Hydroxyl radical-mediated degradation of diclofenac revisited: a computational approach to assessment of reaction mechanisms and by-products

Environmental Science and Pollution Research - Advanced oxidation processes (AOPs) are based on the in situ production of hydroxyl radicals (•OH) and reactive oxygen species (ROS) in water...     

Sonochemical degradation of a pharmaceutical waste,atenolol, in aqueous medium

Atenolol is a β-blocker drug and an identified emerging pollutant. Advanced oxidation processes (AOPs) utilise the reaction of a highly oxidising species (hydroxyl radicals, ^?OH) for the mineralisation of emerging pollutants since conventional treatment methodologies generally fail to degrade these compounds. In the present work, degradation of atenolol was carried out using ultrasound with frequencies ranging from 200 kHz to 1 MHz as a source of hydroxyl radical. The degradation was monitored by HPLC, total organic carbon (TOC) and chemical oxygen demand (COD) reduction and ion chromatography (IC). Nearly 90 % of degradation of atenolol was observed with ultrasound having 350 kHz. Both frequency and power of ultrasound affect the efficiency of degradation. Nearly 100 % degradation was obtained at a pH of 4. Presence of various additives such as sodium dodecyl sulphate, chloride, sulphate, nitrate, phosphate and bicarbonate was found to reduce the efficiency of degradation. Although nearly 100 % degradation of atenolol was observed under various experimental conditions, only about 62 % mineralisation (from TOC and COD measurements) was obtained. Nearly eight intermediate products were identified using high-resolution mass spectrometry (LC-Q-TOF). These products were understood as the results of hydroxyl radical addition to atenolol. The degradation studies were also carried out in river water which also showed a similar degradation profile. A mechanism of degradation and mineralisation is presented.     

Sonochemical substrate selectivity and reaction pathway of systematically substituted azo compounds

The sonochemical degradation of the systematically substituted azo compound 2,7-dihydroxy-1-phenylazonaphthaline-3,6-disulfonic acid was investigated using a frequency of 850 kHz and an acoustic input power of 61 W. All derivatives were degraded completely within 6h by the ultrasonic treatment. Trifluoromethyl substituted azo compounds exhibited 2-3-fold higher degradation rates in comparison to the reference hydrogen substituted azo compound (k=0.54 h(-1)). In contrast to enzymatic processes (azoreductase or laccase), the ultrasonic treatment for these ortho-, meta-, and para-substituted azo compound showed 1.5-50-fold higher degradation rates. Additionally the ultrasound treatment was characterized by shorter reaction times. As a result of the detection and identification of specific intermediates using LC-MS a reaction pathway of the sonochemical degradation of the analysed azo compound is proposed indicating the formation of cyclohexadienone and naphthalene quinone derivatives.     

Growth-corruption-health triaca and environmental degradation: empirical evidence from Indonesia,Malaysia, and Thailand

Environmental Science and Pollution Research - This study examines the impact of economic growth, corruption, health, and poverty on environmental degradation for three countries from ASEAN, namely...     

Economic complexity,ICT, biomass energy consumption,and environmental degradation: evidence from Iran

Economic complexity, biomass energy consumption, and information communication technology (ICT) have diverse impacts on energy consumption and carbon dioxide (CO₂) emissions. Nevertheless, analysis of these variable effects is not addressed in the previous literature; the antiqueness of this article is stuffing this gap. This study assessed the relationship between gross domestic product (GDP) per capita, biomass consumption, economic complexity index (ECI), ICT, and CO₂ emissions in Iran in 1994–2018. The autoregressive distributed lag (ARDL) model and the quantile regression (QR) econometric technique were used to investigate the factors affecting CO₂ emissions in the tails of the conditional distribution. The share of each influential factor was predicted through the variance decomposition analysis (VD) for the next 10 years. The empirical results showed a long-run relationship between the variables. So, the variables of biomass consumption, ECI, and ICT improve the quality of the environment in Iran by reducing CO₂ emissions, and the per capita GDP variable increases CO₂ emissions. Results suggest no evidence indicating the presence of environmental Kuznets curve (EKC); however, QR demonstrated the existence of EKCs in the lower quantiles of the conditional distribution. The ECI will have the most share to change the CO₂ emissions in the future. The income threshold should be determined at the turning point of the EKC to increase economic development. Moreover, investing in increasing biomass consumption is vital. Policymakers also need to consider strict added value for the export of products.

     

Direct degradation of methylene blue by unactivated peroxymonosulfate: reaction parameters,kinetics, and mechanism

Environmental Science and Pollution Research - Advanced oxidation processes (AOPs) are efficient methods for water purification. However, there are few studies on using peroxymonosulfate (PMS) to...     

