Oxidation of resin and fatty acids by ozone: kinetics and toxicity study

The ozonation of resin and fatty acids (RFAs) found in pulp mill effluents was investigated using rapid-scan stopped-flow spectrophotometry. RFAs oxidation (i.e., degradation) efficiency increased with increasing the amount of used ozone and temperature. The degradation process with respect to the acid was found to follow first-order kinetics. The ozonation of RFAs was modeled as an overall second-order reaction for both reactants. The apparent overall second-order rate constants were calculated based on the pseudo first-order rate constants obtained from the kinetic data fitting for the acid degradation. The apparent overall second-order rate constant was affected by pH and temperature. At 20 degrees C and when pH increased from 8 to 11, the apparent overall second-order rate constant increased almost by a factor of 5 (from 3.9 x10(3) to 1.8 x10(4)M(-1)s(-1)) for 9 mgL(-1) resin acid and a factor of 4 (from 9.6 x10(3) to 3.9 x10(4)M(-1)s(-1)) for 8 mgL(-1) fatty acid. At pH 8 and as temperature increased from 10 to 20 degrees C, the apparent overall second-order rate constant increased almost by a factor of 5 (from 8.2 x10(2) to 3.9 x10(3)M(-1)s(-1)) for 9 mgL(-1) resin acid and a factor of 3 (from 3.5 x10(3) to 9.6 x10(3)M(-1)s(-1)) for 8 mgL(-1) fatty acid. Microtox bioassay tests were completed to evaluate the toxicity of RFAs samples before and after ozonation. For the resin acid, there was an increase in toxicity as a result of ozonation. Meanwhile, toxicity of fatty acid samples decreased as a result of ozonation.     

Carbamazepine in water: persistence in the environment,ozonation treatment and preliminary assessment on algal toxicity

The presence of carbamazepine (CBZ), an antiepilectic drug, has been reported in sewage treatment plant (STP) effluents as a result of its low biodegradability. In the present work, the persistence of CBZ in aquatic environment with respect to abiotic transformation processes along with its toxicity and capability of accumulating in single aquatic organisms (algae) are evaluated. The possibility of removing CBZ from STP effluents is studied by characterizing its ozonation process through the assessment of kinetics and the distribution of oxidation products.     

Kinetics of the transformation of phenyl-urea herbicides during ozonation of natural waters: rate constants and model predictions

Oxidation of four phenyl-urea herbicides (isoproturon, chlortoluron, diuron, and linuron) was studied by ozone at pH=2, and by a combination of O3/H2O2 at pH=9. These experiments allowed the determination of the rate constants for their reactions with ozone and OH radicals. For reactions with ozone, the following rate constants were obtained: 1.9 +/- 0.2, 16.5 +/- 0.6, 393.5 +/- 8.4, and 2191 +/- 259 M(-1) s(-1) for linuron, diuron, chlortoluron, and isoproturon, respectively. The rate constants for the reaction with OH radicals were (7.9 +/- 0.1) x 10(9) M(-1) s(-1) for isoproturon, (6.9 +/- 0.2) x 10(9) M(-1) s(-1) for chlortoluron, (6.6 +/- 0.1) x 10(5) M(-1) s(-1) for diuron, and (5.9 +/- 0.1) x 10(9) M(-1) s(-1) for linuron. Furthermore, the simultaneous ozonation of these selected herbicides in some natural water systems (a commercial mineral water, a groundwater, and surface water from a reservoir) was studied. The influence of operating conditions (initial ozone dose, nature of herbicides, and type of water systems) on herbicide removal efficiency was established, and the parameter Rct (proposed by Elovitz, M.S., von Gunten, U., 1999. Hydroxyl radical/ozone ratios during ozonation processes. I. The Rct concept. Ozone Sci. Eng. 21, 239-260) was evaluated from simultaneous measurement of ozone and OH radicals. A kinetic model was proposed for the prediction of the elimination rate of herbicides in these natural waters, and application of this model revealed that experimental results and predicted values agreed fairly well. Finally, the partial contributions of direct ozone and radical pathways were evaluated, and the results showed that reaction with OH radicals was the major pathway for the oxidative transformation of diuron and linuron, even when conventional ozonation was applied, while for chlortoluron and isoproturon, direct ozonation was the major pathway.     

