The fate of chlorine in recirculating cooling towers Field results

Chlorine and chloramines are volatile compounds which are stripped (“flashed off”) from recirculating cooling water systems by the large volumes of air which flow through the water in the cooling tower. The fraction of a volatile gas, such as hypochlorous acid (HOCl), which is removed by stripping is determined by Henry's constant H for that gas: H = X_G/X_L, where X_G is the mole fraction of the gas in the air and X_L is the mole fraction of the gas in the water. We have measured H for HOCl, OCl⁻, NH₃, NH₂Cl, NHCl₂ and NCl₃ at 20 and 40°C. We found H = 0.076 for HOCl, compared to 0.71 for NH₃, at 20°C. At 40°C, H was about 2.5-fold larger for HOCl. This means that 10–15% of the HOCl is stripped from cooling water on each passage through a typical cooling tower. The measured flashoff of free available chlorine (HOCl + OCl⁻) was markedly pH-sensitive with a pK of 7.5, exactly as expected if HOCl is volatile but OCl⁻ is not. The data permit a quantitative understanding of the fate of chlorine in cooling systems. The values of H at 40°C for NH₂Cl, NHCl₂ and NCl₃ were 1.28, 3.76 and 1067. This means that all of the chloramines are quickly stripped in a cooling tower.     

Observations and impacts of bleach washing on indoor chlorine chemistry

Ambient levels of chlorinated gases and aerosol components were measured by online chemical ionization and aerosol mass spectrometers after an indoor floor were repeatedly washed with a commercial bleach solution. Gaseous chlorine (Cl₂, 10's of ppbv) and hypochlorous acid (HOCl, 100's of ppbv) arise after floor washing, along with nitryl chloride (ClNO₂), dichlorine monoxide (Cl₂O), and chloramines (NHCl₂, NCl₃). Much higher mixing ratios would prevail in a room with lower and more commonly encountered air exchange rates than that observed in the study (12.7 h^?1). Coincident with the formation of gas‐phase species, particulate chlorine levels also rise. Cl₂, ClNO₂, NHCl₂, and NCl₃ exist in the headspace of the bleach solution, whereas HOCl was only observed after floor washing. HOCl decays away 1.4 times faster than the air exchange rate, indicative of uptake onto room surfaces, and consistent with the well‐known chlorinating ability of HOCl. Photochemical box modeling captures the temporal profiles of Cl₂ and HOCl very well and indicates that the OH, Cl, and ClO gas‐phase radical concentrations in the indoor environment could be greatly enhanced (>10⁶ and 10⁵ cm^?3 for OH and Cl, respectively) in such washing conditions, dependent on the amount of indoor illumination.     

Volatile disinfection by-product analysis from chlorinated indoor swimming pools

Chlorination of indoor swimming pools is practiced for disinfection and oxidation of reduced compounds that are introduced to water by swimmers. However, there is growing concern associated with formation for chlorinated disinfection by-products (DBPs) in these settings. Volatile DBPs are of particular concern because they may promote respiratory ailments and other adverse health effects among swimmers and patrons of indoor pool facilities. To examine the scope of this issue, water samples were collected from 11 pools over a 6 month period and analyzed for free chlorine and their volatile DBP content. Eleven volatile DBPs were identified: monochloramine (NH₂Cl), dichloramine (NHCl₂), trichloramine (NCl₃), chloroform (CHCl₃), bromoform (CHBr₃), dichlorobromomethane (CHBrCl₂), dibromochloromethane (CHBr₂Cl), cyanogen chloride (CNCl), cyanogen bromide (CNBr), dichloroacetonitrile (CNCHCl₂), and dichloromethylamine (CH₃NCl₂). Of these 11 DBPs, 10 were identified as regularly occurring, with CHBrCl₂ only appearing sporadically. Pool water samples were analyzed for residual chlorine compounds using the DPD colorimetric method and by membrane introduction mass spectrometry (MIMS). These two methods were chosen as complementary measures of residual chlorine, and to allow for comparisons between the methods. The DPD method was demonstrated to consistently overestimate inorganic chloramine content in swimming pools. Pairwise correlations among the measured volatile DBPs allowed identification of dichloromethylamine and dichloroacetonitrile as potential swimming pool water quality indicator compounds.     

