygen as oxidant under UV-A irradiation

Perfluorooctanoic acid (PFOA) is of emerging concern owing to its global distribution and environmental persistence. Efficient degradation approaches are so far limited. Herein, we demonstrate for the first time the photochemical degradation of PFOA under UV-A irradiation after adsorption on Fe-doped zeolites with molecular oxygen as the terminal oxidant. In a system containing 1 g L−1 PFOA-loaded Fe-zeolites, outstanding PFOA decomposition (> 99 %) was achieved within 24 h under slightly acidic conditions (pH ≤ 5.5). Short-chain perfluorinated carboxylic acids (PFCAs) are the main intermediates, beside fluoride and CO2. No PFOA degradation occurs with Fe-free zeolites or dissolved ferric ions. Furthermore, we investigated the effects of pH, inorganic ions and gas atmospheres on PFOA degradation. A photochemical degradation mechanism with zeolite-bound iron species as catalytic sites for carboxylate-to-metal charge transfer is proposed. The presented study offers a novel approach for the removal of the highly recalcitrant PFOA from contaminated waters.

Mechanism investigation and stable isotope change during photochemical degradation of tetrabromobisphenol A (TBBPA) in water under LED white light irradiation

Light driven degradation is very promising for pollutants remediation. In the present work, photochemical reaction of tetrabromobisphenol A (TBBPA) under LED white light (λ > 400 nm) irradiation system was investigated to figure out the TBBPA photochemical degradation pathways and isotope fractionation patterns associated with transformation mechanisms. Results indicated that photochemical degradation of TBBPA would happen only with addition to humic acid in air bubbling but not in N2 bubbling. For photochemical reaction of TBBPA, singlet oxygen (1O2) was found to be important reactive oxygen species for the photochemical degradation of TBBPA. 2,6-Dibromo-4-(propan-2-ylidene)cyclohexa-2,5-dienone and two isopropyl phenol derivatives were identified as the photochemical degradation intermediates by 1O2. 2,6-Dibromo-4-(1-methoxy-ethyl)-phenol was determined as an intermediate via oxidative skeletal rearrangement, reduction and O-methylation. Hydrolysis product hydroxyl-tribromobisphenol A was also observed in the reductive debromination process. In addition, to deeply explore the mechanism, carbon and bromine isotope analysis were performed using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) and gas chromatography-multicollector inductively coupled plasma mass spectrometry (GC/MC/ICPMS) during the photochemical degradation of TBBPA. The results showed that photochemical degradation could not result in statistically significant isotope fractionation, indicated that the bond cleavage of C-C and C-Br were not the rate controlling process. Stable isotope of carbon being not fractionated will be useful for distinguishing the pathways of TBBPA and tracing TBBPA fate in water systems. This work sheds light on photochemical degradation mechanisms of brominated organic contaminants.

Mechanism of photochemical degradation of Fe(III)-EDDS complex

In this work, we investigated the photochemical degradation of the complex Fe(III)-EDDS which is increasingly used in studies of advanced oxidation processes. After irradiation of the aqueous solution, HPLC-HRMS analyses are used to identify the degradation products of EDDS. Six different products are separated and identified with specific chemical formulas. Proposed mechanisms based on the initial photo-redox process can explain the formation of all the products. They correspond to oxidized products with a shorter carbon chain and aldehyde and/or carboxylic acid functions. Among, them the formation of formaldehyde is also proposed in the mechanisms. This study is the first one that identifies degradation products of Fe(III)-EDDS complex and proposes a complete mechanism of degradation that can be applied for other iron complexes.

Photochemical degradation kinetics and mechanism of short-chain chlorinated paraffins in aqueous solution: A case of 1-chlorodecane

Short chain chlorinated paraffins (SCCPs) have attracted worldwide attention in recent years, due to their high production volume, persistent, bioaccumulative and toxic properties. In this study, 1-chlorodecane (CD) was selected as a model of SCCPs to explore its photochemical degradation behavior under UV irradiation. The results found that CD could be completely photochemical degradation within 120 min, and the •OH was found to be the main reactive species from both quenching experiments and electron paramagnetic resonance (EPR) results. However, the contribution of triple excited state of CD (3CD*) was still nonnegligible from the results with the absorption peak at 480 nm obtained by laser flash photolysis. Based on the identified intermediates as well as the data from theoretical chemical calculation, the detailed photochemical degradation mechanism of CD was tentatively proposed that CD firstly was excited and photo-ionized under UV irradiation, and the released Cl• in water could result in generating •OH. Then •OH initiates CD degradation mainly through the H-abstraction pathway, leading to the generation of several dehydrogenation radicals, which further generated alcohols or long chain intermediates through radical-radical reactions. The results will provide a comprehensive understanding of the degradation mechanism and environmental fates of SCCPs in water under UV irradiation.