Oxidation of pharmaceuticals during water treatment with chlorine dioxide

The potential of chlorine dioxide (ClO2) for the oxidation of pharmaceuticals during water treatment was assessed by determining second-order rate constants for the reaction with selected environmentally relevant pharmaceuticals. Out of 9 pharmaceuticals only the 4 following compounds showed an appreciable reactivity with ClO2 (in brackets apparent second-order rate constants at pH 7 and T = 20 degrees C): the sulfonamide antibiotic sulfamethoxazole (6.7 x 10(3) M(-1) s(-1)), the macrolide antibiotic roxithromycin (2.2 x 10(2) M(-1) s(-1)), the estrogen 17alpha-ethinylestradiol (approximately 2 x 10(5) M(-1) s(-1)), and the antiphlogistic diclofenac (1.05 x 10(4) M(-1) s(-1)). Experiments performed using natural water showed that ClO2 also reacted fast with other sulfonamides and macrolides, the natural hormones estrone and 17beta-estradiol as well as 3 pyrazolone derivatives (phenazone, propylphenazone, and dimethylaminophenazone). However, many compounds in the study were ClO2 refractive. Experiments with lake water and groundwater that were partly performed at microgram/L to nanogram/L levels proved that the rate constants determined in pure water could be applied to predict the oxidation of pharmaceuticals in natural waters. Compared to ozone, ClO2 reacted more slowly and with fewer compounds. However, it reacted faster with the investigated compounds than chlorine. Overall, the results indicate that ClO2 will only be effective to oxidize certain compound classes such as the investigated classes of sulfonamide and macrolide antibiotics, and estrogens.     

Effects of isocyanuric acid on the monochlorodimedone chlorinating rates with free chlorine and ammonia chloramine in water

Changes in monochlorodimedone (MCD) chlorinating rates with free chlorine (mixture of HOCl and OCl-) and ammonia monochloramine (NH2Cl) in water at pH 7 by the addition of isocyanuric acid (H3Cy) were determined at room temperature. Decreases in MCD absorbance at 290nm in equimolar (0.04mM) reactions of MCD and free available chlorine solutions containing H3Cy (0.01-1.60 mM) were recorded in a stopped-flow spectrophotometer. The rates indicate second-order reactions. Since the rate with free chlorine was high (> 7.6 x 10(6) M(-1) s(-1)), the amounts of free chlorine in the solutions could be distinguished from that of chlorinated cyanurates. The chlorinating rates with chlorinated cyanurates decreased with an increase in H3Cy concentrations. Plotting the rates against the molar ratio of chlorine to H3Cy showed a linear correlation and the rates with chlorinated cyanurates (H2ClCy) was estimated at 0.5 x 10(5) M(-1) s(-1). In contrast, the rates with the NH2Cl solution containing H3Cy increased with an increase in H3Cy concentrations, increasing from 1.2 x 10 to 2.7 x 10 M(-1) s(-1) by the addition of 1.55 mM H3Cy. The DPD color development rates (OD512/t1/2/M) with free available chlorine (0.015mM) declined from 1.3 x 10(5) to 0.9 x 10(5)M(-1) by the addition of 0.61 mM H3Cy.     

Effect of pH on toxicity of kraft pulp and paper mill effluent to salmonid fish in fresh and seawater

In freshwater bioassays with juvenile rainbow trout (Salmo gairdneri), at initial pH values from 4 to 11, kraft mill effluents were considerably less toxic at pH 9–10 than at neutrality. When pH of test solutions was controlled throughout the bioassay period, the least toxic range was 8.5–9.5. Toxicity at typical receiving-water pH values was 50–67% greater.The acute toxicity of effluent samples to yearling coho salmon (Oncorhynchus kisutch) was identical for these effluents in seawater and freshwater respectively, provided that the pH was adjusted and held at the same value, and that test fish were previously acclimated to the dilution water for several months. Thus seawater constituents other than pH did not affect the acute toxicity of pulp and paper mill effluents appreciably.     