Evaluation of a portable bare-electrode amperometric analyzer for determining free chlorine in potable and swimming-pool waters

Chlorine in the forms of HOCl or ClO⁻ was determined rapidly and precisely in the range from 0.10 to 3.0 ppm chlorine, without titration, using a bare-electrode portable amperometric analyzer. The instrument was calibrated with a 1.00 ppm chlorine standard solution or an equivalent permanganate solution which is stable for at least 6 months. The detection limit was 0.10 ppm chlorine, and relative standard deviations (N = 10) were <6.0% in potable or swimming-pool waters containing 0.25, 1.00 and 2.50 ppm or 0.35, 1.40 and 2.70 ppm chlorine respectively. Bromine-, triiodide ion-, and Mn (VII)-generated signals were stoichiometrically equivalent to that of hypochlorite, but MnO₂ suspensions (1.5, 5.0 or 15 ppm) did not produce detectable amperometric signals.Analysis of solutions of hypochlorite with ammonium chloride or selected organic nitrogen compounds indicated that various N-chloro compounds may interfere. In the presence of N-chloroglycine (2.70 ppm chlorine) the amperometric signal was about 5% of that for the equivalent concentration of hypochlorite, but higher relative responses were obtained with NH₂Cl, NHCl₂ or NCl₃ (19, 42 and 70% at 2.60, 1.20 or 1.00 ppm chlorine respectively). Chlorinated urea (2.2 ppm N, 2.90 ppm chlorine), chlorinated bovine albumin (10 ppm albumin, 2.00 ppm chlorine) or monochloroisocyanurate (1.30 ppm chlorine) produced amperometric signals (76, <5 and 50% respectively) which are lower than those obtained by the N,N-diethyl-p-phenylenediamine (DPD) method (100, 12 and 92%).Twenty potable water samples were analyzed for free chlorine by the DPD and amperometric procedures. Statistical analysis showed no significant differences between the two sets of results (P < 0.1). Swimming-pool-water samples were also analyzed by the two methods in the field (22 samples) and in the laboratory (24 samples). In each set of results the mean free-chlorine value by the DPD procedure was significantly higher than that obtained amperometrically (P > 0.005). This discrepancy was associated with the probable presence of chlorinated urea, whose signal by amperometry is lower than that by the DPD method.The advantages of this simple procedure must be weighed against possible inaccurate results in the presence of NH₂Cl, NHCl₂ or NCl₃.     

The effect of pH on the efficiency of chlorine disinfection and virus enumeration

In the light of increasing world-wide water pollution, the controlled and effective chlorination of water is of paramount importance in the treatment of drinking water supplies. A recent publication indicated that hypochlorite ion (OCl⁻) which is formed at high pH levels appeared to be a more effective virucidal form of free chlorine than hypochlorous acid (HOCl), which occurs at lower pH levels. This was a reversal of the findings of many other research workers. The present paper reports on a further study which confirms that HOCl is a more effective virucide than OCl⁻. It also reports on comparative studies between the PFU and TCID₅₀ methods for virus evaluation at two pH levels in an attempt to find the reasons for the reversal in the results obtained.     

