Metal-doped carbon aerogels as catalysts during ozonation processes in aqueous solutions

The efficiency of Co(II)-, Mn(II)-, and Ti(IV)-doped carbon aerogels for the transformation of ozone into (*)OH radicals was investigated. The carbon aerogels had a markedly acid surface character (pH(PZC approximately equal) congruent with 3-4) with very high surface oxygen concentrations (O approximately equal with 20%). X-ray photoelectron spectroscopy (XPS) analyses of the samples showed the oxidation state of the metals was +2 for Co and Mn and +4 for Ti. The presence of Mn(II)-doped carbon aerogel enhanced ozone transformation into (*)OH radicals, whereas the presence of Co(II) and Ti(IV) carbon aerogels presented no activity in this process. Moreover, it was observed that an increase in the concentration of Mn in the surface of the aerogel increases its efficiency to transform ozone into (*)OH radicals, with an Rct value ([OH]/[O(3)]) of 5.36 x 10(-8) for the aerogel doped with 16% of surface Mn(II) compared to an R(ct) of 2.68 x 10(-9) for conventional ozonation. Regardless of the aerogel used, XPS analysis of the ozonated aerogel samples showed an increase in the concentration of surface oxygen when the exposure to ozone was longer. However, presence of oxidized metal species after ozone treatment was only detected in the case of the Mn-doped aerogel, (Mn(III) and Mn(IV)). CO(2) activation of carbon aerogel produced a marked increase in its efficiency to transform ozone into (*)OH radicals compared with non-activated sample. The efficiency of Mn activated carbon aerogel to transform ozone into (*)OH radicals was greater than that of Witco commercial activated carbon or H(2)O(2) in the ozonation of water from Lake Zurich (Zurich, Switzerland).     

Comparison of the efficiency of *OH radical formation during ozonation and the advanced oxidation processes O3/H2O2 and UV/H2O2

Comparison of advanced oxidation processes (AOPs) can be difficult due to physical and chemical differences in the fundamental processes used to produce OH radicals. This study compares the ability of several AOPs, including ozone, ozone+H2O2, low pressure UV (LP)+H2O2, and medium pressure UV (MP)+H2O2 in terms of energy required to produce OH radicals. Bench scale OH radical formation data was generated for each AOP using para-chlorobenzoic acid (pCBA) as an OH radical probe compound in three waters, Lake Greifensee water, Lake Zurich water, and a simulated groundwater. Ozone-based AOPs were found to be more energy efficient than the UV/H2O2 process at all H2O2 levels, and the addition of H2O2 in equimolar concentration resulted in 35% greater energy consumption over the ozone only process. Interestingly, the relatively high UV/AOP operational costs were due almost exclusively to the cost of hydrogen peroxide while the UV portion of the UV/AOP process typically accounted for less than 10 percent of the UV/AOP cost and was always less than the ozone energy cost. As the *OH radical exposure increased, the energy gap between UV/H2O2 AOP and ozone processes decreased, becoming negligible in some water quality scenarios.     

Removal of pharmaceutical compounds, nitroimidazoles, from waters by using the ozone/carbon system

The main objective of this study was to analyze the effectiveness of technologies based on the use of ozone and activated carbon for the removal of nitroimidazoles from water, considering them as model of pharmaceutical compounds. A study was undertaken of the influence of the different operational variables on the effectiveness of each system studied (O(3), O(3)/activated carbon), and on the kinetics involved in each process. Ozone reaction kinetics showed that nitroimidazoles have a low reactivity, with [Formula: see text] values <350M(-1)s(-1) regardless of the nitroimidazole and solution pH considered. However, nitroimidazoles have a high affinity for HO radicals, with radical rate constant (k(HO)) values of around 10(10)M(-1)s(-1). Among the nitroimidazole ozonation by-products, nitrate ions and 3-acetyl-2-oxazolidinone were detected. The presence of activated carbon during nitroimidazole ozonation produces (i) an increase in the removal rate, (ii) a reduction in the toxicity of oxidation by-products, and (iii) a reduction in the concentration of dissolved organic matter. These results are explained by the generation of HO radicals at the O(3)-activated carbon interface.     

