Polar nitrogen compounds and their behaviour in the drinking water treatment process

Aliphatic and alicyclic amines as well as ethanolamines are extremely polar compounds, frequently found in the environment, and some of them have high toxicity. To address the contamination of selected German surface waters examined and the importance of bank filtration in Eastern Germany, investigations on the behaviour of polar organic nitrogen compounds during water treatment were carried out. Test conditions were designed appropriately for drinking water treatment conditions, and the tests were carried out using model water as well as bank filtrate. Test filter studies of microbial degradation of selected compounds demonstrated the following order of biodegradability: ethanolamine > dimethylamine > pyrrolidine > ethylenediamine. piperidine > diethylamine > morpholine > piperazine > cyclohexylamine. Flocculation tests using iron salts as well as aluminium salts as coagulants showed very low removal rates for the amines. The best results for the removal of the polar organic nitrogen compounds from the water were obtained using ozonation. Based on the reaction-rate constants, the order of degradation by ozone is: piperazine > morpholine > ethylenediamine > piperidine, cyclohexylamine > dimethylamine > ethanolamine > pyrrolidine > diethylamine. Disinfection by chlorine-containing agents under drinking water treatment conditions did not give effective elimination of the selected polar nitrogen compounds.     

Biodegradability of ozonation products as a function of COD and DOC elimination by the example of humic acids

Ozone pretreatment studies of humic acids were conducted to evaluate the effects of ozonation on the biodegradability of the oxidation products as a function of COD-, DOC-elimination, decrease of u.v.-absorbance and ozone consumption. A 50–60% decrease of the COD-value and a 30% decrease of the DOC-value lead to biodegradable products (BOD₅/COD = 0.4) in most cases independent of the pH-value and the initial concentration. To reach these results 3.4–4 mg ozone are consumed per mg initial DOC. With this ozone consumption complete decolorization of the solutions is achieved and the value of u.v./DOC decreases from 4 to 0.8 m² g⁻¹.     

Effects of ozone pre-treatment on diclofenac: Intermediates, biodegradability and toxicity assessment

Diclofenac (DCF), a common analgesic, anti-arthritic and anti-rheumatic drug, is one of the most frequently detected compounds in water. This study deals with the degradation of diclofenac in aqueous solution by ozonation. Biodegradability (BOD₅/COD ratio and Zahn-Wellens test), acute ecotoxicity and inhibition of activated sludge activity were determined in ozonated and non-ozonated samples. Liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) was used to identify the intermediates formed in 1 h of ozonation. Eighteen intermediates were identified by these techniques and a tentative degradation pathway for DCF ozonation is proposed.Experimental results show that ozone is efficient at removing DCF: > 99% removal (starting from an initial concentration of 0.68 mmol L^− 1) was achieved after 30 min of ozonation (corresponding to an absorbed ozone dose of 0.22 g L^− 1, which is 4.58 mmol L^− 1). However, only 24% of the substrate was mineralized after 1 h of ozonation. The biodegradability, respiration inhibition in activated sludge and acute toxicity tests demonstrate that ozonation promotes a more biocompatible effluent of waters containing DCF.     

A quantitative investigation of the reaction of ozone with p-toluenesulfonic acid in aqueous solution as a model compound for anionic detergents

The reaction of ozone with p-toluenesulfonic acid (PTA) at initial pH 3 and 12 in aqueous solutions (25°C) has been studied at initial concentration 1 mmol l⁻¹ and ozone dose is 24 mg min⁻¹ 1. and 11 mg min⁻¹ 1. respectively. The substrate elimination follow a zero order rate law. A 98% p-toluenesulfonic acid reduction requires at least 7 mol O₃ per mol PTA, however to remove 100% PTA the consumption of ozone increases to 16 mmol O₃ per mmol PTA. At this point a 28% reduction of DOC and a 74% COD reduction was achieved.The PTA decomposition is quicker at higher ozone flow rate, but the specific ozone consumption increases also. As oxidation products the following compounds were identified and their quantitative variations as function of ozonation time were measured: methylglyoxal, acetic acid, formic acid, pyruvic acid, oxalic acid, H₂SO₄ and H₂O₂. As byproduct mesoxalic acid was identified. At pH 12 lactic acid as a further oxidation product was observed.Balances of carbon, sulfur and methyl as well of the acid equivalents indicate one or more intermediates with a sulfonic acid group. These intermediates with a proportion of about 20% disappear after 100% PTA elimination. On account of these results a reaction mechanism is discussed.     