The effects of active chlorine on photooxidation of 2-methyl-2-butene

Active chlorine comprising hypochlorite (OCl⁻), hypochlorous acid (HOCl) and chlorine (Cl₂) is the active constituent in bleach formulations for a variety of industrial and consumer applications. However, the strong oxidative reactivity of active chlorine can cause adverse effects on both human health and the environment. In this study, aerosolized Oxone® [2KHSO₅, KHSO₄, K₂SO₄] with saline solution has been utilized to produce active chlorine (HOCl and Cl₂). To investigate the impact of active chlorine on volatile organic compound (VOC) oxidation, 2-methyl-2-butene (MB) was photoirradiated in the presence of active chlorine using a 2-m³ Teflon film indoor chamber. The resulting carbonyl products produced from photooxidation of MB were derivatized with O-(2,3,4,5,6-pentafluorobenzyl) hydroxyamine hydrochloride (PFBHA) and analyzed using gas chromatograph-ion trap mass spectrometer (GC/ITMS). The photooxidation of MB in the presence of active chlorine was simulated with an explicit kinetic model using a chemical solver (Morpho) which included both Master Chemical Mechanism (MCM) and Cl radical reactions. The reaction rate constants of a Cl radical with MB and its oxidized products were estimated using a Structure-Reactivity Relationship method. Under dark conditions no effect of active chlorine on MB oxidation was apparent, whereas under simulated daylight conditions (UV irradiation) rapid MB oxidation was observed due to photo-dissociation of active chlorine. The model simulation agrees with chamber data showing rapid production of oxygenated products that are characterized using GC/ITMS. Ozone formation was enhanced when MB was oxidized in the presence of irradiated active chlorine and NO_x.     

Ozonation of water containing chlorine or chloramines. Reaction products and kinetics

Ozone reacts with free aqueous chlorine when present as hypochlorite ion (OCl⁻) with a second order rate constant of 120 ± 15 M⁻¹ s⁻¹ at 20°C. About 77% of the chlorine reacts to produce Cl⁻ and 23% is oxidized to ClO⁻₃. No ClO⁻₄ is formed. Conversion of chlorine to monochloramine reduces the ozone reaction rate to 26 ± 4 M⁻¹ s⁻¹, independent of pH, NH₂Cl is transformed quantitatively to NO⁻₃ and Cl⁻ by O₃. Rate data for other chloramines are also presented. The direct reaction of ozone with chlorine accounts for a significant amount of the chlorine and ozone demand found when the two oxidants are used in combination under water works conditions.     

Rate constants of reactions of ozone with organic and inorganic compounds in water—III. Inorganic compounds and radicals

Second-order rate constants for reactions of ozone with 40 inorganic aqueous solutes are reported. Included are compounds of sulfur (e.g. H₂S, H₂SO₃, HOCH₂SO₃H), chlorine (e.g. Cl⁻, HOCl, NH₂Cl, HClO₂, ClO₂), bromine (e.g. Br⁻, HOBr), nitrogen (e.g. NH₃, NH₂OH, N₂O, HNO₂) and oxygen (e.g. H₂O₂), as well as free radicals (e.g. O₂⁻, OH^•). Most of these compounds exhibit an increase in rate constant with increasing pH corresponding to their degree of dissociation. Rate constants are based on ozone consumption rates measured by conventional batch-type or continuous-flow methods (10⁻³-10⁺⁶ M⁻¹ s⁻¹ range) and determinations of stoichiometric factors. Also listed are data determined by pulse-irradiation techniques using kinetic spectroscopy (10¹⁰ M⁻¹ s⁻¹ range). Additional literature data are reviewed for completeness. Results are discussed with respect to water treatment and environmental processes.     

Effects of UV 254 irradiation on residual chlorine and DBPs in chlorination of model organic-N precursors in swimming pools