Hormesis: considerations and implications for human health risk assessment

The concept of hormesis as a phenomenon is presented, in the context of its evolving definitions. Predominant types of hormetic effect and potential examples thereof are discussed, focusing on chemicals. The potential for hormesis to affect regulatory approaches and several basic processes used in formulating risk assessment parameters, such as study design, interpretation of dose-response information, and extrapolation of toxicity values, is examined. The potential ramifications for human health risk assessment and risk management are discussed.     

Chlorophenols and other related derivatives of environmental concern: properties, distribution and microbial degradation processes

Chlorophenols are chlorinated aromatic compound structures and are commonly found in pesticide preparations as well as industrial wastes. They are recalcitrant to biodegradation and consequently persistent in the environment. A variety of chlorophenols derivatives compounds are highly toxic, mutagenic and carcinogenic for living organisms. Biological transformation by microorganisms is one of the key remediation options that can be exploited to solve environmental pollution problems caused by these notorious compounds. The key enzymes in the microbial degradation of chlorophenols are the oxygenases and dioxygenases. These enzymes can be engineered for enhanced degradation of highly chlorinated aromatic compounds through directed evolution methods. This review underscores the mechanisms of chlorophenols biodegradation with the view to understanding how bioremediation processes can be optimized for cleaning up chloroaromatic contaminated environments.     

Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics,reaction intermediates,and toxicity assessment

The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na₂SO₄ of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe²⁺ and cathodically generated H₂O₂. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe²⁺ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH₄ ⁺, NO₃ ^?, and SO₄ ^2? ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.     

Ultraviolet photolysis of four typical cardiovascular drugs: mechanisms,influencing factors,degradation pathways,and toxicity trends

Environmental Science and Pollution Research - The cardiovascular drugs (CDDs), such as metoprolol (MET), atenolol (ATE), bezafibrate (BZB), and atorvastatin (ATO), have been frequently detected in...     

Kinetics and mechanisms of radiation-induced degradation of acetochlor

The radiation-induced degradation of acetochlor was investigated in this work. In a mixed solvent composed of acetonitrile and water at a ratio of 20/80 in volume, the acetochlor degradation rate was proportional to the radiation dose rate and acetochlor concentration. The acetochlor degradation efficiency was higher under alkali conditions and lower under acidic conditions. The contribution to the acetochlor degradation by the radicals was in the order of: e(aq)->.OH>H.. The quantum efficiency ratios of .OH, e(aq)- and H. for the degradation of acetochlor were calculated as 1:3:1.     

Correction to: Energy productivity and environmental degradation: the case of Greece

Environmental Science and Pollution Research -     

Speciated arsenic in air: measurement methodology and risk assessment considerations

Accurate measurement of arsenic (As) in air is critical to providing a more robust understanding of arsenic exposures and associated human health risks. Although there is extensive information available on total arsenic in air, less is known on the relative contribution of each arsenic species. To address this data gap, the authors conducted an in-depth review of available information on speciated arsenic in air. The evaluation included the type of species measured and the relative abundance, as well as an analysis of the limitations of current analytical methods. Despite inherent differences in the procedures, most techniques effectively separated arsenic species in the air samples. Common analytical techniques such as inductively coupled plasma mass spectrometry (ICP-MS) and/or hydride generation (HG)- or quartz furnace (GF)-atomic absorption spectrometry (AAS) were used for arsenic measurement in the extracts, and provided some of the most sensitive detection limits. The current analysis demonstrated that, despite limited comparability among studies due to differences in seasonal factors, study duration, sample collection methods, and analytical methods, research conducted to date is adequate to show that arsenic in air is mainly in the inorganic form. Reported average concentrations of As(III) and As(V) ranged up to 7.4 and 10.4 ng/m3, respectively, with As(V) being more prevalent than As(III) in most studies. Concentrations of the organic methylated arsenic compounds are negligible (in the pg/m3 range). However because of the variability in study methods and measurement methodology, the authors were unable to determine the variation in arsenic composition as a function of source or particulate matter (PM) fraction. In this work, the authors include the implications of arsenic speciation in air on potential exposure and risks. The authors conclude that it is important to synchronize sample collection, preparation, and analytical techniques in order to generate data more useful for arsenic inhalation risk assessment, and a more robust documentation of quality assurance/quality control (QA/QC) protocols is necessary to ensure accuracy, precision, representativeness, and comparability.     