Biodegradability of ozonation products as a function of COD and DOC elimination by example of substituted aromatic substances

Ozone pretreatment studies of nonbiodegradable substituted aromatic compounds were conducted to evaluate the effects of ozonation on the biodegradability of the oxidation products as a function of COD- DOC-elimination and ozone consumption.In the case of substituted aromatic compounds a 60–70% decrease of the COD-value and a 30–40% decrease of the DOC-value lead to biodegradable products (BOD₅-/COD = 0.4) independent of the pH and the initial concentration of compounds. To reach good biodegradability of the oxidation products 3 mg ozone on average per 1 mg initial DOC are necessary.     

Improved ammonia oxidation by ozone in the presence of bromide ion during water treatment

Ammonia oxidation by ozone proceeds more rapidly in the presence of bromide ion than in its absence. Unlike the direct ozonation of ammonia, the bromide-catalyzed process is little affected by changes in pH. A reaction scheme is proposed in which bromide is oxidized to HOBr, which then brominates ammonia to produce NH₂Br. NH₂Br in turn reacts with O₃ to form NO₃⁻ and also to generate Br⁻, which thus acts as a catalyst. In accordance with the reaction model, zero-order kinetics for ammonia consumption are observed. This work points out once again the importance of Br⁻ as a water quality parameter due to its role as a catalyst in both ozonation and chlorination processes in general.     

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.     

Reaction of ozone with Trans-trans muconic acid in aqueous solution

The ozonation of trans-trans muconic acid in aqueous solution (pH 3) leads to the formation of fumaric acid aldehyde, glyoxal, glyoxylic acid and formic acid which are oxidized into stable end products of oxalic acid, mesoxalic acid and CO₂ as the reaction goes on. Besides unstable organic peroxides H₂O₂ is observed. However, at pH 7 and pH 8 organic peroxides are not detected. Only smaller amounts of H₂O₂ than at pH 3 are formed.The specific ozone consumption was 3.2 mmol of O₃ mmol⁻¹ of acid until complete elimination of muconic acid. The reaction mechanism is discussed on the basis of quantitative tracking of the oxidation products.The reaction rates of muconic acid and of the oxidation products with ozone are compared with those of substituted aromatics.     

Ozonation and biological activated carbon filtration of wastewater treatment plant effluents

This study investigates the fate of trace organic chemicals (TrOCs) in three full-scale reclamation plants using ozonation followed by biological activated carbon (BAC) filtration to treat wastewater treatment plant effluents. Chemical analysis was used to quantify a wide range of TrOCs and combined with bioanalytical tools to assess non-specific toxicity (Microtox assay) and estrogenicity (E-SCREEN assay). Limited dissolved organic carbon (DOC) removal (<10%) was observed in the ozonation stages showing that oxidation leads to the formation of transformation products rather than mineralization. The quantified TrOCs were removed to a degree highly dependent on the compounds’ structures and the specific ozone dose (mg_O3 mg_DOC⁻¹). Non-specific toxicity was reduced by 31-39%, demonstrating that the mixture of remaining parent compounds and their transformation products as well as newly formed oxidation by-products had an overall lower toxic potential than the mixture of parent compounds. Estrogenicity was reduced by more than 87% indicating that the transformation products of the estrogenic chemicals lost their specific toxicity potential. The subsequent BAC filtration removed between 20 and 50% of the DOC depending on the plant configuration, likely due to biodegradation of organic matter. The filtration was also able to reduce the concentrations of most of the remaining TrOCs by up to 99%, and reduce non-specific toxicity by 33-54%. Overall, the combination of ozonation and BAC filtration can achieve removals of 50% for DOC and more than 90% for a wide range of TrOCs as well as a reduction of 70% of non-specific toxicity and more than 95% of estrogenicity. This process combination is therefore suggested as an effective barrier to reduce the discharge of TrOCs into the environment or their presence in water recycling schemes.     