Mechanism of Photochemical Degradation of MC-LR by Pyrite

Pyrite was used as catalyst to degrade Microcystin-LR (MC-LR) at pH 6.8 under visible light irradiation (λ>420 nm). X-ray diffraction (XRD) and scanning electron microscope (SEM) characterization showed that pyrite had the layered structure. The ion state of pyrite before and after the reaction was identified using X-Ray Photoelectron Spectroscopy (XPS), confirming the conversion process of Fe(Ⅱ) to Fe(Ⅲ) on the sulfur defect sites. Electron Spin Resonance (ESR) test showed that pyrite photochemical reaction produced hydroxyl radical (·OH). The results of high performance liquid chromatography (HPLC) and liquid chromatograph-mass spectrometer (LC-MS) showed that visible light irradiation could effectively activate pyrite to degrade MC-LR. The degradation rate of MC-LR reached 100% after 10 hours and the mineralization rate reached 60% after 20 hours. The two reaction pathways of photochemical oxidation of MC-LR by pyrite were discussed.

Investigation of the <i>β</i>-pinene photooxidation by OH in the atmosphere simulation chamber SAPHIR

Abstract. Besides isoprene, monoterpenes are the non-methane volatile organic compounds (VOCs) with the highest global emission rates. Due to their high reactivity towards OH, monoterpenes can dominate the radical chemistry of the atmosphere in forested areas. In the present study the photochemical degradation mechanism of β-pinene was investigated in the Jülich atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber). One focus of this study is on the OH budget in the degradation process. Therefore, the SAPHIR chamber was equipped with instrumentation to measure radicals (OH, HO2, RO2), the total OH reactivity, important OH precursors (O3, HONO, HCHO), the parent VOC β-pinene, its main oxidation products, acetone and nopinone and photolysis frequencies. All experiments were carried out under low-NO conditions ( ≤ 300 ppt) and at atmospheric β-pinene concentrations ( ≤ 5 ppb) with and without addition of ozone. For the investigation of the OH budget, the OH production and destruction rates were calculated from measured quantities. Within the limits of accuracy of the instruments, the OH budget was balanced in all β-pinene oxidation experiments. However, even though the OH budget was closed, simulation results from the Master Chemical Mechanism (MCM) 3.2 showed that the OH production and destruction rates were underestimated by the model. The measured OH and HO2 concentrations were underestimated by up to a factor of 2, whereas the total OH reactivity was slightly overestimated because the model predicted a nopinone mixing ratio which was 3 times higher than measured. A new, theory-derived, first-generation product distribution by Vereecken and Peeters (2012) was able to reproduce the measured nopinone time series and the total OH reactivity. Nevertheless, the measured OH and HO2 concentrations remained underestimated by the numerical simulations. These observations together with the fact that the measured OH budget was closed suggest the existence of unaccounted sources of HO2. Although the mechanism of additional HO2 formation could not be resolved, our model studies suggest that an activated alkoxy radical intermediate proposed in the model of Vereecken and Peeters (2012) generates HO2 in a new pathway, whose importance has been underestimated so far. The proposed reaction path involves unimolecular rearrangement and decomposition reactions and photolysis of dicarbonyl products, yielding additional HO2 and CO. Further experiments and quantum chemical calculations have to be made to completely unravel the pathway of HO2 formation.

The Effect of Explicit Solvent on Photodegradation of Decabromodiphenyl Ether in Toluene: Insights from Theoretical Study

Polybrominated diphenyl ethers (PBDEs) have received special environmental concern because of their potential toxicity to humans and wildlife worldwide. However, their photochemical degradation mechanisms remain largely unknown. Herein, a PCM/TD-DFT scheme (time-dependent density functional theory combined with the polarizable continuum model) augmented with explicit solute-solvent interactions is used to explore the promotive effects of the toluene solvent on the photochemical degradation debromination of deca-BDE (BDE209). The face-to-face π-π interactions between penta-bromine-substituted phenyl and toluene are investigated. The calculations indicate that the face-to-face π-π interaction plays an important role in the low-lying π→σ* transitions of BDE209-toluene π-stacking complex at around 300 nm in the sunlight region, which leads to notable changes for the πσ* excited states and which promotes the breaking of the C-Br bonds. The photodegradation reaction via an intermolecular charge-transfer excited state formed by the electronic transition from a π orbital of toluene to a σ* orbital of BDE209 is found to be a dominant mechanism. Our calculation results reveal the mechanism of how the participation of an explicit toluene solvent molecule catalyzes the photodegradation of BDE209 and explain the experimental results successfully. The present study may provide helpful information for the removal of PBDE contamination.

