Degradation of diethyl phthalate in treated effluents from an MBR via advanced oxidation processes: effects of nitrate on oxidation and a pilot-scale AOP operation.

The major objective of this study was to delineate the oxidation of diethyl phthalate (DEP) in water, using bench-scale UV/H2O2 and O3/H2O2 processes, and to determine the effects of nitrate (NO(3-)-N, 5 mg L(-1)) on this oxidation. The oxidation of DEP was also investigated through a pilot-scale advanced oxidation process (AOP), into which a portion of the effluent from a pilot-scale membrane bioreactor (MBR) plant was pumped. The bench-scale operation showed that DEP could be oxidized via solely UV oxidation or O3 oxidation. The adverse effect of nitrate on the DEP oxidation was remarkable in the UV/H2O2 process, and the nitrate clearly reduced its oxidation. The adverse effect of nitrate on O3 oxidation was also observed. It was noted, however, that the nitrate clearly enhanced the DEP oxidation in the O3/H2O2 process. A series of pilot-scale AOP operations indicated that the addition of H2O2 enhanced DEP oxidation in both the UV/H2O2 and O3/H2O2 processes. No noticeable adverse effect of nitrate was observed in the NO(3-)-N concentration of about 6.0 mg L(-1), which was naturally contained in the treatment stream. About 52% and 61% of the DEP were oxidized by each of these two oxidation processes in this pilot-scale operation. Both the UV/H2O2 and O3/H2O2 processes appeared to be desirable alternatives for DEP oxidation in treatment effluent streams.

Investigation of the Potential Environmental Risks of Phthalate Derivatives Designed To Be Environmentally Friendly.

Phthalate derivatives with low estrogenic activity, high infrared spectrum signals, high Raman characteristic vibration spectrum, high fluorescence intensity, and high ultraviolet sensitivity were selected as precursors from our previous studies, so that the changes in their toxicity and estrogenic activity during biological metabolism, ozone oxidation, photocatalytic degradation, photodegradation, and microbial degradation could be studied.The transformation pathways of these derivatives were simulated, and the reaction energy barriers were calculated. To determine the potential environmental risks of these phthalate derivatives, the pharmacophore models of biotoxicity and estrogen activity of phthalates were used to predict the biotoxicity and estrogen activity of the transformed products. The results showed an increase in the biotoxicity and estrogen activity of the biometabolites, ozonation products, photocatalytic degradation products, and microbial degradation products; the only products that did not follow this trend were the photodegradation products. Notably, the pathways that produced more potentially toxic compounds were the less favorable paths. Our results indicate that the transformation products of the designed environmentally friendly phthalate derivatives potentially pose environmental risks. To avoid such risks, the environmental transformation pathway of these derivatives should be simulated to screen for environmentally friendly phthalate molecules. Environ Toxicol Chem 2020;39:1138-1148. © 2020 SETAC.

Effect of ultrasonic separation on the structure and properties of diallyl phthalate prepolymer.

The bulk polymerization of diallyl phthalate (DAP) was carried out at high temperature (190 degrees C) without using any initiator, and the reaction was stopped before the gelation point in order to get the prepolymer of DAP. The mixture for the prepolymer and the monomer was successfully separated by a novel ultrasonic method for the first time, and the separation efficiency for the new method was obviously higher than that for the traditional reprecipitation. The product obtained by ultrasonic separation was characterized by infrared spectroscopy (IR), gel permeation chromatography (GPC) and iodine number measurement. It was shown that the average molecular weight of the prepolymer got by the ultrasonic method was lower than that of the prepolymer got by the multi-precipitation, moreover, the molecular weight distribution of the prepolymer got by the ultrasonic separation was broader. Besides, the residual unsaturation degree of the prepolymer separated by ultrasonic was slightly higher than that of prepolymer separated by reprecipitation.

Photochemical degradation of diethyl phthalate with UV/H2O2.