Removal of the surfactant sodium dodecylbenzenesulphonate from water by simultaneous use of ozone and powdered activated carbon: comparison with systems based on O3 and O3/H2O2

A study was conducted on the efficacy of the system based on the simultaneous use of ozone and powdered activated carbon (PAC) in removing sodium dodecylbenzenesulphonate (SDBS) from drinking waters and on the influence of operational parameters (PAC dose, ozone dose and presence of radical scavengers [HCO3-]) on this process. Results obtained showed that low doses of PAC during SDBS ozonation markedly increased the rate of SDBS removal from the medium. These results are due to the combined effect of two processes: (i) SDBS adsorption on the activated carbon surface and (ii) transformation of the dissolved ozone into .OH radicals. At higher ozone and PAC doses, there was a higher rate of SDBS removal from the medium. The presence of HCO3- in the medium reduced the SDBS removal rate of the O3/PAC system. This finding confirms that the presence of PAC during SDBS ozonation favours ozone transformation into .OH radicals. Comparison of the O3/PAC system with systems based on the use of O3 or O3/H2O2 showed that the efficacy of the O3/PAC system to remove SDBS is much greater than that of the traditional oxidation methods. Thus, in the first 5 min of treatment (usual hydraulic retention time), the percentage of SDBS removed was 18% and 30% for the O3 and O3/H2O2 systems, respectively, compared with 70% for the O3/PAC system. SDBS ozonation in surface waters intended for human consumption demonstrated that the O3/PAC approach is the most efficacious of the studied systems, considerably increasing the SDBS removal rate and also reducing the concentration of dissolved organic carbon. Therefore, the results of this study show that the system based on O3/PAC is a highly attractive option for the treatment of drinking water.     

Decomposition of aqueous ozone in the presence of aromatic organic solutes

The decomposition of aqueous ozone is mainly due to the OH(*) radical chain reaction. Some aromatic compounds have been found to tremendously accelerate ozone decomposition in buffered water although their direct reactions with ozone are very low. Hydrogen peroxide has been detected as an important intermediate product in this process. Therefore, a reaction pathway (aromatic ring=>olefin=>H(2)O(2)=>HO(2)(-)) is proposed in this study. Aromatic rings react with OH(*) radicals or ozone to yield olefins. The olefin formed immediately reacts with ozone and is converted to H(2)O(2). Parts of H(2)O(2) dissociate to HO(2)(-), which strongly accelerates aqueous ozone decomposition. Therefore, a new chain reaction appears. The proposed reaction pathway is much faster than another promotion pathway, such as aqueous ozone decomposition promoted by methanol, formic acid or glucose.     

The effect of preliminary ozonization on the bioregeneration of activated carbon during its long-term service

The activated carbon (AC) bioregeneration was shown to proceed more efficiently during the filtration of preozonized tap water as compared with bioregeneration under the similar conditions during the filtration of non-ozonized water. The enhanced efficiency of AC bioregeneration after the filtration of preozonized water is determined by transformation of the total organic carbon into a better biodegrading form, increased microbiological activity in the depth of AC bed, and enhanced hydrophilicity of the AC surface area due to its chemical interaction with dissolved ozone.     

Oxidation of chlorfenvinphos in ultrapure and natural waters by ozonation and photochemical processes

The chemical oxidation of the organophosphorus insecticide chlorfenvinphos, a priority pollutant in aquatic environments, has been conducted in ultrapure water, by means of single degradation agents (ozone and UV radiation), and by the Advanced Oxidation Processes constituted by combinations of these oxidants (O(3)/H(2)O(2) and UV/H(2)O(2)). The influence of the operating variables was discussed, and the degradation rates were evaluated by determining the rate constants for the reactions with ozone ( [Formula: see text] =3.7+/-0.2 L mol(-1)s(-1)) and OH radicals (k(OH)=(3.2+/-0.2)x10(9) L mol(-1)s(-1)), as well as the quantum yield for the photodegradation (around 0.1 mol E(-1), depending on the pH). Additionally, the ozonation of chlorfenvinphos in a natural water system (a surface water from a reservoir) was studied. The influence of the operating conditions on the insecticide removal efficiency was established, and the R(ct) parameter was evaluated. A kinetic model was proposed for the prediction of the elimination rate of chlorfenvinphos in the ozonation process and the results obtained reveal a good agreement between experimental results and predicted values.     

Characterization of raw water for the ozone application measuring ozone consumption rate.

This study was conducted to illustrate an ideal method for characterizing natural waters for ozonation processes in drinking water treatment plants. A specific instrument designed with the flow injection analysis (FIA) technique enabled us to measure accurately the ozone decomposition rate, which was found to consist of two stages: the instantaneous ozone consumption stage and the slower ozone decay stage. The ozone consumption rate was measured at the initial and secondary stages by determining certain parameters called the instantaneous ozone demand (ID) and the pseudo first-order decay rate constant (k(c)). Using the OH*-probe, the yield of OH* per consumed ozone was also measured to determine its potential to produce OH* for the oxidation of micropollutants during the ozonation process. The ozone consumption of the ID values was significant in most natural waters, and substantial amounts of OH* were found to generate during the instantaneous ozone consumption stage. This study also investigated the effects of particulates, ozone doses, and sequential ozone injection on ozone decomposition kinetics and OH* formation yield.     

