A level change in mutagenicity of Japanese tap water over the past 12 yr

A relative comparison study of mutagenicity in Japanese tap water was conducted for 1993 and 2005 surveys. It intended to assess the effects of advanced water treatment installations to water works, improvement of raw water quality and improvement of residual HOCl concentration controlling. Sampling points (taps) were the same in both surveys. The results of 245 samples obtained by the Ames Salmonella mutagenicity test (Ames test) were analyzed. The Ames tests were conducted by using Salmonella typhimurium TA98 and TA100 strains with and without exogenous activation (S9). With the exception of TA100-S9, the other conditions needed no discussion as a factor in the mutagenicity level change. The average mutagenicity in 1993 and 2005 under the conditions of TA100-S9 were 2600 and 1100 net revertant L⁻¹, respectively. This indicated that the mutagenicity level of Japanese tap water decreased during the 12-yr period. Particularly a remarkable decrease in mutagenicity was observed in the water works where the advanced water treatments were installed during the 12-yr period. The advanced water treatments were effective in decreasing the mutagenicity of tap water. Mutagenicity also decreased in the water works with conventional water treatments; the improvement of residual HOCl concentration controlling was also considered to be effective in decreasing the mutagenicity of tap water.     

Elimination of diclofenac from water using irradiation technology

The effluents of wastewater treatment plants, usually directly emitted to the environment, often contain the anti-inflammatory drug diclofenac (DCF). The paper investigates DCF elimination using irradiation technology. Hydroxyl radical and hydrated electron reactive intermediates resulting from water radiolysis effectively degrade DCF and strongly reduce the toxicity of the solutions. OH attaches to one of the rings of DCF, and hydroxylated molecules, 2,6-dichloroaniline and quinoid type compounds are the products. Hydrated electron adds to the chlorine atom containing ring, in the reaction quinoid type compounds and 4-chloroacridine form. At a 0.1 mM DCF concentration, a ∼1 kGy absorbed dose is needed for the degradation of DCF molecules, but for mineralization of the products (in presence of O₂) an order of magnitude higher dose is required.For irradiation of wastewater after biological treatment a ∼1 kGy dose is suggested. At this dose DCF and other drugs or metabolites present at μg L⁻¹ level are eliminated together with microorganism deactivation.     

The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Treating solid dairy manure using microwave-enhanced advanced oxidation process

The microwave enhanced advanced oxidation process (MW/H₂O₂-AOP) was used to treat separated solid dairy manure for nutrient release and solids reduction. The MW/H₂O₂-AOP was conducted at a microwave temperature of 120°C for 10 minutes, and at three pH conditions of 3.5, 7.3 and 12. The hydrogen peroxide dosage at approximately 2 mL per 1% TS for a 30 mL sample was used in this study, reflecting a range of 0.53–0.75 g H₂O₂/g dry sludge. The results indicated that substantial quantities of nutrients could be released into the solution at pH of 3.5. However, at neutral and basic conditions only volatile fatty acids and soluble chemical oxygen demand could be released. The analyses on orthophosphate, soluble chemical oxygen demands and volatile fatty acids were re-examined for dairy manure. It was found that the orthophosphate concentration for untreated samples at a higher % total solids (TS) was suppressed and lesser than actual. To overcome this difficulty, the initial orthophosphate concentration had to be measured at 0.5% TS.     

Treatment of coking wastewater by an advanced Fenton oxidation process using iron powder and hydrogen peroxide

In this study the treatment of coking wastewater was investigated by an advanced Fenton oxidation process using iron powder and hydrogen peroxide. Particular attention was paid to the effect of initial pH, dosage of H₂O₂ and to improvement in biodegradation. The results showed that higher COD and total phenol removal rates were achieved with a decrease in initial pH and an increase in H₂O₂ dosage. At an initial pH of less than 6.5 and H₂O₂ concentration of 0.3 M, COD removal reached 44-50% and approximately 95% of total phenol removal was achieved at a reaction time of 1 h. The oxygen uptake rate of the effluent measured at a reaction time of 1 h increased by approximately 65% compared to that of the raw coking wastewater. This indicated that biodegradation of the coking wastewater was significantly improved. Several organic compounds, including bifuran, quinoline, resorcinol and benzofuranol were removed completely as determined by GC-MS analysis. The advanced Fenton oxidation process is an effective pretreatment method for the removal of organic pollutants from coking wastewater. This process increases biodegradation, and may be combined with a classical biological process to achieve effluent of high quality.     

Whole effluent toxicity assessment at a wastewater treatment plant upgraded with a full-scale post-ozonation using aquatic key species

Ozonation as final wastewater (WW) polishing step, following conventional activated sludge treatment is increasingly implemented in sewage treatment for contaminant degradation to prevent surface water pollution. While the oxidative degradation of chemicals has been extensively investigated, the in vivo toxicological characteristics of ozonated whole effluents are rarely a matter of research.In the present study, whole effluents were toxicologically evaluated with an in vivo test battery before and after full-scale ozonation and subsequent sand filtration on site at a treatment plant. One aquatic plant (duckweed, Lemna minor) and five invertebrate species of different systematic groups (Lumbriculus variegatus, Chironomus riparius, Potamopyrgus antipodarum, Daphnia magna) were exposed to the effluents in a flow-through-designed test system with a test duration of 7-28 d.None of the considered toxicity endpoints correlated with the pollutant elimination. A tendency towards an increased toxicity after ozonation was apparent in three of the test systems showing [statistically] significant adverse effects in the L. variegatus toxicity test (decrease in reproduction and biomass). After sand filtration, adverse effects were reduced to a similar level like after conventional treatment. Solely the Daphnia reproduction test revealed beneficial effects after ozonation in combination with sand filtration.Results of the test battery indicate the formation of adverse oxidation products during WW ozonation. L. variegatus appeared to be the most sensitive of the five test species. Sand filtration effectively removes or detoxifies toxic oxidation products, as toxic effects were subsequently reduced to the level after conventional treatment.     