Role of pH on photolytic and photocatalytic degradation of antibiotic oxytetracycline in aqueous solution under visible/solar light: Kinetics and mechanism studies

In this study, the photochemical degradation of the antibiotic oxytetracycline (OTC) at different pH values was investigated in aqueous solution under visible and solar light irradiation. Particular emphasis was given to the kinetics and mechanism during the photolytic and photocatalytic degradation of OTC. A comparative study of the photolysis of OTC under solar light, with different initial concentrations and in the presence of scavengers of reactive oxygen species (ROS), revealed a self-photosensitization pathway with evidence of singlet oxygen generation at pH 8.5 and 11.0 during OTC photolysis. The three-dimensional fluorescence spectra of OTC at different pH values demonstrate that OTC only exhibits significant emission spectra at pH 8.5 and 11.0. The change of the internal electrostatic force between the electron withdrawing group and the dehydrogenation moiety of OTC as a function of solution pH values was proposed as a critical factor influencing the energy states and observed reaction pathways of OTC under light irradiation. Moreover, the mechanism of photochemical degradation of OTC was investigated with nitrogen and fluorine doped titanium dioxide (NF-TiO2) film at different pH values under visible and solar light in the presence of tert-butyl alcohol (TBA), sodium azide (NaN3), potassium iodine (KI) and catalase as scavengers. Five pathways, including direct photolytic degradation, UV/vis light-induced photocatalytic oxidation and reduction, and visible light-induced self-photosensitized oxidation and reduction, were proposed and verified during the photocatalytic degradation of OTC with NF-TiO2 film.

Photochemical Degradation of Azo Dyes in the Presence of Hydrogen Peroxide and Hematite under Visible Light Irradiation: Surface Complex Forming and Reaction Mechanism

The photochemical degradation mechanisms of an azo dye Direct Red 4BS and Methyl Orange on hematite in the presence of H2O2 were investigated. The decolorization of azo dyes was attributed to the forming surface complex between specific bond of the dyes and hematite, which facilitate the electron transfer from hematite to azo bond. No mineralization of azo dyes occurred in the presence of visible irradiation, only chromogenic group destroyed in the photo-chemical reaction process. Surface complex between azo dyes and hematite will be destroyed under alkaline solution which suggested the active site or the formed surface complex had been destroyed by OH–. Chemical adsorption of the azo dyes on hematite was critical factor which affect the decolorization efficiency of the photoreaction.

Degradation of Cellulose Acetate-Based Materials: A Review

Cellulose acetate polymer is used to make a variety of consumer products including textiles, plastic films, and cigarette filters. A review of degradation mechanisms, and the possible approaches to diminish the environmental persistence of these materials, will clarify the current and potential degradation rates of these products after disposal. Various studies have been conducted on the biodegradability of cellulose acetate, but no review has been compiled which includes biological, chemical, and photo chemical degradation mechanisms. Cellulose acetate is prepared by acetylating cellulose, the most abundant natural polymer. Cellulose is readily biodegraded by organisms that utilize cellulase enzymes, but due to the additional acetyl groups cellulose acetate requires the presence of esterases for the first step in biodegradation. Once partial deacetylation has been accomplished either by enzymes, or by partial chemical hydrolysis, the polymer’s cellulose backbone is readily biodegraded. Cellulose acetate is photo chemically degraded by UV wavelengths shorter than 280 nm, but has limited photo degradability in sunlight due to the lack of chromophores for absorbing ultraviolet light. Photo degradability can be significantly enhanced by the addition of titanium dioxide, which is used as a whitening agent in many consumer products. Photo degradation with TiO2 causes surface pitting, thus increasing a material’s surface area which enhances biodegradation. The combination of both photo and biodegradation allows a synergy that enhances the overall degradation rate. The physical design of a consumer product can also facilitate enhanced degradation rate, since rates are highly influenced by the exposure to environmental conditions. The patent literature contains an abundance of ideas for designing consumer products that are less persistent in the outdoors environment, and this review will include insights into enhanced degradability designs.