Effects of ozonation on the permeate flux of nanocrystalline ceramic membranes

Titania membranes, with a molecular weight cut-off of 15 kD were used in an ozonation/membrane system that was fed with water from Lake Lansing, which had been pre-filtered through a 0.45 microm glass fiber filter. The application of ozone gas prior to filtration resulted in significant decreases in membrane fouling. The effects of ozonation could not be explained by physical scouring of the filter cake. Decrease in the pH resulted in a concomitant increase in the dissolved ozone concentration in the feed water and in an improvement in permeate flux recovery. Increasing the ozone concentration beyond a threshold value had no beneficial effect on permeate flux recovery. Ozone decomposition, resulting in the formation of OH or other radicals at the membrane surface, is thought to result in the decomposition of organic foulants at the membrane surface and reduce the extent of membrane fouling.     

Photocatalytic degradation of E. coliform in water

This study aims to further investigate the total mineralization of the bacteria to the extent of death and cell-mass inactivation using a TiO2-Fe2O3 membrane photocatalytic oxidation reactor. Experimental results clearly indicated that dissolved oxygen (DO), hydraulic retention time (HRT) and concentration of the model bacteria (Escherichia coliform) affected the removal efficiency. It was found that the ultimate removal efficiency was 99% at DO level of 21.34 mg/l, HRT at 60s and high concentration of E. coli at 10(9)CFU/ml. The morphologic studies also showed that E. coliform could be further mineralized into CO2 and H2O. Dissolved organic carbon, pH and gas chromatograph analysis had justified most importantly the evolution of CO2. Experimental results revealed that the photomineralization rate of E. coliform followed pseudo-first-order kinetics by the role of DO. The derived empirical models were found consistent with the proposed reaction pathways of a combined UV breakdown on mass cell and a dual-site Langmuir-Hinshelwood mechanism where the rate-controlling step is the surface interaction between the adsorbed cleavage bacterial cells and hydroxyl radicals.     

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.     

Oxidative degradation of N-nitrosodimethylamine by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide

This study investigates the oxidative degradation of N-nitrosodimethylamine (NDMA), a probable human carcinogen, by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide (AOP O(3)/H(2)O(2)). The rate constants of reactions of NDMA with ozone and hydroxyl radical ((*)OH) were determined to be 0.052+/-0.0016M(-1)s(-1) and (4.5+/-0.21)x10(8)M(-1)s(-1), respectively. The experiments performed with buffered deionized water varying solution pH and employing H(2)O(2) and HCO(3)(-) clearly showed that the reaction with (*)OH dominates the NDMA oxidation during ozonation. Conventional ozonation with up to 160 microM (=7.7 mgL(-1)) ozone led to less than 25% NDMA oxidation in natural waters. The AOP O(3)/H(2)O(2) required 160-320 microM ozone ([O(3)](0)/[H(2)O(2)](0)=2:1) to achieve 50-75% NDMA oxidation. However, multiple injections of ozone of the same overall dose somewhat improved the oxidant utilization efficiency by minimizing (*)OH scavenging contribution of oxidants. Methylamine (MA) was found to be a major amino product from NDMA oxidation initiated by (*)OH. The mechanism of NDMA oxidation to MA is discussed based on the results obtained in this study and the previous literature. Bromate formation may be the limiting factor for NDMA oxidation during ozonation and ozone-based AOPs in bromide-containing waters.     

Ozonation of drinking water: part I. Oxidation kinetics and product formation

The oxidation of organic and inorganic compounds during ozonation can occur via ozone or OH radicals or a combination thereof. The oxidation pathway is determined by the ratio of ozone and OH radical concentrations and the corresponding kinetics. A huge database with several hundred rate constants for ozone and a few thousand rate constants for OH radicals is available. Ozone is an electrophile with a high selectivity. The second-order rate constants for oxidation by ozone vary over 10 orders of magnitude, between < 0.1 M(-1)s(-1) and about 7 x 10(9) M(-1)s(-1). The reactions of ozone with drinking-water relevant inorganic compounds are typically fast and occur by an oxygen atom transfer reaction. Organic micropollutants are oxidized with ozone selectively. Ozone reacts mainly with double bonds, activated aromatic systems and non-protonated amines. In general, electron-donating groups enhance the oxidation by ozone whereas electron-withdrawing groups reduce the reaction rates. Furthermore, the kinetics of direct ozone reactions depend strongly on the speciation (acid-base, metal complexation). The reaction of OH radicals with the majority of inorganic and organic compounds is nearly diffusion-controlled. The degree of oxidation by ozone and OH radicals is given by the corresponding kinetics. Product formation from the ozonation of organic micropollutants in aqueous systems has only been established for a few compounds. It is discussed for olefines, amines and aromatic compounds.     