Ultraviolet (UV) irradiation is commonly applied as a secondary disinfection process in chlorinated pools. UV-based systems have been reported to yield improvements in swimming pool water and air chemistry, but to date these observations have been largely anecdotal. The objectives of this investigation were to evaluate the effects of UV irradiation on chlorination of important organic-N precursors in swimming pools.Creatinine, L-arginine, L-histidine, glycine, and urea, which comprise the majority of the organic-N in human sweat and urine, were selected as precursors for use in conducting batch experiments to examine the time-course behavior of several DBPs and residual chlorine, with and without UV₂₅₄ irradiation. In addition, water samples from two natatoria were subjected to monochromatic UV irradiation at wavelengths of 222 nm and 254 nm to evaluate changes of liquid-phase chemistry. UV₂₅₄ irradiation promoted formation and/or decay of several chlorinated N-DBPs and also increased the rate of free chlorine consumption. UV exposure resulted in loss of inorganic chloramines (e.g., NCl₃) from solution. Dichloromethylamine (CH₃NCl₂) formation from creatinine was promoted by UV exposure, when free chlorine was present in solution; however, when free chlorine was depleted, CH₃NCl₂ photodecay was observed. Dichoroacetonitrile (CNCHCl₂) formation (from L-histidine and L-arginine) was promoted by UV₂₅₄ irradiation, as long as free chlorine was present in solution. Likewise, UV exposure was observed to amplify cyanogen chloride (CNCl) formation from chlorination of L-histidine, L-arginine, and glycine, up to the point of free chlorine depletion. The results from experiments involving UV irradiation of chlorinated swimming pool water were qualitatively consistent with the results of model experiments involving UV/chlorination of precursors in terms of the behavior of residual chlorine and DBPs measured in this study.The results indicate that UV₂₅₄ irradiation promotes several reactions that are involved in the formation and/or destruction of chlorinated N-DBPs in pool settings. Enhancement of DBP formation was consistent with a mechanism whereby a rate-limiting step in DBP formation was promoted by UV exposure. Promotion of these reactions also resulted in increases of free chlorine consumption rates.     

Trichloramine in swimming pools--formation and mass transfer

Trichloramine is a volatile, irritant compound of penetrating odor, which is found as a disinfection by-product in the air of chlorinated indoor swimming pools from reactions of nitrogenous compounds with chlorine. Acid amides, especially urea, ammonium ions and α-amino acids have been found as most efficient trichloramine precursors at acidic and neutral pH. For urea a relative NCl₃ formation of 96% at pH 2.5 and 76% at pH 7.1 was determined. Even under sub-stoichiometric molar ratios of Cl/N the formation of NCl₃ is favored over mono and dichlorinated products. However, the reaction kinetics of urea with chlorine is slow under conditions relevant for swimming pools. Also the mass transfer of NCl₃ from water to the gas phase which was calculated by the Deacon’s boundary layer model could be shown as a relatively slow process. Mass transfer would take 20 h or 5.8 d for a rough or a quiescent surface of the water, respectively. This is much more than a typical turnover rate of 6-8 h of a treatment cycle of a 25 m swimming pool. Therefore processes to remove NCl₃ and its precursors can help to minimize the exposure of bathers.     

Refining the use of evaporation in an experimental down-draft cool tower

Direct evaporative cooling has long been recognized as an energy-efficient and cost-effective means for space conditioning in hot dry areas. In order to extend the use of evaporative cooling to include exterior or semi-enclosed spaces, a down-draft evaporative ‘cool tower’ was integrated in the project of a 500 m² glazed courtyard located at the heart of a building complex in the arid Negev Highlands of southern Israel, designed by the authors. The present article describes the development of the cooling tower system, undertaken in three phases: (i) Prototype analysis. Performance of a small-scale tower was monitored, and comparisons were drawn between varying rates and mechanisms of water and air supply. The results indicated a potential for substantial temperature reduction in the order of 10 °C under summer daytime conditions, but a meager cooling output when using a natural draft system. Mechanical-forced air flow was thus utilized in the actual tower. (ii) Field monitoring. The cool tower, approximately 10 m in height and 10 m² in cross-sectional area, was operated and monitored during a summer season; its performance was analyzed using a series of water supply mechanisms and operating modes. The system produced a peak cooling output of just over 100 kW, with a wet bulb temperature depression of close to 85–95% during all hours of operation, and a water consumption rate of approximately 1–2 m³/day. (iii) Refinement. Potential improvement in the system's operation was investigated through the development of a wind capture mechanism for increasing inlet pressure and air flow to the space. Both fixed and dynamic capture units were investigated, with wind speed and direction as well as internal air speeds measured in the small-scale prototype tower. The wind capture unit with the simplest configuration and best performance is recommended for future integration in the full-scale tower.     

pH significantly affects removal of trace antibiotics in chlorination of municipal wastewater