The decomposition of diethyl phthalate (DEP) in water using UV-H2O2 process was investigated in this paper. DEP cannot be effectively removed by UV radiation and H2O2 oxidation alone, while UV-H2O2 combination process proved to be effective and could degrade this compound completely. With initial concentration about 1.0mg/L, more than 98.6% of DEP can be removed at time of 60 min under intensity of UV radiation of 133.9 microW/cm2 and H2O2 dosage of 20mg/L. The effects of applied H2O2 dose, UV radiation intensity, water temperature and initial concentration of DEP on the degradation of DEP have been examined in this study. Degradation mechanisms of DEP with hydroxyl radicals oxidation also have been discussed. Removal rate of DEP was sensitive to the operational parameters. A simple kinetic model is proposed which confirms to pseudo-first order reaction. There is a linear relationship between rate constant k and UV intensity and H2O2 concentration.

Leaching of phthalate esters from different drinking stuffs and their subsequent biodegradation.

Phthalate esters (PAEs) are mainly used as plasticizers, and their release in the environment during the manufacturing, use, and disposal has caused serious environmental health concerns, since some of them are suspected to be mutagens, hepatotoxic agents, and carcinogens. In the present study, leaching of PAEs from different drinking stuffs (water cooler, mineral water bottles) exposed to sunlight and baby feeders subjected to different heating treatments (boiling, autoclave and oven) was studied. Results showed that a total of 10 PAEs were leached and identified. Among them, dimethyl phthalate, bis(2-methoxyethyl) phthalate, diethyl phthalate, and dibutyl phthalate were the major leached PAEs found in the range 9-112.50 µg L-1. Boiling treatment was found safer for baby feeders as PAE leaching was ~26-54% less as compared to other two treatments. The leached PAEs in water samples were then subjected to biodegradation experiment with Bacillus thuringiensis strain at optimized conditions (time 72 h and 30 °C). Hence, leaching of hazardous PAEs from different water stuffs is alarming and needs immediate attention. Moreover, B. thuringiensis strain was found effective for PAE remediation (75-96% degradation) at neutral pH. Graphical abstract ᅟ.

Studies on the adsorption and kinetics of photodegradation of a model compound for heterogeneous photocatalysis onto TiO(2).

An investigation was made on the adsorption and kinetics of photodegradation of potassium hydrogenphthalate in an aqueous suspension of TiO(2). Two models, Langmuir and Freundlich, were used to describe the adsorption process and the model proposed by Langmuir-Hinshelwood (L-H) was employed to describe the kinetics of the photodecomposition reactions of hydrogenphthalate. The results of the adsorptions were fitted to the models proposed by Langmuir and Freundlich. Adsorption was found to be a function of the temperature, with adsorption capacity increasing from 2.4 to 4.5 mg/g when the temperature rose from 20 to 30 degrees C. The kinetic model indicates that the rate constant, k, of the first order reaction, is high in the 10.0 to 100 mg/l interval, which is coherent with the low value of the adsorption constant, K. The results fitted to the L-H model led to an equation that, within the range of concentrations studied here, theoretically allows one to evaluate the photodegradation rate.

A study to determine whether cavitation occurs around dental ultrasonic scaling instruments.

The aim of this investigation was to determine if cavitation occurred around dental ultrasonic scalers and to estimate the amount of cavitation occurring. Three styles of tip (3 x TFI-10, 3 x TFI-3, 3 x TFI-1) were used, in conjunction with a Cavitron SPS ultrasonic generator (Dentsply, USA), to insonate terephthalic acid solution. The hydroxyl radical, [*OH], concentration, produced due to cavitation from the scaler tips, was monitored by fluorescence spectroscopy. Cavitational activity was enhanced at higher power settings and at longer operating times. The tip dimensions and geometry as well as the generator power setting are both important factors that affect the production of cavitation.