The influence of disinfection on aquatic biodegradable organic carbon formation

The aim of this paper was to assess the extent of biodegradable dissolved organic carbon formation upon disinfection of water with chlorine dioxide. Wide diversity of natural waters has been subjected to reactions with various amounts of ClO₂. For comparison examined waters have also been treated with ozone and chlorine. The application of chlorine dioxide and ozone significantly changed the molecular weight distribution of aquatic organic matter. As a result significant amounts of biodegradable carboxylic acids and aldehydes were generated. The formic, acetic, oxalic and ketomalonic acids as well as formaldehyde, acetaldehyde, glyoxal, methylglyoxal were identified. The productivity of aldehydes calculated for all examined waters and disinfectants amounted 12.7-47.7 μg mg⁻¹ DOC in the case of ozonation, 1.3-8.1 μg mg⁻¹ DOC after chlorination and 1.7-9.4 μg mg⁻¹ DOC for ClO₂ treatment. The highest total concentration of carboxylic acids was determined after the ozonation processes. In this case the organic acids' formation potential was in the range 10.8-62.8 μg mg⁻¹ DOC. Relatively high formation potential (5.3-17.9 μg mg⁻¹ DOC) was determined after the oxidation with ClO₂ as well. In the case of chlorination, the productivity of organic acids was low and did not exceed 3.4 μg mg⁻¹ DOC. The relatively high correlation between BDOC formation and carboxylic acids' formation potential was observed. Thus, carboxylic acids' formation potential may be used as a measure of water potential to form BDOC.     

Evaluation of the prediction of trace organic compound removal during ozonation of secondary effluents using tracer substances and second order rate kinetics

The application of the R_CT-concept for predicting the removal of trace organic compounds (TrOCs) in organic rich WWTP effluents is often problematic due to the fast ozone depletion with instantaneous ozone demand in the range of typically applied ozone dosages. In this study, the determination of OH-radical and ozone exposure from second order rate kinetics with two internal tracer substances was evaluated as alternative approach for these waters. Results from batch and semi-batch experiments showed a linear correlation of OH-radical exposure with ozone consumption, characterized by its slope indicating the formation efficiency of OH-radicals and a lag ozone consumption without significant formation of OH-radicals. Evaluation of data from the project PILOTOX on ozonation of secondary effluent confirmed reasonable prediction of ozone resistant compound removal from relative residual concentration of an internal tracer substance. In contrast, predicting the reduction of TrOCs by direct reactions with ozone from internal tracers was not feasible. Similar removal efficiencies for fast reacting compounds with different rate constants from k_O3 = 10⁴ M⁻¹ s⁻¹ to k_O3 = 10⁶ M⁻¹ s⁻¹ were observed indicating a limitation of the reaction by mass transfer. This effect was observed at low ozone dosages in semi-batch and pilot experiments as well as in batch experiments, where mass transfer from gas to liquid phase is not limiting. It is assumed that consumption of low ozone dosages is faster than sample homogenization in the batch reactors used. Thus, prediction of compound removal by direct reaction with ozone always needs to consider reactor design and geometry.     

Removal and transformation of recalcitrant organic matter from stabilized saline landfill leachates by coagulation-ozonation coupling processes

The Bordo Poniente sanitary landfill in Mexico City currently receives 11,500 ton/day of solid wastes. The landfill has been in operation since 1985, in what was formerly Texcoco Lake, now a dried-up lakebed. The physico-chemical characteristics of the leachate generated by this particular landfill are altered by the incorporation of freatic saline water present in the area. This paper reports the results from a study evaluating coagulation and ozonation as alternative processes for removing and transforming recalcitrant organic matter from stabilized saline landfill leachate. Coagulation with ferric sulfate was found to remove up to 67% of COD and 96% of leachate color. The remaining 33% COD was removed with ozone. Recalcitrant organic matter removal by ozonation is limited by the reaction kinetic due mainly to ozone's low reactivity with the organic compounds present in the leachates (amines, amides, alcohols, aliphatic compounds, and carboxylic acids). However, ozone contributes greatly to changing the recalcitrant characteristics of organic matter. Leachate biodegradability was found to be significantly enhanced through ozonation: BOD(5) values reach 265%, and the BOD(5)/COD ratio increases from 0.003 to 0.015. Infrared analysis of ozonated leachates shows that the main by-products of recalcitrant organic matter ozonation are an increase in the hydroxyl and carboxylic groups, and the presence of aldehydes groups.     

Optimization of Coagulation and Ozonation Processes for Disinfection by–Products Formation Potential Reduction

Optimization of coagulation and ozonation processes for removal of disinfection by–products (DBP) formation potential in raw water was conducted by a pilot scale system. Proper poly–aluminum–chloride–sulfates (PACS), pre–ozone and post–ozone dosages are required for improving the removal performance of DBP formation potential to guarantee the safety of drinking water. Considering the treatment performances and economic costs, the optimum PACS, pre–ozone and post–ozone dosages for treating raw water with high organic concentration should be around 8.9 mg/L Al₂O₃, 0.5 and 2.5 mg/L, respectively. The combined drinking water treatment system of pre–ozonation, coagulation/sedimentation, sand filtration, post–ozonation, granular activated carbon filtration and disinfection is a promising process to reduce DBP formation potential from raw water in southern China. Under the optimum conditions, this combined system removed total trihalomethanes and haloacetic acids formation potential 50.16 and 69.10%, respectively.     

