Electro-oxidation of the dye azure B: kinetics,mechanism, and by-products

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (^?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ^?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?10⁹ M^?1 s^?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.     

Enhanced degradation of the antibiotic tetracycline by heterogeneous electro-Fenton with pyrite catalysis

There is actually increasing concern about the accumulation of antibiotics, such as tetracycline, in soil and water bodies. There is therefore a need for efficient methods to degrade antibiotics and thus clean waters. Here we tested the degradation of tetracycline using the heterogeneous electro-Fenton-pyrite method and compared the results with the conventional electro-Fenton method. The reaction was performed with a boron-doped diamond or Pt anode and carbon-felt cathode allowing electrogeneration of H₂O₂ from O₂ reduction. Results show an increasing tetracycline mineralization using the following methods: anodic oxidation with electrogenerated H₂O₂, electro-Fenton and then electro-Fenton-pyrite using boron-doped diamond. Ion-exclusion HPLC revealed the complete removal of malic malonic, succinic, acetic, oxalic and oxamic acids. Nitrogen present in tetracycline was mainly mineralized in NH₄ ⁺. The higher efficiency of electro-Fenton-pyrite is explained by self-regulation of soluble Fe²⁺ and pH to 3.0 from pyrite catalyst favoring larger ^·OH generation from Fenton’s reaction.     

Assessment of heavy metals and their interrelationships with some physicochemical parameters in eco-efficient rivers of Himalayan region

Most precious and world famed Himalayan rivers like Ganga, Yamuna, and their tributaries are originated from Uttarakhand state of India. Over the years, increased industrial activities and urban growth along the rivers and lakes have resulted in increased load over the water bodies. In the present study, a comparison of characteristics of water quality with respect to heavy metals (Fe, Zn, Cu, and Pb) and their interrelationships with some physiological parameters during different seasons of year 2010 has been made in the water bodies flowing through the two geographical regions, namely Garhwal and Kumaon regions of the Himalayan State of India. All observed values of Pb, 02 observation of the Cu, and 59 observations of Fe are found exceed with the WHO standard for drinking water; 83 observations of Pb, 110 observations of Cu, and 59 observations of Fe are found exceed with the Bureau of Indian Standards. However, none of the observation of Zn is found exceeding with the standard limit. Cu shows the highest concentration 7.30 mg/l among all observations and also its higher concentration in Kumaon rivers. All the metals show negative correlation with dissolved oxygen and pH. Fe in river Yamuna system and Zn in Kumaon rivers show significant temporal variations at 90 % level of significance (LOS). However, no significant temporal difference of remaining metals is observed even at 95 % LOS. All metals except Fe in river Yamuna system show very significant variation in spatial distribution in different river systems at 95 % LOS.     

Kinetic behavior of anti-inflammatory drug ibuprofen in aqueous medium during its degradation by electrochemical advanced oxidation

The electrochemical abatement of the drug ibuprofen (2-(4-isobutylphenyl)propionic acid) from aqueous solution has been carried out by anodic oxidation. The electrolyses have been performed at constant current using a small, undivided cell equipped with a Pt or thin-film boron-doped diamond (BDD) anode and a carbon-felt cathode. The results have shown that ibuprofen has been destroyed under all the conditions tested, following pseudo-first-order kinetics; however, BDD enables higher removal rates than Pt, because the former produces greater quantity of ^?OH. Using BDD anode, the pseudo-first-order rate constant increased with applied current and when NaCl replaced Na₂SO₄ as supporting electrolyte, while it is almost unaffected by ibuprofen concentration. Mineralization of ibuprofen aqueous solutions was followed by total organic carbon (TOC) measurements. After 8 h of electrolysis, TOC removal varied from 91 % to 96 % applying a current in the range of 50–500 mA. The reaction by-products were quantified by chromatographic techniques, and in particular, aliphatic acids (oxalic, glyoxylic, formic, acetic, and pyruvic) have been the main intermediates formed during the electrolyses. The absolute rate constant for the oxidative degradation of ibuprofen have also been determined, by competition kinetic method, as 6.41?×?10⁹ M^?1?s^?1.     