The effect of pH on chlorination behaviors of 12 antibiotics, including β-lactams, sulfonamides, fluoroquinolones, tetracyclines, macrolides, and others at environmentally relevant concentrations was systematically examined in the effluent matrix of activated sludge process. The removal of most antibiotics (except cefalexin and tetracycline) significantly depended on pH in the range of 5.5-8.5. The elimination rates of ciprofloxacin, norfloxacin, anhydro-erythromycin, and roxithromycin increased while that of sulfamethoxazole decreased significantly with the increase of pH. Sulfadiazine, ofloxacin, and trimethoprim exhibited the highest reactivity with free available chlorine under the pH of 6-7, 7, and 7.5, respectively. Not only the free available chlorine species (HOCl and OCl⁻), but also the antibiotics species (cationic, neutral and anionic) affected the overall reaction rate. Anionic antibiotic species are usually much more reactive (1-3 orders of magnitude greater) than cationic antibiotic species toward free available chlorine. Although OCl⁻ is a weaker oxidant than HOCl, chlorination of sulfadiazine, sulfamethoxazole, ciprofloxacin, norfloxacin, and trimethoprim with OCl⁻ became significant at pH > 7.5. The observed kinetics rate constants calculated from species-specific rate constants could accurately (0.91 < R² < 0.99) predict the antibiotic removal in chlorination of activated sludge effluent with similar DOC and ammonia concentration to this study at a given pH value.     

Characterization of the heterotrophic biomass and the endogenous residue of activated sludge

The activated sludge process generates an endogenous residue (X_E) as a result of heterotrophic biomass decay (X_H). A literature review yielded limited information on the differences between X_E and X_H in terms of chemical composition and content of extracellular polymeric substances (EPS). The objective of this project was to characterize the chemical composition (x, y, z, a, b and c in C_xH_yO_zN_aP_bS_c) of the endogenous and the active fractions and EPS of activated sludge from well designed experiments. To isolate X_H and X_E in this study, activated sludge was generated in a 200 L pilot-scale aerobic membrane bioreactor (MBR) fed with a soluble and completely biodegradable synthetic influent of sodium acetate as the sole carbon source. This influent, which contained no influent unbiodegradable organic or inorganic particulate matter, allowed the generation of a sludge composed essentially of two fractions: heterotrophic biomass X_H and an endogenous residue X_E, the nitrifying biomass being negligible. The endogenous decay rate and the active biomass fraction of the MBR sludge were determined in 21-day aerobic digestion batch tests by monitoring the VSS and OUR responses. Fractions of X_H and X_E were respectively 68% and 32% in run 1 (MBR at 5.2 day SRT) and 59% and 41% in run 2 (MBR at 10.4 day SRT). The endogenous residue was isolated by subjecting the MBR sludge to prolonged aerobic batch digestion for 3 weeks, and was characterized in terms of (a) elemental analysis for carbon, nitrogen, phosphorus and sulphur; and (b) content of EPS. The MBR sludge was characterized using the same procedures (a and b). Knowing the proportions of X_H and X_E in this sludge, it was possible to characterize X_H by back calculation. Results from this investigation showed that the endogenous residue had a chemical composition different from that of the active biomass with a lower content of inorganic matter (1:4.2), of nitrogen (1:2.9), of phosphorus (1:5.3) and of sulphur (1:3.2) but a similar content of carbon (1:0.98). Based on these elemental analyses, chemical composition formulae for X_H and X_E were determined as CH_1.240O_0.375N_0.200P_0.0172S_0.0070 and CH_1.248O_0.492N_0.068P_0.0032S_0.0016, respectively. Data from EPS analyses also confirmed this difference in structure between X_E and X_H with an EPS content of 11-17% in X_Eversus 26-40% in X_H.     