Eco-toxicity and human estrogenic exposure risks from OH-initiated photochemical transformation of four phthalates in water: A computational study.

Transformation products (TPs) of emerging organic contaminates (EOCs) in water are still rarely considered in environmental risk assessment, although some have been found to be concern. OH is believed as an important reactive species both in indirect phototransformation and advanced oxidation technology. Thus, eco-toxicity and human estrogenic exposure risks of four phthalates and TPs during the OH-initiated photochemical process were investigated using computational approach. Four phthalates can be degraded through OH-addition and H-transfer pathways. The OH-addition TPs were predominant for dimethyl phthalates, while H-transfer TPs were predominant for other three phthalates. Compared with phthalates, OH-addition TPs (o-OH-phthalates) were one level more toxic to aquatic organisms, and m-OH-phthalates exhibit higher estrogenic activity. Although H-transfer TPs were less harmful than OH-addition TPs, some of them still have aquatic toxicity and estrogenic activity. Therefore, more attentions should be paid to photochemical TPs and original EOCs, particularly those exhibiting high estrogenic activity to humans.

Fe(III)-solar light induced degradation of diethyl phthalate (DEP) in aqueous solutions.

The degradation of diethyl phthalate (DEP) photoinduced by Fe(III) in aqueous solutions has been investigated under solar irradiation in the compound parabolic collector reactor at Plataforma Solar de Almeria. Hydroxyl radicals *OH, responsible of the degradation, are formed via an intramolecular photoredox process in the excited state of Fe(III) aquacomplexes. The primary step of the reaction is mainly due to the attack of *OH radicals on the aromatic ring. For prolonged irradiations DEP and its photoproducts are completely mineralized due to the regeneration of the absorbing species and the continuous formation of *OH radicals that confers a catalytic aspect to the process. Consequently, the degradation photoinduced by Fe(III) could be an efficient method of DEP removal from water.

[Polyamides and esters of terephthalic acid used in the production of medical articles to be sterilized by accelerated electrons]. / Krajowe poliamidy i poliestry kwasu tereftalowego stosowane do wyrobów medycznych wyjalawianych przyspieszonymi elektronami

The paper concerns the study on the resistance of home-made polyamides and polyterephthalic acid esters used for manufacture of medical equipment to the effect of accelerated electron radiation. The studied polyamides were found to be unfit for medical articles manufacture without removal of soluble components of the plastics. Sterilization with accelerated electrons results in limited advantageous changes in polyamide properties. Medical articles made of polyethylene terephthalate can be successfully sterilized in electron accelerator with no changes in characteristics even upon prolonged storage.

Removal of diethyl phthalate from water solution by adsorption, photo-oxidation, ozonation and advanced oxidation process (UV/H2O2, O3/H2O2 and O3/activated carbon).

The objective of this work was to compare the effectiveness of conventional technologies (adsorption on activated carbon, AC, and ozonation) and technologies based on advanced oxidation processes, AOPs, (UV/H(2)O(2), O(3)/AC, O(3)/H(2)O(2)) to remove phthalates from aqueous solution (ultrapure water, surface water and wastewater). Diethyl phthalate (DEP) was chosen as a model pollutant because of its high water solubility (1,080 mg/L at 293 K) and toxicity. The activated carbons showed a high adsorption capacity to adsorb DEP in aqueous solution (up to 858 mg/g), besides the adsorption mechanism of DEP on activated carbon is governed by dispersive interactions between π electrons of its aromatic ring with π electrons of the carbon graphene planes. The photodegration process showed that the pH solution does not significantly affect the degradation kinetics of DEP and the first-order kinetic model satisfactorily fitted the experimental data. It was observed that the rate of decomposition of DEP with the O(3)/H(2)O(2) and O(3)/AC systems is faster than that with only O(3). The technologies based on AOPs (UV/H(2)O(2), O(3)/H(2)O(2), O(3)/AC) significantly improve the degradation of DEP compared to conventional technologies (O(3), UV). AC adsorption, UV/H(2)O(2), O(3)/H(2)O(2), and O(3)/AC showed a high yield to remove DEP; however, the disadvantage of AC adsorption is its much longer time to reach maximum removal. The best system to treat water (ultrapure and natural) polluted with DEP is the O(3)/AC one since it achieved the highest DEP degradation and TOC removal, as well as the lower water toxicity.

