- [Show abstract] [Hide abstract] ABSTRACT: In this study a comparative assessment using various advanced oxidation processes (UV/H(2)O(2), UV/H(2)O(2)/Fe(II), O(3), O(3)/UV, O(3)/UV/H(2)O(2) and O(3)/UV/H(2)O(2)/Fe(II)) was attempted to degrade efficiently two fluoroquinolone drugs ENR [enrofloxacin (1-Cyclopropyl-7-(4-ethyl-1-piperazinyl)-6-fluoro-1,4-dihydro-4-oxo-3-quinolonecarboxylic acid)] and CIP [ciprofloxacin (1-cyclopropyl-6-fluoro-4-oxo-7-(piperazin-1-yl)-quinoline-3-carboxylic acid)] in aqueous solutions at a concentrations of 0.15 mM for each drug. The efficiency of the applied oxidation processes (AOPs) has been estimated by the conversion of the original substrate (X(ENR) and X(CIP)) and the reduction of chemical oxygen demand (COD), total organic carbon (TOC). Special emphasis was laid on the effect of varying reaction pH as well as of the applied oxidant doses on the observed reaction kinetics for each advanced oxidation processes. High degradation efficiencies, particularly in terms of rates of TOC and COD abatement, were obtained for photo-Fenton assisted ozonation [O(3)/UV/H(2)O(2)/Fe(II)], compared to other advanced oxidation processes. At pH 3 and 25°C best results for the degradation of both investigated drugs were achieved when 10 mM H(2)O(2), 0.5 mM Fe(II) and an initial dose of 8.5 mg L(-1) ozone were applied. In addition, the evolution of toxicity of the reaction mixtures for different AOPs has been studied by the bioluminescence test (LUMIStox 300).
- [Show abstract] [Hide abstract] ABSTRACT: Surface sediments from 12 different locations of the Istanbul Strait and Marmara Sea, Turkey were analysed for five antibiotics belonging to two different groups of widely used pharmaceuticals, tetracyclines (TCs) and fluoroquinolones (FQs), by solid-phase extraction and high performance liquid chromatography. These two groups of antibiotics, mainly used to prevent or treat illness for humans as well as for animals, are frequently detected in the effluent of municipal sewage plants, in the aquatic environments and in soils after being spread by liquid manure. The results of analysis revealed that measured concentrations of individual antibiotics were significantly different depending on sampling location. Chlortetracycline (CTC) was not detected in any of the samples. High concentrations were mainly found in urbanized regions of the Strait. The concentrations of the two tetracyclines ranged from not detectable to 27.3 μg kg(-1) in freeze-dried marine sediments. Comparable results were obtained for the two fluoroquinolones with concentration levels from 1.3 μg kg(-1) up 34.1 μg kg(-1). This study is the first attempt to show the contamination degree of the Istanbul Strait sediments by emerging contaminants. Particular concern should be given concerning their potential side effects caused by the frequent consumption of mussels and fishes captured in the Istanbul Strait.
- [Show abstract] [Hide abstract] ABSTRACT: This study evaluates the degradation efficiency of enrofloxacin (ENR) by catalytic wet air oxidation (CWAO) and ozonation. Results obtained by CWAO experiments show that 99.5% degradation, 37.0% chemical oxidation demand (COD) removal and 51.0% total organic carbon (TOC) conversion were obtained when 100mol% FeCl(3) and 25mol% NaNO(2) at 150°C under 0.5MPa oxygen pressure after 120min are used. The degradation products are identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS), gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC). The oxidation end products, F(-), NO(3)(-) and NH(4)(+) were determined by IC. The BOD(5)/COD ratio as a measure of the biodegradability of the parent compound increased from 0.01 to 0.12 after 120min of reaction time, indicating an improved biodegradability of the parent compound. The inhibition of bioluminescence of the marine bacteria V. fischeri decreased from 43% to 12% demonstrating a loss in toxicity of ENR during CWAO. Ozonation of 0.2mM ENR was carried out with an ozone concentration of 7.3gm(-3) at pH 7. ENR decomposition with a degradation rate of 87% was obtained corresponding to the reaction time. Moderate changes in COD (18%) and TOC (17%) removal has been observed. The bioluminescence inhibition increased from 8% to 50%, due to the generation of toxic degradation products during ozonation. In comparison to the widely use of well developed method of ozonation CWAO exhibits better performance in terms of COD, TOC removals and generates less toxic products.