Chlorine photolysis and subsequent OH radical production during UV treatment of chlorinated water

The photodegradation of chlorine-based disinfectants NH(2)Cl, HOCl, and OCl(-) under UV irradiation from low- (LP) and medium-pressure (MP) Hg lamps was studied. The quantum yields of aqueous chlorine and chloramine under 254nm (LP UV) irradiation were greater than 1.2molEs(-1) for free chlorine in the pH range of 4-10 and 0.4molEs(-1) for monochloramine at pH 9. Quantum yields for MP (200-350nm) ranged from 1.2 to 1.7molEs(-1) at neutral and basic pH to 3.7molEs(-1) at pH 4 for free chlorine, and 0.8molEs(-1) for monochloramine. Degradation of free chlorine was enhanced under acidic water conditions, but water quality negatively impacted the MP Hg lamp degradation of free chlorine, compared to the LP UV source. The production of hydroxyl radical via chlorine photolysis was assessed along with the rate of reaction between ()OH and HOCl using radical scavengers (parachlorobenzoic acid and nitrobenzene) in chlorinated solutions at pH 4. The quantum yield of OH radical production from HOCl at 254nm was found to be 1.4molEs(-1), while the reaction of HOCl with OH radical was measured as 8.5x10(4)M(-1)s(-1). NH(2)Cl was relatively stable in all irradiated solutions, with <0.3mgL(-1) increase in nitrate following a UV dose of 1000mJcm(-2). For water treatment plants, no significant changes in chlorine concentration would be expected under typical pH levels and UV doses; however, the formation of ()OH could have implications for chlorinated byproducts or decay of unwanted chemical contaminants.     

Plasmachemical degradation of azo dyes by humid air plasma: Yellow Supranol 4 GL, Scarlet Red Nylosan F3 GL and industrial waste

A recent non-thermal plasma technique (i.e., a gliding arc discharge which generates reactive species at atmospheric pressure) is tested for pollution abatement of dyes dispersed in synthetic solutions and industrial effluents. Yellow Supranol 4 GL (YS) and Scarlet Red Nylosan F3 GL (SRN) are toxic synthetic dyes widely used in the Algerian textile industry and frequently present in liquid wastes of manufacture plants. Classical removal treatment processes are not efficient enough, so that the presence of dyes in liquid effluents may cause serious environmental problems, in connection with reusing waste waters for irrigation. The degradation processes achieved by the oxidising species formed in the plasma are followed by UV/VIS spectroscopy and by chemical oxygen demand measurements. They are almost complete (i.e., 92.5% for YS and 90% for dilute SRN) and rapidly follow pseudo-first-order laws, with overall estimated rate constants 3 x 10(-4) and 4 x 10(-4)s-1 for YS and SRN, respectively. The degradation rate constant for the industrial mixture (i.e., k = 1.45 x 10(-3)s-1) is a mean value for two consecutive steps (210(-3) and 6 x 10(-5)s-1) measured at the absorption peaks of the major constituent dyes, YS and SRN.     

Coprecipitation of arsenate with iron(III) in aqueous sulfate media: effect of time, lime as base and co-ions on arsenic retention