Sonophotolytic diethyl phthalate (DEP) degradation with UVC or VUV irradiation.

This study investigated the degradation of diethyl phthalate (DEP) by sonolytic, photolytic and sonophotolytic processes. Two types of UV lamps, UVC (254 nm) and VUV (185 nm+254 nm), were combined with ultrasound (283 kHz). The pseudo-first order degradation rate constants were in the order of 10(-1)-10(-3) min(-1) depending on the processes. The sonolytic DEP degradation rate increased with increasing applied power. Photolytic or sonophotolytic degradation of DEP when using a VUV lamp appeared to be effective because the photo ІІ (UVC/VUV) resulted in a significantly faster degradation than the photo І (UVC) processes due to the higher photon energy and higher hydroxyl radical generation by homolysis of water by VUV. Significant degradation and mineralization (TOC) of DEP were observed with the combined sonophotolytic processes. Moreover, synergistic effects of 1.68 and 1.23 were exhibited at DEP degradation of the sonophoto I and sonophoto II processes, respectively. This was attributed to the UV-induced dissociation of hydrogen peroxide (H(2)O(2)) generated by the application of US to hydroxyl radicals. Therefore, US in sonophotolytic processes can play an important role in enhancing DEP degradation. Moreover, the sonophoto ІІ process is more effective on the mineralization and biodegradability of DEP.

Enhanced decomposition of dimethyl phthalate via molecular oxygen activated by Fe@Fe2O3/AC under microwave irradiation.

In this study, we demonstrate that the decomposition of dimethyl phthalate under microwave irradiation could be greatly enhanced over Fe@Fe(2)O(3) nanowires supported on activated carbon (Fe@Fe(2)O(3)/AC). The great enhanced decomposition of dimethyl phthalate could be attributed to a unique microwave induced molecular oxygen activation process. Upon microwave irradiation, electrons could be transferred from activated carbon to zero-valent iron, and then react with molecular oxygen to form O(2)(-) and OH radicals for the decomposition of dimethyl phthalate. The deactivation and the regeneration of Fe@Fe(2)O(3)/AC catalyst were systematically studied. We also found that microwave heating could accelerate the electron transferring from AC to Fe@Fe(2)O(3) to generate more reactive oxygen species for the decomposition of DMP than conventional oil bath heating. This novel molecular oxygen activation approach may find applications for wastewater treatment and drinking water purification.

Simulated sunlight photodegradation of aqueous phthalate esters catalyzed by the polyoxotungstate/titania nanocomposite.

A series of porous polyoxotungstate/titania nanocomposites (PW(12)/TiO(2)) with particle size lower than 10nm and BET surface area of ca. 200 m(2)g(-1) was prepared by sol-gel chemistry combined with solvothermal treatment. The composites were successfully applied to the degradation of aqueous phthalate esters (PAEs) including di-n-butyl phthalate (DBP), diethyl phthalate (DEP), and dimethyl phthalate (DMP) under the simulated sunlight irradiation (lambda=320-680 nm) for the first time, and the conversion of DBP, DEP, and DMP reached to 98%, 84%, and 80%, respectively, after the simulated sunlight irradiation the suspension including PAE (5 mg L(-1), 100 mL) and PW(12)/TiO(2)-19.8 (100 mg) for 90 min. In addition, nearly total mineralization of DBP and DEP was realized by further increasing light irradiation time to 12h. Based on the intermediates identified in the reaction system, the photocatalytic degradation pathway of PAEs was put forward.