- [Show abstract] [Hide abstract] ABSTRACT: The leaching behaviors of enrofloxacin (ENR), a fluoroquinolone group antibiotic, in three different standard soils, namely sandy, loamy sand and sandy loam were investigated according to OECD guideline 312. In addition, the effects of tenside, sodium dodecylbenzenesulfonate (DBS) on the mobility of ENR in two different soils were studied. The mobility of ENR in all three standard soils was very similar and was mostly (98%) concentrated on the top 0-5 cm segment of the soils at pH 5.7. The DBS can enhance the mobility of ENR in soils but the impact was in general negligible under the studied conditions.
- [Show abstract] [Hide abstract] ABSTRACT: The textile industry worldwide involves a large number of washing, bleaching, dyeing, and conditioning processes. The industry is well-known for its extensive water consumption and discharges. Each process wastewater stream has a unique pollutant characteristics and flow rate. The segregation of weakly polluted streams, and their separate treatment and reuse for appropriate processes may result in a considerable reduction in water consumption and wastewater discharge. A wool and blends textile enterprise was investigated in an attempt to achieve optimum water management. The segregated streams were selected by assessment of the processes and comprehensive characterization of the wastes generated. Cleaner Production (CP) implementation options were developed and compared. The methodology was applied as a case study for an integrated wool, wool-PES blends and clothing industry study in Istanbul. Economical and applicable treatment alternatives complying with the criteria for reuse and discharge were designed and operated under laboratory conditions. Furthermore, a cost assessment of the CP options was made based on the stream segregation and reuse.
- [Show abstract] [Hide abstract] ABSTRACT: A treatability study for highly polluted and recalcitrant azo reactive dye-baths from cotton textile dyeing processes was conducted by using fixed and up-flow fluidized bed type reactors packed with brown coal. Ozone oxidation was carried out to assess the combination of biological and chemical oxidation. COD removal efficiencies ranged from 70% to 93%, and up to 99% color removal was attained. At a COD loading rate of 25.5 x 10(-6) gCOD/m(2)-d, COD removal was 85%. Breakthrough of the brown coal used occurred at total organic loading of 0.090 gCOD/g coal. Biodegradable and inert COD fractions of the remazol dye-bath were assessed by BOD(28) and oxygen uptake rate (OUR) measurements. 50% of total COD was initially inert. The inert fraction was reduced by adsorption and ozone oxidation by 65% and 40%, respectively. Brown coal is an inexpensive material and the system has economical and operational advantages as compared to treatment options such as advanced oxidation processes (AOPs) using UV, O(3), H(2)O(2) or electrocoagulation.
- [Show abstract] [Hide abstract] ABSTRACT: A pot trial was carried out to investigate the adverse effects of tetracycline (TC) on soil microbial communities, microbial activities, and the growth of ryegrass (Lolium perenne L). The results showed that the presence of TC significantly disturbed the structure of microbial communities and inhibited soil microbial activities in terms of urease, acid phosphatase and dehydrogenase (p < 0.05). Plant biomass was adversely influenced by TC, especially the roots with a reduction of 40% when compared with the control. Furthermore, TC decreased the assimilation of phosphorus by the plant although the concentration of phosphorus was increased by 20% due to decreased plant biomass. TC seemed to increase the concentration of dissolved organic carbon (by 20%) in soil. The findings implied that the agricultural use of animal manure or fishpond sediment containing considerable amounts of antibiotics may give rise to ecological risks.
- [Show abstract] [Hide abstract] ABSTRACT: Five fulvic acid samples were characterized by elemental analyses, the ratio of optical density at 465 nm and 665 nm (E 4/E 6), gel‐permeation chromatography, Fourier transform infrared spectroscopy (FT‐IR), and 1H and I3C nuclear magnetic resonance spectroscopy ('H‐NMR and 13C‐NMR). Out of these fulvic acids, two were extracted from Kaschin‐Beck disease prone areas drinking water, and three from disease free sources like water, soil and peat. The physical and chemical properties varied with the sources of fulvic acids but no distinct relation to Kaschin‐Beck disease has been found.
- [Show abstract] [Hide abstract] ABSTRACT: Photo-assisted Fenton mineralization of ciprofloxacin (CFX), a broad-spectrum antibiotic used in human and veterinary medicine was studied using a modified laponite clay-based Fe nanocomposite (Fe-Lap-RD) as a heterogeneous catalyst in the presence of hydrogen peroxide and UV light. The catalytic performance has been monitored in terms of CFX (0.15 mM) and total organic carbon (TOC) conversions, whereas the catalyst stability was evaluated according to the metal leached from the solid structure into the aqueous solution. The Fe-Lap-RD was characterized by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) techniques. Further, the effects of reaction parameters such as H2O2 concentration, Fe-Lap-RD catalyst loading and initial solution pH on the mineralization of CFX were investigated. It was found that at the optimal reaction conditions (60 mM H2O2, 1.0 g L−1 Fe-Lap-RD, initial solution pH 3.0), complete CFX degradation and over 57% total organic carbon (TOC) removal of CFX can be achieved after 30 min reaction. In addition degradation and mineralization kinetics of CFX was also studied to obtain apparent reaction rate constants. The photo-Fenton degradation of CFX follows the pseudo-first-order kinetics. Fe-Lap-RD exhibits good catalytic activity in the photodegradation and mineralization of CFX, with negligible leaching of Fe ions from the catalyst structure.