Degradation of paracetamol by advance oxidation processes using modified reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3

The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO₂ and CuO/TiO₂/Al₂O₃ by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO₂/RVC, 90% degradation was achieved in 2 h while with CuO/TiO₂/Al₂O₃/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO₂/RVC/UV and 99% with CuO/TiO₂/Al₂O₃/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.     

Recent progress on application of UV excilamps for degradation of organic pollutants and microbial inactivation

Excilamps as modern mercury-free sources of narrow-band UV radiation represent an attractive alternative in environmental applications. This review focuses on recent studies on the water and surface decontamination with excilamps by means of direct photolysis and advanced oxidation processes. To date, direct photolysis and advanced oxidation processes (AOPs) such as UV/H₂O₂, UV/Fenton and UV/O₃ have been applied for degradation of organic compounds (mainly, phenols, dyes and herbicides) in model aqueous solutions. Special emphasis is placed on studies combining UV irradiation (as a pre-treatment or post-treatment step) with biological treatment. In this review, the efficiencies of direct UV, UV/H₂O₂ and UV/TiO₂ processes for inactivation of a variety of pathogenic microorganisms in water and on surfaces are discussed. The analysis of the literature shows that more works need to be done on scaling up the processes, degradation/mineralization of target pollutant(s) in real effluents and evaluation of energy requirements.     

Ambient nitrogen oxides exposure and early childhood respiratory illnesses

Acute respiratory infections are common in children below 5 years and recent studies suggest a possible link with air pollution. In this study, we investigated the association between ambient nitrogen oxides (NO_x) and bronchitis or upper airway inflammation.This longitudinal study was conducted in Teplice and Prachatice districts, Czech Republic. Children were followed from birth to 4.5 years of age. Data were compiled from medical records at delivery and at follow up, and from self-administered questionnaires from the same two time points. Air pollution monitoring data were used to estimate exposure over five different averaging periods ranging from three to 45 days prior to an episode. To quantify the association between exposure and outcome, while accounting for repeated measure correlation we conducted logistic regression analysis using generalized estimating equations.During the first 2 years of life, the adjusted rate ratio for bronchitis associated with interquartile increase in the 30-day average NO_x was 1.31 [95% confidence interval (CI): 1.07, 1.61] and for two to 4.5 year olds, it was 1.23 (95% CI: 1.01, 1.49). The 14-day exposure also had stable association across both age groups: below 2 years it was 1.25 (95% CI: 1.06, 1.47) and for two to 4.5 years it was 1.21 (95% CI: 1.06, 1.39). The association between bronchitis and NO_x increased with child's age in the under 2 years group, which is a relatively novel finding.The results demonstrate an association between NO_x and respiratory infections that are sufficiently severe to come to medical attention. The evidence, if causal, can be of public health concern because acute respiratory illnesses are common in preschool children.     

Multi-response optimization of Fenton process for applicability assessment in landfill leachate treatment

Fenton process, as a pretreatment method, was found to be effective in the primary treatment of mature/medium landfill leachate. However, the main problem of the process is the large amount of produced sludge that requires an accurate feasibility evaluation for operational applications. In this study, the response surface methodology was applied for the modeling and optimization of Fenton process in three target responses, (1) overall COD removal, (2) sludge to iron ratio (SIR) and (3) organics removal to sludge ratio (ORSR), where the latter two were new self-defined responses for prediction of sludge generation and applicability assessment of the process, respectively. The effective variables included the initial pH, [H₂O₂]/[Fe²⁺] ratio and Fe²⁺ dosage. According to the statistical analysis, all the proposed models were adequate (with adjusted R² of 0.9116–0.9512) and had considerable predictive capability (with prediction R² up to 0.9092 and appropriate adequate precision). It was found that all the variables had significant effects on the responses, specifically by their observed role in dominant oxidation mechanism. The optimum operational conditions obtained by overlay plot, were found to be initial pH of 5.7, [H₂O₂]/[Fe²⁺] ratio of 17.72 and [Fe²⁺] of 195 mM, which led to 69% COD removal, 2.4 (l sludge/consumed mole Fe²⁺) of SIR and 16.5 (gCOD removed/l produced sludge) for ORSR in verification test, in accordance with models-predicted values. Finally, it was observed that [H₂O₂]/[Fe²⁺] ratio and Fe²⁺ dosage had significant influence on COD removal, while Fe²⁺ dosage and [H₂O₂]/[Fe²⁺] ratio had remarkable effects on SIR and ORSR responses, respectively.