The removal and immobilization of arsenic from industrial mineral-processing effluents typically involves lime neutralization and coprecipitation of arsenate with ferric iron. Despite the wide practice and environmental importance of this technique, no laboratory study has focused on the roles of lime as base and third ions like Ca2+, Ni2+ and SO(2)4(-) on the kinetics of arsenic retention by the coprecipitates. In this work, coprecipitation was performed at 22 degrees C by fast (10 min) neutralization of industrially relevant concentrated arsenate-iron(III) (Fe/As=2, 4) acidic sulfate solutions to different pHs (4, 6, 8) in batch reactors, and the concentration of arsenic was monitored up to 1 year. The tests showed that maximum removal of arsenic was achieved upon neutralization to the target pH. Arsenic was found to be released back into solution from the precipitates upon continuing mild agitation at constant pH. Near-equilibrium was attained at different times depending on the applied pH: 10 days at pH 4, 6 months at pH 6 and 9 months at pH 8. An aging treatment at pH 4 significantly enhanced arsenic retention (arsenic release was reduced by at least 50%) after the system was finally stabilized at pH 8. The retention of arsenic at pH 8 was multifold improved (by a factor x 25) when lime was used instead of NaOH. Similarly, the retention of arsenic was enhanced by the presence of calcium and nickel ions in the starting solution. Finally, evidence of Ca(II)-Fe(III)-As(V) association was found, but not sulfate incorporation at pH 8.     

Kinetics of triclosan oxidation by aqueous ozone and consequent loss of antibacterial activity: relevance to municipal wastewater ozonation

Oxidation of the antimicrobial agent triclosan by aqueous ozone (O(3)) was investigated to determine associated reaction kinetics, reaction site(s), and consequent changes in antibacterial activity of triclosan. Specific second-order rate constants, k(O(3)), were determined for reaction of O(3) with each of triclosan's acid-base species. The value of k(O(3)) determined for neutral triclosan was 1.3(+/-0.1)x10(3)M(-1)s(-1), while that measured for anionic triclosan was 5.1(+/-0.1)x10(8)M(-1)s(-1). Consequently, triclosan reacts very rapidly with O(3) at circumneutral pH (the pH-dependent, apparent second-order rate constant, K(app,O(3)) , is 3.8x10(7)M(-1)s(-1) at pH 7). The pH-dependence of K(app,O(3)) and comparison of triclosan reactivity toward O(3) with that of other phenolic compounds indicates that O(3) reacts initially with triclosan at the latter's phenol moiety. k(O(3)) values for neutral and anionic triclosan were successfully related to phenol ring substituent effects via Brown-Okamoto correlation with other substituted phenols, consistent with electrophilic attack of the triclosan phenol ring. Biological assay of O(3)-treated triclosan solutions indicates that reaction with O(3) yields efficient elimination of triclosan's antibacterial activity. In order to evaluate the applicability of these observations to actual wastewaters, triclosan oxidation was also investigated during ozonation of effluent samples from two conventional wastewater treatment plants. Nearly 100% triclosan depletion was achieved for a 4 mg/L(8.3x10(-5)mol/L)O(3) dose applied to a wastewater containing 7.5 mg/L of DOC, and approximately 58% triclosan depletion for dosage of 6 mg/L(1.3x10(-4)mol/L)O(3) to a wastewater containing 12.4 mg/L of DOC. At O(3) doses greater than 1mg/L(2.1x10(-5)mol/L), hydroxyl radical reactions accounted for <35% of observed triclosan losses in these wastewaters, indicating that triclosan oxidation was due primarily to the direct triclosan-O(3) reaction. Thus, ozonation appears to present an effective means of eliminating triclosan's antibacterial activity during wastewater treatment.     

Degradation and byproduct formation of parathion in aqueous solutions by UV and UV/H(2)O(2) treatment

The photodegradation of parathion in aqueous solutions by UV and UV/H(2)O(2) processes was evaluated. Direct photolysis of parathion both by LP (low pressure) and MP (medium pressure) lamps at pH 7 was very slow with quantum yields of 6.67+/-0.33x10(-4) and 6.00+/-1.06x10(-4)molE(-1), respectively. Hydrogen peroxide enhanced the photodegradation of parathion through the reaction between UV generated hydroxyl radical and parathion with a second-order reaction rate constant of 9.70+/-0.45x10(9)M(-1)s(-1). An optimum molar ratio between hydrogen peroxide and parathion was determined to be between 300 and 400. Photodegradation of parathion yielded several organic byproducts, of which the paraoxon, 4-nitrophenol, O,O,O-triethyl thiophosphate and O,O-diethyl-methyl thiophosphate were quantified and their occurrence during UV/H(2)O(2) processes were discussed. NO(2)(-), PO(4)(3-), NO(3)(-) and SO(4)(2-) were the major anionic byproducts of parathion photodegradation and their recover ratios were also discussed. A photodegradation scheme suggesting three simultaneous pathways was proposed in the study.     