Photostability studies of π-conjugated chromophores with resonant and nonresonant light excitation for long-life polymeric telecommunication devices

Theoretical and experimental studies of molecular photodegradation in π-conjugated chromophores with resonant and nonresonant excitation relative to the lowest-energy electronic transition of the chromophore are performed. The limitations of previous photodegradation models are discussed, and new models that overcome these limitations and provide more accurate estimates of chromophore photostability are presented. In particular, the necessity of considering multiple degradation pathways in the analysis of photobleaching studies is shown. Photostability studies of a dihydrofuran thiophene-bridged dicyanomethylene based chromophore (FTC) employing 1.55-μm excitation reveal that the photoinitiated decay kinetics are biphasic. We present what we believe to be a new, double-pathway photodegradation model capable of describing this behavior. Through investigations employing the singlet-oxygen quencher bis(dithiobenzil)nickel, photooxidation is shown to be one of the photodegradation pathways, and the ability of a quencher to inhibit chromophore photooxidation is quantified. The studies presented here provide insight into the mechanism of photochemical degradation of π-conjugated chromophores for devices operating in the visible and at telecommunication wavelengths.

Low Vπ Electrooptic Modulators from CLD-1: Chromophore Design and Synthesis, Material Processing, and Characterization

A ring-locked, phenyltetraene-based, second-order nonlinear optical chromophore (CLD-1) was synthesized. It shows no drop in decomposition temperature compared to its phenyltriene analogue, while the molecular nonlinearity increases by a factor of 2.25 from 6252 × 10-48 to 14065 × 10-48 esu at 1.9 μm. Thin films and waveguide devices were prepared from CLD-1/PMMA and CLD-1/APC (an amorphous polycarbonate) composites to study its electrooptic (EO) activity, optical loss, and photostability. An average EO coefficient of 92 pm/V at 1.06 μm was achieved in a 25 wt % CLD-1/APC composite. Mach−Zender (MZ) modulators fabricated from CLD-1/APC showed good thermal stability, low optical loss, low modulation voltage, and high extinction ratio. The photochemical stability of the CLD-1/APC modulator can be dramatically improved by operating in an inert gas atmosphere. Evidence shows that the predominant photochemical degradation mechanism of the material in air at 1.55 μm is the reaction between oxygen and photoexcited polyene-based chromophores.

Photolysis of Aminoanthraquinones in Matrices

The efficiency of photolysis of aminoanthraquinones in cellulose and cellulose-like matrices depends not only on the chemical nature of the substrate but also on the energy of the excitation radiation and reaction conditions; the latter factors govern the mechanism of photochemical degradation of aminoanthraquinones: reductive (under the action of a labile hydrogen atom of the medium at a carbinol carbon atom) or oxidative (under the action of generated singlet oxygen).

Photochemical Oxidation of Phenanthrene Sorbed on Silica Gel

There have been relatively few detailed studies of PAH photochemical degradation mechanisms and products at solid/air interfaces under controlled conditions. Results from mechanistic studies on particulate simulants are important in understanding the fates of PAH sorbed on similar materials in natural settings. In this study, the photolysis of phenanthrene (PH) on silica gel, in the presence of air, has been carefully examined. Once sorbed onto the silica surface, PH is not observed to repartition into the gas phase, even under vacuum, and dark reactions of PH are not observed at the silica/air interface. Photolysis (254 nm) of PH leads to the formation of 2,2‘-biformylbiphenyl (1), 9,10-phenanthrenequinone (2), cis-9,10-dihydrodihydroxyphenanthrene (3), benzocoumarin (4), 2,2‘-biphenyldicarboxylic acid (5), 2-formyl-2‘-biphenylcarboxylic acid (6), 2-formylbiphenyl (7), 1,2-naphthalenedicarboxylic acid (8), and phthalic acid (9). These products account for 85−90% of the reacted PH. The photoproducts are independent of excitation wavelength (254 and 350 nm), and the reaction proceeds entirely through an initial step involving the addition of singlet molecular oxygen to the ground state of phenanthrene with subsequent thermal and/or photochemical reactions of the initially formed product. Singlet molecular oxygen is produced through quenching of the lowest triplet state of PH at the silica gel/air interface. The high material balance and detailed mechanistic information provided by this study serve as a standard for comparisons with the products and mechanism of PH photochemical oxidation on environmentally derived inorganic oxide particulates.

Photochemical degradation mechanism of stilbene-1 examined by spectroscopic and chromatographic methods

The prerequisite of any quantitative evaluation of a photochemical reaction is to known the mechanism. To increase the photostability of the laser dye stilbene-1 the optimal photodegradation reaction conditions must be found, and thus the mechanism was determined using a combination of chromatographic and spectroscopic techniques. Employing an optical multi-channel analyser made it possible to use fluorescence spectroscopy data in the sophisticated photokinetic calculations. The mechanism and the results are discussed in detail.