- [Show abstract] [Hide abstract] ABSTRACT: Antibiotic formulation effluents are well known for their difficult elimination by traditional bio-treatment methods and their important contribution to environmental pollution due to its fluctuating and recalcitrant nature. In the present study the effect of ozonation on the degradation of oxytetracycline (OTC) aqueous solution (100mgl(-1)) at different pH values (3, 7 and 11) was investigated. Ozone (11mgl(-1) corresponds the concentration of ozone in gas phase) was chosen considering its rapid reaction and decomposition rate. The concentration of oxytetracycline, chemical oxygen demand (COD), biochemical oxygen demand (BOD) and BOD5/COD ratio were the parameters to evaluate the efficiency of the ozonation process. In addition, the toxic potential of the OTC degradation was investigated by the bioluminescence test using the LUMIStox 300 instrument and results were expressed as the percentage inhibition of the luminescence of the marine bacteria Vibrio fischeri. The results demonstrate that ozonation as a partial step of a combined treatment concept is a potential technique for biodegradability enhancement of effluents from pharmaceutical industries containing high concentration of oxytetracycline provided that the appropriate ozonation period is selected. At pH 11 and after 60min of ozonation of oxytetracycline aqueous solutions (100 and 200mgl(-1)) the BOD5/COD ratios were 0.69 and 0.52, respectively. It was also shown that COD removal rates increase with increasing pH as a consequence of enhanced ozone decomposition rates at elevated pH values. The results of bioluminescence data indicate that first by-products after partial ozonation (5-30min) of OTC were more toxic than the parent compound.
- [Show abstract] [Hide abstract] ABSTRACT: A simple analytical method for the quantitative analysis of fluoroquinolone group antibiotics, enrofloxacin (ENR) and ciprofloxacin (CIP) in soil was developed based on the mechanical extraction with vortex and ultrasonication and solid phase extraction followed by high pressure liquid chromatography-fluorescence detection (HPLC-FLD). Type of extraction solvents and number of extraction cycles were optimized during the method development. The most efficient extraction solvent was found as phosphate buffer at pH3 in combination with 50% of organic modifier acetonitrile with the extraction cycle of four. Overall method was applied on three different types of soils, namely, sandy, loamy sand and sandy loam and recovery rates ranged between 71–100% for ENR and 61–89% for CIP depending on the portion of organic and clay content in soils. The analytical method was also used for the estimation of fluoroquinolone concentrations in manure amended agricultural soils sampled from the different parts of Turkey and enrofloxacin was detected in the concentration range of 0.013–0.204mg/kg. In addition, sorption of fluoroquinolone antibiotics on all types of soils was investigated and the highest distribution coefficients (Kd and Kf) of fluoroquinolone compounds were obtained for loamy sand (Kd = 1.29l/g and Kf = 0.66 for CIP; Kd = 0.97l/g and Kf = 0.56 for ENR) with the highest organic carbon.
- [Show abstract] [Hide abstract] ABSTRACT: In this study, an aqueous solution of purified, hydrolyzed C.I. Reactive Red 120 (RR 120, Color Index), was selected as a model to investigate the degradation pathways and to obtain additional information on the reaction intermediate formation. The dye was purified to avoid the influence of the impurities on the ozonation process and on the formation of oxidation by-products. To simulate the dye-bath effluents from dyeing processes with azo reactive dyes, a hydrolyzed form of the dye was chosen as a representative compound. High performance liquid chromatography/mass spectrometry and its tandem mass spectrometry was chosen to identify the decomposition pathways and reaction intermediate formation during the ozonation process. In addition total organic carbon and high performance ion chromatography analysis were employed to obtain further information on the reaction processes during ozonation. Purified, hydrolyzed RR 120 was decomposed under the direct nucleophilic attack by ozone resulting in oxidation and cleavage of azo group and aromatic ring, while the triazine group still remained in the solution even after prolonged oxidation time (120 min) due to its high resistance to ozonation. Phenol, 1,2-dihydroxysulfobezene, 1-hydroxysulfonbezene were detected as the degradation intermediates, which were further oxidized by O(3) and *OH to other open-ring products and then eventually led to simple oxalic and formic acid identified by HPIC.