Two-phase ozonation of hazardous organics in single and multicomponent systems

The destruction of pentachlorophenol (PCP), oxalic acid, chlorendic acid, and a mixture of pentachlorophenol, 1,3-dichlorobenzene (DCB), and trichloroethylene (TCE) were studied using a two-phase ozonation system. A two-phase ozonation system consists of water containing the pollutant and a second solvent phase which houses the ozone. The solvent phase is an inert fluorinated hydrocarbon (FC40) that is nonpolar and reusable. The solvent phase is desirable because it has a high ozone stability (k = 0.0033 min⁻¹) and an ozone solubility of 120 mg/L at 25°C, 10 times that of water. In addition to an enhanced oxidation rate of PCP, less ozone was utilized. At high pH (10.3), a first-order rate constant of 200 min⁻¹ in the two-phase system was found for PCP degradation compared to k_app = 0.154 min⁻¹ in a single aqueous-phase system. Within 15 s, the concentration of PCP (100 mg/L initially) was degraded more than 90%, and 100% dechlorination was obtained with longer reaction times. This system also demonstrated the ability to selectively oxidize PCP while in the presence of free radical scavengers existing in the water phase. PCP was also successfully oxidized using actual wastwater which contained alkalinity, hardness, many inorganics, and trace hazardous organics. Oxalic acid, an intermediate formed during the degradation of PCP, was also degraded by two-phase ozonation. Preliminary work with chlorendic acid showed that two-phase ozonation was faster than single aqueous-phase ozonation at dechlorinating the compound. TCE and DCB degraded slightly faster when PCP was added to the mxture, possibly due to the production of other radicals during the oxidation of PCP.     

Oxidative and photochemical processes for the removal of galaxolide and tonalide from wastewater

Synthetic musks have been reported in wastewaters at concentrations as high as tens of micrograms per litre. The two most significant polycyclic musk fragrance compounds are 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran (HHCB, trade name galaxolide^®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (AHTN, trade name tonalide^®). We report the result of several irradiation and advanced oxidation processes carried out on samples of the effluent of a wastewater treatment plant located in Alcalá de Henares, Madrid. Wastewater samples were pre-ozonated and spiked with 500 ng/L of tonalide or galaxolide in order to obtain final concentrations in the same order as the raw effluent. The treatments assayed were ozonation with and without the addition of hydrogen peroxide (O₃, O₃/H₂O₂), ultraviolet (254 nm low pressure mercury lamp) and xenon-arc visible light irradiation alone and in combination with ozone (UV, O₃/UV, Xe, O₃/Xe) and visible light photocatalytic oxidation using a Ce-doped titanium dioxide photocatalyst performed under continuous oxygen or ozone gas bubbling (O₂/Xe/Ce-TiO₂, O₃/Xe/Ce-TiO₂). In all cases, samples taken at different contact times up to 15 min were analyzed. An analytical method based on stir bar sorptive extraction (SBSE), followed by comprehensive two-dimensional gas chromatography (SBSE-GC × GC-TOF-MS), was used for the automatic searching and evaluation of the synthetic musks and other nonpolar or semipolar contaminants in the wastewater samples. In all cases tonalide was more easily removed than galaxolide. The best results for the latter (more than 75% removal after 5 min on stream) were obtained from ozonation (O₃) and visible light photocatalytic ozonation (O₃/Xe/Ce-TiO₂). A significant removal of both pollutants (∼60% after 15 min) was also obtained during visible light photocatalysis (O₂/Xe/Ce-TiO₂). UV radiation was able to deplete tonalide (+90%) after 15 min but only reduced the concentration of galaxolide to about half of its initial concentration. The toxicity of treated samples decreased for O₃/UV and O₃/Ce-TiO₂, but increased during irradiation processes UV, Xe and Xe/Ce-TiO₂. Ozone treatments tend to decrease toxicity up to a certain dosage, from which point the presence of toxic transformation products has adverse effects on aquatic microorganisms.     