Degradation of n-butyl benzyl phthalate using TiO2/UV.

n-Butyl benzyl phthalate (BBP) has been classified as endocrine disrupting compound and priority pollutant. Effects of TiO(2) dosage, pH, initial BBP concentration and co-existing substances on the degradation of BBP by TiO(2)/UV process were investigated. The optimal TiO(2) dosage and pH value for the BBP degradation were 2.0gL(-1) and 7.0, respectively. The degradation rate of BBP by TiO(2)/UV process could be fitted pseudo-first-order kinetics. The effects of co-existing substances on the degradation rate of BBP revealed that some anions (such as BrO(3)(-), ClO(4)(-) and Cr(2)O(7)(2-)) could enhance BBP degradation, and other anions would restrain BBP degradation. The sequence of inhibition was PO(4)(3-)>CO(3)(2-)>NO(3)(-)>SO(4)(2-)>Cl(-). The cations K(+), Na(+), Mg(2+) and Ca(2+) had the restrained effect on the BBP degradation, and the effect of Ca(2+) was the strongest among four cations tested. The organic compounds acetone and methanol decreased the degradation rate of BBP. The major intermediates of BBP degradation were identified as mono-butyl phthalate, mono-benzyl phthalate and phthalic acid, and a primary degradation mechanism was proposed.

Study of a peak in cavitation activity from HIFU exposures using TA fluorescence.

Methods of measuring the sound field and focal region of a 1.05 MHz high intensity focused ultrasound (HIFU) are described in this paper. 1.05 MHz pulsed HIFU with intensity 2400 W/cm(2) with a 1:1 duty cycle ("on" phase equaled "off" phase) was used to irradiate terephthalic acid (TA). Pulse periods of 0.5 ms, 1 ms, 3.3 ms, 10 ms, 15 ms, 33 ms, 0.1s and 1s were used. The irradiation time was 2 min. To indicate the intensity of inertial cavitation activity, the fluorescence intensity of hydroxyterephthalic acid (HTA) was measured. The result shows that the cavitation activity of pulsed HIFU peaks at a pulse period of 10 ms, cavitation activity is significantly greater for pulse periods from 2 to 20 ms than for others.

Time-resolved EPR spectra of the triplet excited states of diaminoacridine guests in polar potassium hydrogen phthalate single crystals.

Mixed crystals of potassium hydrogen phthalate containing 3,6-diaminoacridine were photoexcited with visible light and the resulting triplet excited states were analyzed by time resolved EPR spectroscopy. Spectra from discrete growth sectors were compared with powders and polycrystalline glasses prepared at various pHs. The data yield the predominant protonation state and orientation of the triplets in each of a pair of growth sectors bounding the positive and negative ends of the polar crystal.

[Radiolytic decontamination of Di-n-butyl phthalate from water (author's transl)].

Recently, a considerable amount of phthalic acid esters (PAE), the most widely utilized plasticizer, has been released into and polluted the environment. Since their toxicity and teratogenicity, although fairly low, to experimental animals have recently been shown, the removal of them from the environment, especially from the drinking water, is desirable. As an attempt for the removal, the radiolytic degradation of 7-14C-di-n-butyl phthalate (14C-DBP) in water was investigated at several pHs. Approximately 50% of 14C-DBP (1 ppm aqueous solution) was decomposed by 60Co gamma-irradiation to a dose of 3 X 10(4) rad at pH 7 and the main product was mono-n-butyl phthalate (MBP). At pHs 3 and 11 14C-DBP was more easily radiolyzed and converted to ether-soluble compounds other than MBP or phthalic acid (PA). By irradiation to 10(6) rad 14C-DBP as well as 14C-MBP and 14C-PA, at pH value tested, was almost completely decomposed to volatile or water-soluble substances of possibly low molecular weight. These findings suggest that the gamma-irradiation is effective to make the PAE-polluted water clean.