Dual roles of CO2*- for degrading synthetic organic chemicals in the photo/ferrioxalate system

In this study, the relative importance of the dual reaction pathways of CO2*- in the photo/ferrioxalate system, where it acts both as a reductant for reducing the ferric ion and as an agent for the formation of H(2)O(2), was investigated as a function of the concentrations of ferrioxalate and oxygen. We studied the two competitive reactions of CO2*- in the photo/ferrioxalate system, which depend on the relative concentrations of ferrioxalate to oxygen, with the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D), which was used as a target pollutant. At high concentrations of ferrioxalate, almost all of the CO2*- reacted with ferrioxalate to reduce Fe(III) to Fe(II), whereas at low concentrations of ferrioxalate, a majority of the CO2*- contributed to the formation of H(2)O(2), as a result of its reaction with oxygen, which allows the Fenton reaction to occur without any external supply of H(2)O(2).     

南方某水厂臭氧/活性炭深度处理工艺运行效果

以南方地区微污染水源水为对象,研究臭氧/活性炭深度处理工艺对有机物综合指标UV(254)、COD(Mn)、TOC的去除效果以及对消毒副产物的控制效果,并结合三维荧光光谱技术分析溶解性有机物的荧光特性。结果表明,与常规处理工艺相比,增加臭氧/活性炭深度处理工艺后,对UV(254)、COD(Mn)、TOC、三卤甲烷前体物的去除率分别提高了47.05%、20.24%、31.11%、37.70%。三维荧光光谱分析结果表明,该地区微污染水源水主要由芳香性蛋白质类物质、溶解性微生物代谢产物类物质和富里酸类物质组成,臭氧/活性炭深度处理工艺对荧光溶解性有机物的去除效果明显。     

A model approach to assess the long-term trends of indirect photochemistry in lake water. The case of Lake Maggiore (NW Italy)

A model-based approach is here developed and applied to predict the long-term trends of indirect photochemical processes in the surface layer (5 m water depth) of Lake Maggiore, NW Italy. For this lake, time series of the main parameters of photochemical importance that cover almost two decades are available. As a way to assess the relevant photochemical reactions, the modelled steady-state concentrations of important photogenerated transients (^•OH, ³CDOM* and CO₃^-•) were taken into account. A multivariate analysis approach was adopted to have an overview of the system, to emphasise relationships among chemical, photochemical and seasonal variables, and to highlight annual and long-term trends. Over the considered time period, because of the decrease of the dissolved organic carbon (DOC) content of water and of the increase of alkalinity, a significant increase is predicted for the steady-state concentrations of the radicals ^•OH and CO₃^−•. Therefore, the photochemical degradation processes that involve the two radical species would be enhanced. Another issue of potential photochemical importance is related to the winter maxima of nitrate (a photochemical ^•OH source) and the summer maxima of DOC (^•OH sink and ³CDOM* source) in the lake water under consideration. From the combination of sunlight irradiance and chemical composition data, one predicts that the processes involving ^•OH and CO₃^−• would be most important in spring, while the reactions involving ³CDOM* would be most important in summer.     

Occurrence of dissolved and particle-bound taste and odor compounds in Swiss lake waters

The occurrence of algal taste and odor (T&O) compounds was investigated in three Swiss lakes which exhibit different nutrient levels from eutrophic to oligotrophic (Lake Greifensee, Lake Zurich and Lake Lucerne). Apart from dissolved T&O compounds, the study also encompassed particle-bound compounds, i.e., compounds that can be released from damaged algal cells during drinking water treatment. A combined instrumental (SPME-GC-MS) and sensory method was applied that allowed to detect and quantify T&O compounds in natural waters in the sub ppt to low ppt-range.In addition to the prominent T&O compounds geosmin and 2-methyl-isoborneol (MIB), four other T&O compounds could be detected in the lake waters, though all at relatively low concentrations (maximum concentrations of geosmin 19 ng L⁻¹, MIB 3 ng L⁻¹, β-ionone 27 ng L⁻¹, β-cyclocitral 7 ng L⁻¹, 2-isobutyl-3-methoxypyrazine 2 ng L⁻¹, 2-isopropyl-3-methoxypyrazine 16 ng L⁻¹). The concentration peaks typically occurred in the epilimnion during summer concurrent with a high phytoplankton biomass. Consistently, the concentration levels for most of the compounds varied substantially between the three lakes and generally decreased in the order eutrophic Lake Greifensee > mesotrophic Lake Zurich > oligotrophic Lake Lucerne. Furthermore, our data revealed that the occurrence of β-ionone was largely influenced by Planktothrix rubescens. This is the first time that a correlation between β-ionone and this cyanobacterium has been reported for natural waters.     