Cyclophosphamide degradation by advanced oxidation processes

Cyclophosphamide is a hazardous cytostatic drug, which should be removed from wastewaters before disposals. Ozonation slowly inactivates this substance, requiring long reaction times to obtain degradation. In this paper, different advanced oxidation processes (AOPs) are studied for cyclophosphamide oxidative degradation in aqueous medium: ozone at several basic pH values, ozone/hydrogen peroxide at neutral and basic pHs with the addition of the peroxide at the beginning of ozonation. The influence of ozone concentration in the gas phase and gas flow is also discussed. Results show that, under the experimental conditions studied, the radical mechanism acting in the AOPs rapidly degrades cyclophosphamide. Additionally, second-order rate constants k_d and k_OH were determined for direct (molecular) and indirect (radical) reactions. Finally, reactions were carried out with the aim of isolating and identifying some of the degradation products. From ozonation at pH 9, 4-ketocyclophosphamide was identified as the main reaction product.     

Ultrafine particle emission from floor cleaning products

The new particle formation due to the use of cleaning products containing volatile organic compounds (VOCs) in indoor environments is well documented in the scientific literature. Indeed, the physical-chemical process occurring in particle nucleation due to VOC-ozone reactions was deepened as well as the effect of the main influencing parameters (ie, temperature, ozone). Nonetheless, proper quantification of the emission under actual meteo-climatic conditions and ozone concentrations is not available. To this end, in the present paper the emission factors of newly generated ultrafine particles due to the use of different floor cleaning products under actual temperature and relative humidity conditions and ozone concentrations typical of the summer periods were evaluated. Tests in a chamber and in an actual indoor environment were performed measuring continuously particle number concentrations and size distributions during cleaning activities. The tests revealed that a significant particle emission in the nucleation mode was present for half of the products under investigation with emission factors up to 1.1 × 10¹¹ part./m² (8.8 × 10¹⁰ part./mL_product), then leading to an overall particle emission comparable to other well-known indoor sources when cleaning wide surfaces.     

Comparative study of ozonation and synthetic goethite-catalyzed ozonation of individual NOM fractions isolated and fractionated from a filtered river water

This study comparatively investigated ozonation and synthetic goethite-catalyzed ozonation of individual natural organic matter (NOM) fractions in terms of ozone consumption, dissolved organic carbon (DOC) and UV-absorbance reduction, molecular weight (MW) distribution, and formation of low-MW oxidation by-products. Hydrophobic acid and neutral (HOA and HON) and hydrophilic acid and base (HIA and HIB) were four major NOM fractions isolated from a filtered river water; so ozonation and catalytic ozonation were carried out on these fractions. Results indicate that in comparison to ozonation alone, catalytic ozonation can enhance ozone consumption, UV(254) and DOC reduction, fragmentation of fraction components with MW>3000Da, and formation of oxalic acid for these fractions under normal reaction conditions commonly adopted in water treatment plants. In addition, catalytic ozonation can enhance aldehydes formation and increase the percentage of easy biodegradable organic carbon compared with ozonation alone for HIA and HIB, but exert much less effect on these items for HOA and HON.     

Nitrogenous disinfection byproducts formation and nitrogen origin exploration during chloramination of nitrogenous organic compounds

Formation of nitrogenous disinfection by-products (N-DBPs) of cyanogen chloride (CNCl), dichloroacetonitrile (DCAN) and chloropicrin was evaluated during chloramination of several selected groups of nitrogenous organic (organic-N) compounds, including α-amino acids, amines, dipeptides, purines, and pyrimidines, The intermediates generated, reaction pathways, and nitrogen origin in N-DBPs were explored as well. CNCl was observed in chloramination of all tested organic-N compounds, with glycine giving the highest yields. DCAN was formed during chloramination of glutamic acid, cytosine, cysteine, and tryptophan. Chloramination of most organic-N compounds except for cysteine and glutamic acid generated chloropicrin. Aldehydes and nitriles were identified as the intermediates by negative mode electrospray ionization mass spectrometry during reactions of NH₂Cl and organic-N compounds. Labeled ¹⁵N-monochloramine (¹⁵NH₂Cl) techniques showed that nitrogen in N-DBPs may originate from both NH₂Cl and organic-N compounds and the nitrogen partition percentages vary as functions of reactants and pH.     

Chromatographic determination of primary aromatic amines in the form of azo derivatives in the presence in waters of monoatomic phenols

Using the difference in the acid-base properties of diazo amino compounds n-amino azo compounds, and azo phenols we have developed the chromatographic method of determination of amines after preliminary extraction of the latter by thermoconcentration in the form of salts. The method makes it possible to carry out determination of amines at the level 6–8 μg/dm³. The technique has been approved on fortified model solutions and on a real object.