Occurrence and removal of organic pollutants in sewages and landfill leachates

Sewages of different composition and the effluents of four sewage treatment plants (STPs), plus sewage sludges were analysed for semivolatile organic priority pollutants. Furthermore, 11 landfill leachates were analysed to evaluate their contribution to sewage pollutants when co-treated. Bis(2-ethylhexyl) phthalate (DEHP) was the pollutant occurring at highest concentrations (up to 122 microg/l) and it was present in all sewages and leachates; concentrations of other phthalates were usually below 17 microg/l. Some polycyclic aromatic hydrocarbons (PAH) (<1 microg/l) and 2,6-dinitrotoluene (< or =5.9 microg/l) were also present in many of the sewages and leachates. Phthalates were present in STP effluents in low concentrations (<8 microg/l), while PAHs were usually not present. DEHP concentrations were at the same level in the sewage consisting of household wastewater and stormwater runoff and the sewages also including industrial discharges and landfill leachates, while PAHs were present in sewages containing industrial discharges. Leachate contribution to the total pollutant load to the STP was less than 1%. Sorption of DEHP to different particle size fractions in sewage was studied by serial membrane filtration. Most of the DEHP (71-84%) was attached to the particles 0.1-41 microm in size, and approximately 10-27% of the DEHP was sorbed on particles larger than 41 microm. Less than 6% of the DEHP was in the fraction below 0.1 microm and readily available for microbial degradation.     

Spectrophotometric determination of ferrate (Fe(VI)) in water by ABTS

A new method for the determination of low concentrations (0.03-35 microM) of the aqueous ferrate (Fe(VI)) was developed. The method is based on the reaction of Fe(VI) with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) which forms a green radical cation (ABTS(+)) that can be measured spectrophotometrically at 415 nm (ABTS method). The reaction of Fe(VI) with ABTS has a stoichiometry of 1 : 1 in excess of ABTS (73 microM). The increase in absorbance at 415 nm for ABTS*+ generation was linear with respect to Fe(VI) added (0.03-35 microM) in buffered solutions (acetate/phosphate buffer at pH = 4.3) and was (3.40+/-0.05) x 10(4) M(-1) cm(-1). The reaction of Fe(VI) with ABTS was very rapid with a half-life time below 0.01 s at pH 4.3 and 73 microM of ABTS. This enables the ABTS method to measure Fe(VI) selectively. The residual absorbance of ABTS*+ was found to be stable in several water matrices (synthetic buffer solution and natural waters) and concentrations of Fe(VI) spiked in natural waters could be determined with high accuracy. The ABTS method can also be used as a tool to determine rate constants of reactions of Fe(VI). The second-order rate constant for the reaction of phenol with Fe(VI) was determined to be 90 M(-1) s(-1) at pH 7.     

Advanced oxidation of the pharmaceutical drug diclofenac with UV/H2O2 and ozone

Diclofenac, a widely used anti-inflammatory drug, has been found in many Sewage Treatment Plant effluents, rivers and lake waters, and has been reported to exhibit adverse effects on fish. Advanced oxidation processes, ozonation and H2O2/UV were investigated for its degradation in water. The kinetic of the degradation reaction and the nature of the intermediate products were still poorly defined. Under the conditions adopted in the present study, both ozonation and H2O2/UV systems proved to be effective in inducing diclofenac degradation, ensuring a complete conversion of the chlorine into chloride ions and degrees of mineralization of 32% for ozonation and 39% for H2O2/UV after a 90 min treatment. The reactions were found to follow similar, but not identical, reaction pathways leading to hydroxylated intermediates (e.g. 2-[(2,6-dichlorophenyl)amino]-5-hydroxyphenylacetic acid) and C-N cleavage products (notably 2,5-dihydroxyphenylacetic acid) through competitive routes. Subsequent oxidative ring cleavage leads to carboxylic acid fragments via classic degradation pathways. In the pH range 5.0-6.0 kinetic constants (1.76 x 10(4)-1.84 x 10(4) M(-1) s(-1)) were estimated for diclofenac ozonation.     