- [Show abstract] [Hide abstract] ABSTRACT: The antibacterial drug furazolidone belonging to the group of nitrofuran antibacterial agents has been widely used as an antibacterial and antiprotozoal feed additive for poultry, cattle, and farmed fish in China. During application a large proportion of the administered drug may reach the environment directly or via feces. Although the use of furazolidone is prohibited in numerous countries, there are indications of its illegal use. It is known that furazolidone can be rapidly metabolized to 3-amino-2-oxazolidinone (AOZ) in the body of the target organism. In this study, a total of 21 fish feed samples, including 17 commercial fish feeds from local markets in China (representing 15 different formulations) and 4 fish feeds obtained from Germany and Turkey, respectively, are analyzed to determine whether the drug is still illegally used or commercially available feeds are contaminated by this drug. High-performance liquid chromatography (HPLC) and liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) methods have been implemented to determine furazolidone and its metabolite AOZ in fish feeds containing animal protein, respectively. An efficient and convenient cleanup method for the determination of furazolidone in fish feeds is developed, and a simple cleanup method for the determination of AOZ is used. Method recoveries for samples used were determined as 87.7-98.3% for furazolidone at two spike levels of 2.0 and 5.0 ng g-1 and as 95.6-102.8% for AOZ at spike levels of 0.4 and 0.8 ng g-1. Limits of detections were 0.4 ng g-1 for furazolidone and 0.05 ng g-1 for AOZ. The established methods are therefore suitable for the determination of furazolidone and its metabolite AOZ in fish feeds at trace contamination levels. Using the established methods, all fish feed samples have been proved to be furazolidone negative; however, AOZ is tested in 16 of 17 fish feeds obtained from local markets in the Hubei province of China, with a positive rate as high as 94.1%.
- [Show abstract] [Hide abstract] ABSTRACT: The aim of this work was to evaluate the effect of linear alkylbenzene sulfonate (LAS, 200 mg l(-1)) on the fate of phenanthrene in a model ecosystem "water-lava-hydrophytes-air". The experiments were conducted using two closed cultivation chamber systems. Rushes (Juncus effesus) were selected as a representative hydrophyte. Five hundred micrograms per liter of phenanthrene in a culture solution containing a 14C-activity of 75 microCi per chamber was applied (i) to investigate the degradation of the labeled test substance and the transfer processes within the system; (ii) to determine the mass-balance possible and (iii) to detect the occurrence of volatile test substances, their volatile metabolites and the degradation end-product CO2 in the gas phase. Most of the applied 14C-activity was found in the plant (41-45%), in which approximately 95% was associated with plant roots and approximately 5% with shoots. The 14C-activity recovered in the form of VOCs and CO2 was measured in lava (18-29%, 8-11%), and in the culture solution (10-14% and 1%), respectively. Majority of the applied 14C-activity existed in two forms, i.e. (1) polar metabolites (26%), of which 91% were found in plant roots, and (2) un-extractable residues (23%), most of which were in plant roots (40%) and bounded to lava (58%). The presence of LAS significantly increased the volatilization of phenanthrene and its metabolites, inhibited its mineralization and decreased the level of 14C-activity in lava. Moreover, LAS reduced the phenanthrene level in plant roots.
- [Show abstract] [Hide abstract] ABSTRACT: The optimum conditions for decolorization of an azo dye, C.I. Reactive Black 5 (RB5) and the kinetic characteristics of manganese-dependent peroxidase (MnP) production by yeast isolate, Debaryomyces polymorphus, were investigated. D. polymorphus could completely degrade 200 mg l−1 of non-hydrolyzed and hydrolyzed C.I. Reactive Black 5 within 24 h of cultivation at an inoculum size of 1.4 g l−1 wet cells in 50 ml medium consisting of 5 g l−1 glucose and 0.5–1.0 g l−1 ammonium sulphate (pH 5–7). In addition, the MnP activities during the cultivation were evaluated in the absence and presence of 200 mg l−1C.I. Reactive Black 5. Maximum activity of MnP (1555.6 U l−1) was detected at 24 h cultivation in the presence of the dye, and a significant reduction of the enzyme activity was observed thereafter. The presence of C.I. Reactive Black 5 in the culture was found to be indispensable to the production of MnP by D. polymorphus. A good correlation was found between the dye degradation and the enzyme production.
