Theoretical Aspects Of The Kinetics Of Competitive First Reactions Of Ozone In The O3/H2O2 And O3/UV Oxidation Processes

Kinetics of competition between the ozone direct reaction with compounds in water, ozone-hydroperoxide ion reaction leading to free radicals in the O₃/H₂O₂ process, and the photolysis of ozone in the O₃/UV process are discussed in terms of diffusion and reaction times to establish conditions for these reactions to be competitive. Film theory and chemical kinetic concepts then are applied to estimate initial rates of ozone absorption and consumption, removal rates of compounds present in water, and the importance of the radical oxidation path versus direct ozone and/or photolysis reactions.     

Computer-Assisted Determination of Reaction Parameters for the Simulation of Micropollutant Abatement in Wastewater Ozonation

For the purpose of the simulation of the kinetics of the reaction of ozone with wastewater in a bubble column, the kinetics can be adequately described by two components and their respective rate constants. Ozone uptake and ozone steady states along a bubble column have been determined. A modeling procedure has been developed that allows us to describe this behavior and to simulate the degradation of micropollutants. For fast (diclofenac) and moderately fast (bezafibrate) reacting micropollutants this model describes their measured elimination well.     

Characterization of Natural Water for Potential to Oxidize Organic Pollutants with Ozone

A laboratory study has been designed to investigate the decomposition of ozone in natural water and to determine its potential to produce hydroxyl free radicals for the oxidation of micropollutants during the ozonation process of drinking water. This report describes the first data obtained using a continuous flow reactor capable of observing reactions with relatively short time scales (Q = 34 mL/min; 1.4 < t_c < 27 sec). Rates of ozone decay were studied in fulvic acid solution in the presence, or in the absence of radical scavenger (tert-butyl alcohol) or of promoter of ozone decomposition (formic acid), and a micropollutant of interest (tetrachloroethylene). Also, three natural waters were studied, illustrating that OH radical formation depends on chemical composition of the waters.     

Nanofiltration for the separation of pharmaceuticals from nutrients in source-separated urine

The potential of nanofiltration for the separation of pharmaceutical and estrogenic compounds from salts in urine was investigated with the aim of producing a micropollutant-free nutrient solution that can be used as a fertilizer. A fresh urine solution and a synthetic solution of similar inorganic composition were tested at different pH values in order to investigate their separation behavior. These solutions were spiked with the micropollutants propranolol, ethinylestradiol, ibuprofen, diclofenac and carbamazepine. Among the membranes tested, NF270 showed the best performance with respect to the retention of micropollutants. The optimum retention of micropollutants was obtained at values of around pH 5. At this point, the retention of all micropollutants in non-hydrolysed urine was above 92%, while the corresponding value for the synthetic urine solution was above 73%. From the results, it can be concluded that the retention mechanism is determined by steric and electrostatic effects as well as by the partitioning of the micropollutants in the membrane. The nutrients urea and ammonia were well permeated, but phosphate and sulfate were almost completely retained. Nanofiltration can consequently be used to produce a permeate which contains most of the nitrogen and a greatly reduced proportion of micropollutants.     

Performances of RO and NF processes for wastewater reuse: Tertiary treatment after a conventional activated sludge or a membrane bioreactor

Wastewater reclamation requires processes and technologies having the ability to reduce the presence of micropollutants which are not wholly treated in conventional WWTP. Due to the complexity of membrane-solute interactions and the diversity of secondary treatment effluent (STE) matrices, deeper investigations are required to identify the major foulant species and more specifically their behaviour at high concentration in real waters. This study investigates the rejection and fouling potential of nanofiltration (NF) and low-pressure reverse osmosis (RO) membranes with two STEs sampled from i) a conventional activated sludge process coupled with ultrafiltration (CAS-UF) and from ii) a membrane bioreactor MBR (AquaRM^®, SAUR (France)). Whatever the origin of the effluent, RO seems to be the best solution to prevent pollution of tertiary effluents (expected result) but also to obtain low fouling levels. The different composition and molecular weight distribution of MBR and CAS-UF effluents can explain the different fouling behaviours that were observed.     