Effects of lipids and oleic acid on biomass development in anaerobic fixed-bed reactors. Part II: Oleic acid toxicity and biodegradability

Oleic acid toxicity and biodegradability were followed during long-term operation of two similar anaerobic fixed-bed units. When treating an oleate based effluent, the sludge from the bioreactor that was acclimated with lipids during the first operation period, showed a higher tolerance to oleic acid toxicity (IC50 = 137 mg/l) compared with the sludge fed with a non-fat substrate (IC50 = 80 mg/l). This sludge showed also the highest biodegradation capacity of oleic acid, achieving maximum methane production rates between 33 and 46 mlCH4(STP)/gVS.day and maximum percentages of methanization between 85 and 98% for the range of concentrations between 500 and 900 mg oleate/l. When oleate was the sole carbon source fed to both digesters, the biomass became encapsulated with organic matter, possibly oleate or an intermediate of its degradation, e.g. stearate that was degraded at a maximum rate of 99 mlCH4(STP)/gVS.day. This suggests the possibility of using adsorption-degradation cycles for the treatment of LCFA based effluents. Both tolerance to toxicity and biodegradability of oleic acid were improved by acclimatization with lipids or oleate below a threshold concentration.     

Occurrence of antibiotics in the aquatic environment

The recent monitoring of drug residues in the aquatic environment has gained much interest as many pharmaceutical compounds can frequently be found in sewage treatment plant (STP) effluents and river water at concentrations up to several microgram/l. This article describes the analysis of various water samples for 18 antibiotic substances, from the classes of macrolid antibiotics, sulfonamides, penicillins and tetracyclines. Samples were preconcentrated via lyophilization and quantified using HPLC-electrospray-tandem-mass spectrometry. The investigated STP effluents and surface water samples showed frequent appearance of an erythromycin degradation product, roxithromycin and sulfamethoxazole with concentrations up to 6 micrograms/l. Neither tetracyclines nor penicillins could be detected at concentration levels above 50 and 20 ng/l, respectively. From the large number of ground water samples that were taken from agricultural areas in Germany, no contamination by antibiotics was detected except for two sites. This indicates that intake from veterinary applications to the aquatic environment is of minor importance.     

Ozonation of reverse osmosis concentrate: kinetics and efficiency of beta blocker oxidation

Reverse osmosis (RO) concentrate samples were obtained from a RO-membrane system that uses effluents of wastewater treatment plants (WWTP) as feed water for the production of drinking water. A number of different pharmaceuticals (e.g. antibiotics, contrast media, beta blockers) were found in the WWTP effluent as well as in the RO-concentrate. Overall, a concentration factor (feed:concentrate) of approximately 3-4 was measured. Beta blockers (acebutolol, atenolol, bisoprolol, celiprolol, metoprolol, propranolol, timolol) were found in the range of low ng/L to low microg/L. Because metoprolol and propranolol are classified as potentially toxic to aquatic organisms and all beta blocker molecules have moieties, which are reactive towards ozone (amine groups, activated aromatic rings), it was tested whether ozonation can be applied for their mitigation. Rate constants for the reaction of acebutolol, atenolol, metoprolol and propranolol with ozone and OH radicals were determined. At pH 7 acebutolol, atenolol and metoprolol react with ozone with an apparent second-order rate constant ( [Formula: see text] ) of about 2,000 M(-1)s(-1), whereas propranolol reacts with approximately 10(5)M(-1)s(-1). The rate constants for the reaction of the selected compounds with OH radicals were determined to be 0.5-1.0 x 10(10)M(-1)s(-1). Experiments with RO concentrate showed that an ozone dose of only 5mg/L resulted in a quantitative removal of propranolol in 0.8s and 10mg O(3)/L oxidized 70% of metoprolol in only 1.2s. Tests with chlorinated and non-chlorinated WWTP effluent showed an increase of ozone stability but a decrease of hydroxyl radical exposure in the samples after chlorination. This may shift the oxidation processes towards direct ozone reactions and favor the degradation of compounds with high [Formula: see text].     