Linear correlation between inactivation of E. coli and OH radical concentration in TiO2 photocatalytic disinfection

The biocidal action of the TiO2 photocatalyst has been now well recognized from massive experimental evidences, which demonstrates that the photocatalytic disinfection process could be technically feasible. However, the understanding on the photochemical mechanism of the biocidal action largely remains unclear. In particular, the identity of main acting photooxidants and their roles in the mechanism of killing microorganisms is under active investigation. It is generally accepted that reactive oxygen species (ROS) and OH radicals play the role. The aim of this study is to determine how the OH radical, acting either independently or in collaboration with other ROS, is quantitatively related to the inactivation of E. coli. The steady-state concentrations of OH radicals ([*OH]ss) in UV-illuminated TiO2 suspensions could be quantified from the measured photocatalytic degradation rates of p-chlorobenzoic acid (a probe compound) and its literature bimolecular rate constant with OH radicals. The results demonstrated an excellent linear correlation between [*OH]ss and the rates of E. coli inactivation, which indicates that the OH radical is the primary oxidant species responsible for inactivating E. coli in the UV/TiO2 process. The CT value of OH radical for achieving 2 log E. coli inactivation was initially found to be 0.8x10(-5) mg min/l, as predicted by the delayed Chick-Watson model. Although the primary role of OH radicals in photocatalytic disinfection processes has been frequently assumed, this is the first quantitative demonstration that the concentration of OH radicals and the biocidal activity is linearly correlated.     

Evaluation of granular activated carbon technology for the removal of methyl tertiary butyl ether (MTBE) from drinking water

This study evaluated granular activated carbons (GACs) using rapid small-scale column tests (RSSCTs) on methyl tert-butyl ether (MTBE) levels from 20 to 2000 microg/L, with or without the presence of tert-butyl alcohol, benzene, toluene, p-xylene (BTX) in two groundwater (South Lake Tahoe Utility District [Lake Tahoe, CA] and Arcadia Well Field [Santa Monica, CA]) and a surface water source (Lake Perris, CA). Direct comparison between two GACs was made for RSSCTs conducted with surface water from Lake Perris. The impact of natural organic matter on GAC performance was investigated and found to correspond with total organic carbon concentration in the three source waters. Significant reduction in GAC performance for MTBE due to competitive adsorption from soluble fuel components (e.g., BTX) was observed. Little or no difference in GAC usage rate or bed life was detected as the empty-bed contact time is changed from 10 to 20 min for RSSCTs conducted in the two groundwater sources, whereas the RSSCTs conducted in the surface water source exhibited significant increase in GAC usage rate as the empty-bed contact time is decreased from 20 to 10 min. This finding suggests that the higher NOM content of the surface water over the groundwater sources caused a greater competitive-adsorption effect that made more sites on the GAC to be unavailable to MTBE, thus decreasing its rate of adsorption and GAC performance for MTBE. Finally, the impact of differential influent MTBE concentration on GAC performance was demonstrated.     

The formation of trichloronitromethane (chloropicrin) and chloroform in a combined ozonation/chlorination treatment of drinking water

Chlorination of waters from mesotrophic Lake Zurich and eutrophic Greifensee formed about 0.4 and 2 μg 1⁻¹ of trichloronitromethane (TCNM) respectively. Pre-ozonation increased these values to about 2 and 6 μg 1⁻¹. The formation of chloroform was about 40 times higher than that of TCNM, but decreased somewhat, when pretreatment with ozone was performed. Posttreatment with activated carbon eliminates most TCNM but only part of the chloroform. The addition of nitrilotriacetic acid (NTA) or ethylenediamine tetraacetic acid (EDTA) complexing agents applied in detergents and other products, had only a small incremental effect on the formation of chloropicrin, which became significant only when the combined oxidation process was performed in distilled water. In contrast, the addition of triethanolamine to water greatly increased the TCNM formation when ozonation preceded chlorination of water. The possible role of NTA as a presursor for TCNM is further discussed by considering the kinetics of the reaction of ozone with NTA and its ozonolytic products, the iminodiacetic acid and glycine.