Kinetic assessment and modeling of an ozonation step for full-scale municipal wastewater treatment: Micropollutant oxidation, by-product formation and disinfection

The kinetics of oxidation and disinfection processes during ozonation in a full-scale reactor treating secondary wastewater effluent were investigated for seven ozone doses ranging from 0.21 to 1.24 g O₃ g⁻¹ dissolved organic carbon (DOC). Substances reacting fast with ozone, such as diclofenac or carbamazepine (kP,O₃ > 10⁴ M⁻¹ s⁻¹), were eliminated within the gas bubble column, except for the lowest ozone dose of 0.21 g O₃ g⁻¹ DOC. For this low dose, this could be attributed to short-circuiting within the reactor. Substances with lower ozone reactivity (kP,O₃ < 10⁴ M⁻¹ s⁻¹) were only fully eliminated for higher ozone doses.The predictions of micropollutant oxidation based on coupling reactor hydraulics with ozone chemistry and reaction kinetics were up to a factor of 2.5 higher than full-scale measurements. Monte Carlo simulations showed that the observed differences were higher than model uncertainties. The overestimation of micropollutant oxidation was attributed to a protection of micropollutants from ozone attack by the interaction with aquatic colloids. Laboratory-scale batch experiments using wastewater from the same full-scale treatment plant could predict the oxidation of slowly-reacting micropollutants on the full-scale level within a factor of 1.5. The Rct value, the experimentally determined ratio of the concentrations of hydroxyl radicals and ozone, was identified as a major contribution to this difference.An increase in the formation of bromate, a potential human carcinogen, was observed with increasing ozone doses. The final concentration for the highest ozone dose of 1.24 g O₃ g⁻¹ DOC was 7.5 μg L⁻¹, which is below the drinking water standard of 10 μg L⁻¹. N-Nitrosodimethylamine (NDMA) formation of up to 15 ng L⁻¹ was observed in the first compartment of the reactor, followed by a slight elimination during sand filtration. Assimilable organic carbon (AOC) increased up to 740 μg AOC L⁻¹, with no clear trend when correlated to the ozone dose, and decreased by up to 50% during post-sand filtration. The disinfection capacity of the ozone reactor was assessed to be 1-4.5 log units in terms of total cell counts (TCC) and 0.5 to 2.5 log units for Escherichia coli (E. coli). Regrowth of up to 2.5 log units during sand filtration was observed for TCC while no regrowth occurred for E. coli. E. coli inactivation could not be accurately predicted by the model approach, most likely due to shielding of E. coli by flocs.     

Screening of 47 organic microcontaminants in agricultural irrigation waters and their soil loading

Reclaimed water usage for crop irrigation is viewed both as an excellent sustainable water source and as a potential entrance for emerging organics into the food chain. This concern is backed by the already documented pollutant crop uptake potential. In the present study, irrigation waters used in agricultural fields (Torroella de Montgri, NE Spain) were screened for 47 analytes in a two year study (2007-2008). A total of 26 contaminants belonging to different chemical classes namely, pesticides, pharmaceuticals, personal care products, phenolic estrogens, antioxidants and disinfection by-products, were detected. Marked differences in concentration trends for the different chemical classes were evidenced from 2007 to 2008, and attributed to a persistent drought endured by the region in 2008. Also, loading mass rates of chemical classes were estimated based on crop irrigation regimes and they ranged from 0.8 to 121.3 g ha⁻¹ per crop cycle. These values were contrasted with those obtained for other water sources from countries where crop irrigation is commonly practiced. Finally, crops grown under these irrigation regimes, namely alfalfa and apple, were analyzed and 5 anthropogenic compounds were identified and quantitated, whose concentrations ranged from 13.9 to 532 ng g⁻¹ (fresh weight).     