Occurrence of acidic pharmaceuticals in raw and treated sewages and in receiving waters

The occurrence of five acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, diclofenac and bezafibrate, in seven different sewage treatment plants (STP) and three receiving waters were determined. The analytical procedure included solid phase extraction, liquid chromatographic separation and detection by a triple-quadrupole mass spectrometer. The studied pharmaceuticals were found in all the STPs. The pattern of the occurrence of individual compounds was the same in every STP and matched the consumption figures reported in the literature. Ibuprofen is the most used pharmaceutical in Finland and was accordingly found to be the most abundant compound in the raw sewage. In the treatment processes, the highest removal rate was observed for ibuprofen and the lowest for diclofenac, 92%+/-8% and 26%+/-17%, respectively. Due to the incomplete removal in the STPs, the pharmaceuticals were found in rivers at the discharge points of the STP effluents. Downstream from the discharge points, the concentrations decreased significantly mainly due to dilution in the river water. The risk to the aquatic environment was estimated by a ratio of measured environmental concentration (MEC) and predicted no-effect concentration (PNEC). At the concentrations the compounds were found in the surface waters, they should not pose risk for the aquatic environment. However, at dry seasons and/or during malfunctions of STPs, ibuprofen could be associated with a risk in small river systems.     

Fenton's oxidation of MTBE with zero-valent iron

Methyl tert-butyl ether (MTBE) has become a contaminant of increasing concern in the U.S. Traditional remediation technologies are successful in removing MTBE from contaminated water, but usually transfer the contaminant from the aqueous to another phase. Fenton's oxidation of MTBE provides a promising alternative to traditional remediation techniques in that it may mineralize the contaminant rather than just phase transfer. This bench-scale study investigated the feasibility of Fenton's oxidation of MTBE using zero-valent iron as the source of catalytic ferrous iron. The oxidation reactions were able to degrade over 99% of the MTBE within 10 min, and showed significant generation, and subsequent degradation, of the MTBE oxidation byproduct acetone. Second-order rate constants for MTBE degradation were 1.9 x 10(8) M(-1) s(-1) at pH 7.0 and 4.4 x 10(8) M(-1) s(-1) at pH 4.0. The total organic carbon was reduced by over 86% when a H2O2:MTBE ratio of 220:1 or greater was used.     

Identification of organic compounds and ecotoxicological assessment of sewage treatment plants (STP) effluents

An integrated approach combining chemistry and biological methods was conducted to assess the toxicity of seven sewage treatment plant effluents. Solid phase concentration procedures were applied to facilitate the study of organic micro pollutants. A chemical analysis was performed by GC/MS. Organic fraction toxicity was determined by using bioassays such as Daphnia magna and Chlorella vulgaris tests and sub-lethal effects were also evaluated by using Salmonella typhimurium Test (mutagenicity), recombinant yeast screen (estrogenicity), and Oryzias latipes embryo-larval test. More than 49 compounds were detected in the organic fraction due to the various inputs of each effluents. The most frequently detected compounds in the effluents were bisphenol A (BPA), octylphenol (OP), 1,2-benzenedicarboxylic acid, bis(2-ethylhexyl) ester (DEHP) and 1,2-benzenedicarboxylic acid, bis(methylpropyl) ester (DBP). Biological assays showed toxicity effects on D. magna tests in all samples, whereas toxicity on C. vulgaris or S. typhimurium tests were not observed. Estrogenicity and teratogenicity were observed in several samples. The cause-effect relationship could not be established given the high chemical complexity of the effluents and the lack of information available on 70% of the detected compounds subsequent to reviewing various data bases. Nevertheless, due to the high chemical variability revealed by STP effluents, bioassay sets may provide a very useful amount of information for detecting potential toxicity risks.