Polychlorinated biphenyls and organochlorine pesticides in amniotic fluids of pregnant women in south-central Turkey†

The concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) were determined in amniotic fluid of 200 pregnant women from the Cukurova region of Turkey. The concentrations of OCPs [hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), dichlorodiphenyl trichloroethane (p,p′-DDT), and various metabolites], and different PCB congeners (28, 52, 101, 118, 138, 153, 180) were determined by gas chromatography with electron capture detection as follows: HCB 6.6 ± 4.7, ΣHCH 21.6 ± 14.2, ΣDDT 12.5 ± 7.5, and ΣPCBs 74.0 ± 54 ng mL^?1. Correlations of maternal or gestational age and levels of OCPs and PCBs were not significant. The levels of these organochlorine compounds (OCs) were below detection limit for 5% of the samples, 80% contained more than one OC. This study illustrates that prenatal exposure of a fetus to OCs is prevalent in the Cukurova region.     

Fast and complete removal of the 5-fluorouracil drug from water by electro-Fenton oxidation

Cytostatic drugs are a troublesome class of emerging pollutants in water owing to their potential effects on DNA. Here we studied the removal of 5-fluorouracil from water using the electro-Fenton process. Galvanostatic electrolyses were performed with an undivided laboratory-scale cell equipped with a boron-doped diamond anode and a carbon felt cathode. Results show that the fastest degradation and almost complete mineralization was obtained at a Fe²⁺ catalyst concentration of 0.2 mM. The absolute rate constant for oxidation of 5-fluorouracil by hydroxyl radicals was 1.52 × 10⁹ M^?1 s^?1. Oxalic and acetic acids were initially formed as main short-chain aliphatic by-products, then were completely degraded. After 6 h the final solution mainly contained inorganic ions (NH₄ ⁺, NO₃ ^? and F^?) and less than 10% of residual organic carbon. Hence, electro-Fenton constitutes an interesting alternative to degrade biorefractory drugs.     

Isolation and Identification of Enterococci from Seawater Samples: Assessment of Their Resistance to Antibiotics and Heavy Metals

A hundred Enterococcus strains were isolated from seawater samples collected from coastal areas of Istanbul. Isolates were identified to the species level using standard biochemical tests specified by Facklam and Collins. The species distribution was as follows Enterococcus faecalis (96%), Enterococcus gallinarum (3%) and Enterococcus solitarius (1%). The resistance of bacteria to both heavy metals (zinc [Zn], iron [Fe], cadmium [Cd], chrome [Cr], cobalt [Co]) and antibiotics (ampicillin 10 μg [AP], penicillin G 10 Units [PG], gentamycin 10 μg [GM], streptomycin 10 μg [S], chloramphenicol 10 μg [C], erythromycin 15 μg [E], kanamycin 30 μg [K], amikacin 30 μg [AK], nalidixic acid 30 μg [NA], and vancomycin 30 μg [VA]) was evaluated. None of the strains was resistant to VA. It was found that among the 100 isolates, those that exhibit resistance to antibiotics, particularly NA, S and K, were also resistant all the heavy metals tested. To our knowledge this is the first report focusing on determination of resistance of environmental enterococci found in Istanbul against heavy metals and antibiotics. Thus, combined expressions of antibiotic and heavy metal resistance may help to reinforce ecological and epidemiological studies and to determine the role of these strains in antibiotic and heavy metal resistance dissemination.     

Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process "electro-Fenton"

Diuron (N'-[3,4-dichlorophenyl]-N,N-dimethylurea) is a herbicide belonging to the phenylurea family, widely used to destroy weeds on uncultivated surfaces. Because of its toxicity for aquatic organisms and suspicion of being carcinogenic for humans, diuron is the object of growing environmental concern. Therefore, we have developed the electro-Fenton method, an electrochemical advanced oxidation process (EAOP), to degrade diuron in aqueous medium, and we have studied the evolution of the toxicity of treated solution during the process. Indeed, the EAOPs catalytically generate hydroxyl radicals that oxidize the persistent organic pollutants, and can ultimately destroy and mineralize them. But, sometimes, relatively toxic organic metabolites are formed during the oxidation reaction. In this work, the evolution of toxicity of diuron aqueous solutions was studied at different initial concentrations, during treatment by the electro-Fenton method. Samples were collected at various electrolysis times and mineralization degrees during the treatment. The toxicity of the samples was measured using the bacteria Vibrio fischeri (Microtox) and the green alga Scenedesmus obliquus. Our results demonstrated that the toxicity of diuron aqueous solutions (concentrations=3.0-27.6 mg L(-1)) varied considerably with time. The formation and disappearance of several metabolites, having toxicity often stronger than that of the initial herbicide, were observed. To improve the efficiency of water decontamination, the electro-Fenton method should be applied during a time long enough (several hours) and at relatively high electrolysis current (I=250 mA) to reach a nearly complete mineralization of the herbicide in the aqueous medium.     

Degradation of anti-inflammatory drug ketoprofen by electro-oxidation: comparison of electro-Fenton and anodic oxidation processes

The electrochemical degradation of the nonsteroidal anti-inflammatory drug ketoprofen in tap water has been studied using electro-Fenton (EF) and anodic oxidation (AO) processes with platinium (Pt) and boron-doped diamond (BDD) anodes and carbon felt cathode. Fast degradation of the parent drug molecule and its degradation intermediates leading to complete mineralization was achieved by BDD/carbon felt, Pt/carbon felt, and AO with BDD anode. The obtained results showed that oxidative degradation rate of ketoprofen and mineralization of its aqueous solution increased by increasing applied current. Degradation kinetics fitted well to a pseudo-first-order reaction. Absolute rate constant of the oxidation of ketoprofen by electrochemically generated hydroxyl radicals was determined to be (2.8?±?0.1)?×?10⁹ M^?1 s^?1 by using competition kinetic method. Several reaction intermediates such as 3-hydroxybenzoic acid, pyrogallol, catechol, benzophenone, benzoic acid, and hydroquinone were identified by high-performance liquid chromatography (HPLC) analyses. The formation, identification, and evolution of short-chain aliphatic carboxylic acids like formic, acetic, oxalic, glycolic, and glyoxylic acids were monitored with ion exclusion chromatography. Based on the identified aromatic/cyclic intermediates and carboxylic acids as end products before mineralization, a plausible mineralization pathway was proposed. The evolution of the toxicity during treatments was also monitored using Microtox method, showing a faster detoxification with higher applied current values.     

Investigation of the bacterial load and antibiotic susceptibility of dental units

The aim of this study was to evaluate the bacterial contamination level and to determine the antibiotic susceptibility of the isolated bacteria from dental unit waterlines (DUWLs) in Istanbul. Bacterial quality of DUWLs is very important, as patients and dental staff are regularly exposed to water and aerosols generated by the unit. If opportunistic pathogens such as Staphylococcus aureus, Pseudomonas aeruginosa, and Legionella pneumophila are present in DUWLs, patient and dental staff can be infected. One hundred water samples were collected from high-speed drills and input waters from 50 dental units. Aerobic heterotrophic bacteria counts and the presence of Legionella, Pseudomonas, oral streptococci, and Staphylococcus were investigated in dental unit waters and aerosol samples. In addition, the antibiotic susceptibility of the isolated and identified bacteria from DUWLs was examined. This research found that 37 out of 50 dental unit water samples exceeded the American Dental Association’s limit of 200 colony-forming units (CFU)/mL^?1. Legionella, oral streptococci, and S. aureus were not detected in any water or aerosol samples, but P. aeruginosa was isolated in three DUWLs. Also, Pseudomonas and Staphylococcus were found in water and aerosol samples. Cefoperazone, ofloxacin, gentamicin, ciprofloxacin, and piperacillin were the most effective antibiotics against the isolated bacteria from DUWLs.