Sonochemical degradation of 2,3,7,8-tetrachlorodibenzo-p-dioxins in aqueous solution with Fe(III)/UV system

2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8-TeCDD) was rapidly decreased by sonication in aqueous solution. The degradation efficiency was strongly influenced by ultrasonic power and reaction temperature. An initial 2,3,7,8-TeCDD concentration of 20 ng l(-1) was completely degraded within 60 min under sonochemical conditions using a 20 kHz frequency with a 150 W ultrasound power. The activation energy is 21.9 kJ/mol in the temperature range of 10-40 degrees C, suggesting a diffusion-controlled reaction. To increase the efficiency of 2,3,7,8-TeCDD treatment, degradation system combined ultrasound with Fe(III) (2 x 10(-4)mol l(-1)) and UV irradiation. Both UV and Fe(III) induced Fenton, Fenton-like and photo-Fenton reactions, leading to additional OH radicals and rapid 2,3,7,8-TeCDD removal.     

Non-linear relationship between tourism,economic growth,urbanization, and environmental degradation: evidence from smooth transition models

Environmental Science and Pollution Research - The study aims to analyze two objectives: first is to explore the non-linear relationship between tourism development, economic growth, urbanization,...     

Photochemical degradation kinetics and mechanisms of norfloxacin and oxytetracycline

Environmental Science and Pollution Research - The photochemical degradation of norfloxacin (NOR) and oxytetracycline (OTC) was investigated under ultraviolet (UV) irradiation. The results...     

Risk assessment of environmental chemicals

This article is a summary from eleven important symposia. In these meetings, critical facts were discussed which are the necessary basis for the important legislation about toxic substances in Europe, in the U.S.A. and in Japan. This review article should also be of some help to the readers of “Chemosphere” for direct contacts with the experts mentioned. It is therefore an informative and coordinative survey, in which chemical and ecotoxicological details are largely omited.     

Identifying ecological indicators: an environmental monitoring and assessment program

The U.S. Environmental Protection Agency is initiating the Environmental Monitoring and Assessment Program (EMAP) to monitor the status and trends of the nation's near-coastal waters, forests, freshwater wetlands, surface waters, agroecosystems, and arid lands. This program is intended to evaluate the effectiveness of Agency policies for protecting ecological resources within these systems. Monitoring data collected for all ecosystems will be integrated for national status and trends assessments.     

Ozonation of metoprolol in aqueous solution: ozonation by-products and mechanisms of degradation

This study investigated the degradation pathway of metoprolol, a widely used β-blocker, in the ozonation via the identification of generated ozonation by-products (OPs). Structure elucidation of OPs was performed using HPLC coupled with quadrupole time-of-flight high-resolution mass spectrometry. Seven OPs were identified, and four of these have not been reported elsewhere. Identified OPs of metoprolol included aromatic ring breakdown by-products; aliphatic chain degraded by-products and aromatic ring mono-, di-, and tetrahydroxylated derivatives. Based on the detected OPs, metoprolol could be degraded through aromatic ring opening reaction via reaction with ozone (O₃) and degradation of aliphatic chain and aromatic ring via reaction with hydroxyl radical (?OH).     

Gamma irradiation-induced decomposition of sulfamethoxazole in aqueous solution: the influence of additives,biological inhibitory,and degradation mechanisms

Sulfamethoxazole (SMX) was decomposed by using gamma irradiation in the presence of different additives such as NO₃ ⁻, NO₂ ⁻, Cr(VI), 2-propanol, and tert-butanol. The results demonstrated that NO₃ ⁻, NO₂ ⁻, 2-propanol, and tert-butanol inhibited SMX radiolytic removal. However, there existed a synergetic effect for radiolytic removal of the mixture containing SMX and Cr(VI). At an absorbed dose of 150 Gy, the removal percentages of SMX and Cr(VI) in the mixture were 73.5 and 84.6%, respectively, which was higher than the removal percentages of 70.6 and 4.1% for the single component of SMX and Cr(VI). This provides us an insight into treating the combined pollution in micro-polluted water. The SMX radiolytic removal followed a pseudo first-order reaction kinetic model, and the rate constant ratios of ·OH, e_aq ⁻, and H· towards SMX radiolysis were 10.4:1:2.9. In addition, 24-h bio-inhibitory to the macroalgae of SMX solution during gamma irradiation reached the maximum of 0.85 at an adsorbed dose of 100 Gy, then gradually decreased with the increasing adsorbed dose. Based on LC-MS analysis and quantum chemical calculation, the degradation intermediates were determined and concluded that SMX radiolytic removal was mainly via ·OH radical attack and direct decomposition of SMX molecule by gamma ray.