Electrochemical degradation of the β-blocker metoprolol by Ti/Ru 0.7 Ir 0.3 O 2 and Ti/SnO 2-Sb electrodes

Electrochemical oxidation has been proposed for the elimination of pesticides, pharmaceuticals and other organic micropollutants from complex waste streams. However, the detrimental effect of halide ion mediators and the generation of halogenated by-products in this process have largely been neglected thus far. In this study, we investigated the electrochemical oxidation pathways of the β-blocker metoprolol in reverse osmosis concentrate (ROC) from a water reclamation plant using titanium anodes coated with Ru_0.7Ir_0.3O₂ or SnO₂-Sb metal oxide layers. The results of liquid chromatography-mass spectrometry analysis indicated that irrespective of the electrode coating the same oxidant species participated in electrochemical transformation of metoprolol in ROC. Although Ti/SnO₂-Sb exhibited higher oxidizing power for the same applied specific electrical charge, the generation of large fractions of chloro-, chloro-bromo- and bromo derivatives was observed for both electrode coatings. However, degradation rates of metoprolol and its degradation products were generally higher for the Ti/SnO₂-Sb anode. Chemical analyses of metoprolol and its by-products were complemented with bioanalytical tools in order to investigate their toxicity relative to the parent compound. Results of the bioluminescence inhibition test with Vibrio fischeri and the combined algae test with Pseudokirchneriella subcapitata indicated a substantial increase in non-specific toxicity of the reaction mixture due to the formed halogenated by-products, while the specific toxicity (inhibition of photosynthesis) remained unchanged.     

Loss rates of urban biocides can exceed those of agricultural pesticides

Biocides and pesticides are used to control unwanted organisms in urban and agricultural areas. After application, they can be lost to surface waters and impair water quality. Several national consumption studies have shown that urban and agricultural use may be in the same range. It is difficult to judge whether this results in similar loadings of surface waters because there is a lack of sound, comparative studies addressing urban and agricultural losses simultaneously.The aim of this study is thus to relate the biocide and pesticide loads found in surface waters to their respective urban and agricultural usage (loss rates). To simultaneously assess the loss rates, we conducted a comprehensive field study in a catchment of mixed land use on the Swiss Plateau. The study area was divided into four sub-catchments with different degrees of urban and agricultural land use. In addition, we studied the only wastewater treatment plant, a combined sewer overflow and a storm sewer within the area. Rain events were sampled at high temporal resolution from March to November, 2007. Information on agricultural applications was gained from local farmers. For urban uses, consumption estimations were conducted based on statistical and product information.Despite substantially lower amounts used, the measured loads of urban biocides were in the same range as the most widely-used agricultural pesticides. The lower usage was compensated by urban loss rates that were up to ten times higher than agricultural ones (0.6 to 15% for urban, 0.4 to 0.9% for agricultural compounds). For most biocides and pesticides, the loads were controlled by rain events. Besides the rain-controlled losses, some urban-used biocides (e.g. diazinon) showed a continuous load independent of rain events and season. This study demonstrates that in catchments with mixed land use, mitigation strategies have to pay sufficient attention to the urban sources.     

PAH fate during the anaerobic digestion of contaminated sludge: Do bioavailability and/or cometabolism limit their biodegradation?

The anaerobic removal of 13 Polycyclic Aromatic Hydrocarbons (PAHs) was measured in five continuous anaerobic digestors with different feed sludge, in which abiotic losses were neglected. These feeds were chosen to generate different levels of PAH bioavailability and cometabolism within the reactors. Based on the accurate modelling of PAH sorption in sludge, the aqueous fraction (including free and sorbed-to-dissolved-and-colloidal-matter PAHs) was demonstrated to be bioavailable, which validated a widespread assumption about micropollutants bioavailability in sludge.It was also demonstrated that bioavailability is not the only influencing factor. Indeed, PAHs biodegradation resulted from a combination of bioavailability and cometabolism. An equation adapted from Criddle (1993, The Kinetics of Cometabolism. Biotechnology and Bioengineering 41, 1048-1056) that takes into account both mechanisms was shown to fit the experimental data, with dry matter removal rate identified as the criteria for cometabolism. The existence of a threshold of dry matter cometabolism was suggested, below which PAHs removal would not be possible. The parameters of the Criddle equation were demonstrated to depend on PAH molecular structure, and the results suggest that they would also be influenced by substrate composition and microbial population.This research provided original outcomes for the assessment of micropollutants fate. Indeed, the understanding of the driving mechanisms was improved, which has implications for the optimization of micropollutants removal.