- [Show abstract] [Hide abstract] ABSTRACT: Textile dyeing and finishing industry involves considerable amount of water usage as well as polluted and highly colored wastewater discharges. Biological treatability by means of mineralization, nitrification and denitrification of high strength woolen textile dye bathes, first- and second-rinses is presented. COD fractionation study was carried out and kinetic parameters were determined. Biodegradability of organic compounds in highly loaded composite wastewater after segregation and the effluent of applied biological treatment of high strength composite wastewater were measured by determining oxygen consumption rates. The results were used in terms of assessing an alternative method for inert COD fractionation. The study implied that about 80% soluble COD, 50% color and 75% toxicity reduction were possible by single sludge biological processes. Sixteen per cent of total COD was found to be initially inert. Inert fraction was increased to 22% by production of soluble and particulate microbial products through biological treatment.
- [Show abstract] [Hide abstract] ABSTRACT: A method based on high performance liquid chromatography/mass spectrometry (HPLC-MS) hyphenation technique for analysis of hydrolysis products of Reactive Black 5 by ozonation was investigated. The effect of linear gradient eluent program on the separation and the effect of pH on the hydrolysis process were explored. MS was used to identify the hydrolysis products. It indicates that pH influences significantly the hydrolysis products. The results show that there exists unknown reaction process except the conventional hydrolysis process. The variation of reactive group in the dye might result in the increase of toxicity during hydrolysis process.
- [Show abstract] [Hide abstract] ABSTRACT: This paper evaluates the degradation of a reactive azo dye, Procion Marine H-EXL, by catalytic wet hydrogen peroxide oxidation (CWHPO). The catalyst was prepared by ion-exchange, starting from a commercially available ultrastable Y zeolite. All experiments were performed on a laboratory scale set-up. The effects of different reaction parameters such as initial pH, catalyst and hydrogen peroxide concentrations on the oxidation of the dye aqueous solution were assessed. Apart from the conventional parameters, the toxic potential of the dye’s degradation products was investigated using the bioluminescence test. HPICE analysis was also performed to obtain detailed information on the resulting oxidation products (organic and inorganic anions). The results indicate that after only 10min at 50°C, 20mmol/l H2O2 and 1g/l FeY11.5 the color removal was as high as of 97% at pH=3 and 53% at pH=5. More than 96% removal of the dye could be attained in 30min at pH=5, t=50°C, 20mmol/l H2O2 and 1g/l FeY11.5 which corresponds to about 76% reduction of the initial COD and 37% removal of the initial TOC. A preliminary study of catalytic oxidation with hydrogen peroxide of the synthetic textile wastewater containing the specific dye is also presented. Leaching tests indicate that the activity of the catalyst is not due to leached iron ions, although an amount of 0.1–4.0ppm of iron ions was found in aqueous solution. The catalyst allows almost total elimination of the dye and a significant removal of COD and TOC without the significant leaching of Fe ions. It was also observed that by using this catalyst, it is possible to extend the range of pH values for which Fenton-type oxidation can occur and no iron hydroxide sludge is formed.
- [Show abstract] [Hide abstract] ABSTRACT: Advanced closed chamber system was used to study the fate of phenanthrene (3-rings PAHs) in the presence of linear alkylbenzene sulphonates (LAS). The results showed mineralization and metabolism of phenanthrene are fast in the "culture solution-lava-plant-air" model ecological system. The distribution proportions of applied 14C-activity in this simulative ecological system were 41%-45%, 14% to 10% and 1% in plant, lava and culture solution respectively, and 18% to 29%, 11% to 8% recovered in the forms of VOCs and CO2. Main parts of the applied 14C-activity exist in two forms, one is polar metabolites (25%) which mainly distribute in the root (23%), the other is unextractable part (23%) which have been constructed into plant root (8.98%), shoot (0.53%) or bonded to lava (13.2%). The main metabolites of phenanthrene were polar compounds (25% of applied 14C-activity), and small portion of 14C-activity was identified as non-polar metabolites (6% of applied 14C-activity) and apparent phenanthrene (1.91% of applied 14C-activity). Phenanthrene and its metabolites can be taken up through plant roots and translocated to plant shoots. The presence of LAS significantly increased the the concentration of 14C-activity in the plant and production of VOCs, at the same time it decreased the phenanthrene level in the plant and the production of CO2 at the concentration of 200 mg/L.
Helmholtz Zentrum München
München, Bavaria, Germany
- Institute of Ecological Chemistry
Chinese Academy of SciencesPeping, Beijing, China
Gheorghe Asachi Technical University of IasiSocola, Iaşi, Romania
Istanbul Technical University
İstanbul, Istanbul, Turkey
- Department of Environmental Engineering