Biodegradation of the endogenous residue of activated sludge

This study evaluated the potential biodegradability of the endogenous residue in activated sludge subjected to batch digestion under either non-aerated or alternating aerated and non-aerated conditions. Mixed liquor for the tests was generated in a 200 L pilot-scale aerobic membrane bioreactor (MBR) operated at a 5.2 days SRT. The MBR system was fed a soluble and completely biodegradable synthetic influent composed of sodium acetate as the sole carbon source. This influent, which contained no influent unbiodegradable organic or inorganic materials, allowed to generate sludge composed of essentially two fractions: a heterotrophic biomass X_H and an endogenous residue X_E, the nitrifying biomass being negligible (less than 2%). The endogenous decay rate and the active biomass fraction of the MBR sludge were determined in 21-day aerobic digestion batch tests by monitoring the VSS and OUR responses. Fractions of X_H and X_E: 68% and 32% were obtained, respectively, at a 5.2 days SRT. To assess the biodegradability of X_E, two batch digestion units operated at 35 °C were run for 90 days using thickened sludge from the MBR system. In the first unit, anaerobic conditions were maintained while in the second unit, alternating aerated and non-aerated conditions were applied. Data for both units showed apparent partial biodegradation of the endogenous residue. Modeling the batch tests indicated endogenous residue decay rates of 0.005 d⁻¹ and 0.012 d⁻¹ for the anaerobic unit and the alternating aerated and non-aerated conditions, respectively.     

Indoor acids and bases

Numerous acids and bases influence indoor air quality. The most abundant of these species are CO₂ (acidic) and NH₃ (basic), both emitted by building occupants. Other prominent inorganic acids are HNO₃, HONO, SO₂, H₂SO₄, HCl, and HOCl. Prominent organic acids include formic, acetic, and lactic; nicotine is a noteworthy organic base. Sources of N-, S-, and Cl-containing acids can include ventilation from outdoors, indoor combustion, consumer product use, and chemical reactions. Organic acids are commonly more abundant indoors than outdoors, with indoor sources including occupants, wood, and cooking. Beyond NH₃ and nicotine, other noteworthy bases include inorganic and organic amines. Acids and bases partition indoors among the gas-phase, airborne particles, bulk water, and surfaces; relevant thermodynamic parameters governing the partitioning are the acid-dissociation constant (K_a), Henry's law constant (K_H), and the octanol-air partition coefficient (K_oa). Condensed-phase water strongly influences the fate of indoor acids and bases and is also a medium for chemical interactions. Indoor surfaces can be large reservoirs of acids and bases. This extensive review of the state of knowledge establishes a foundation for future inquiry to better understand how acids and bases influence the suitability of indoor environments for occupants, cultural artifacts, and sensitive equipment.     

The stability of particulate nitrate in the Los Angeles atmosphere

Simultaneous measurements of atmosphere particulate nitrate (NO₃^?) and its gas phase precursor nitric acid (HONO₂) were conducted in Los Angeles during severe smog episodes, and the results were compared to those predicted on the basis of thermodynamic data for the HONO₂ (g) + NH₃ (g) = NH₄ NO₃ (s) equilibrium. Over the wide range of conditions studied (four-hour averaged NO₃^? = 0.5?44.3 μg m^?3 HONO₂ = 1.4?36.0 μg m^?3, T = 10?33°C, humidity = 16?99%, ozone up to 460 ppb) the solid equilibrium model was found to be applicable to only about one-third of the total number of data sets. In this case good agreement was found between measured nitrate values and those expected from comparison of measured and equilibrium nitric acid concentrations. Samples collected at humidities above the deliquescent point of ammonium nitrate at the sampling temperature, for which the solid NH₄ NO₃ equilibrium no longer applies and solution chemistry must be considered, accounted for two-thirds of the data sets. For this subset, good agreement was also found between experimental results and theoretical considerations.     

Disinfection by-product dynamics in a chlorinated, indoor swimming pool under conditions of heavy use: national swimming competition

Anecdotal evidence suggests that water quality in chlorinated, indoor pools deteriorates under conditions of heavy use. However, data to define these dynamics have not been reported. To address this issue, a study was performed in which water chemistry was monitored in a chlorinated, indoor pool before and during a national swimming competition, a period of heavy, intense use. NCl₃ concentration was observed to double after the first day, and increased by a factor of 3-4 over the 4 days of competition. CNCHCl₂ and CH₃NCl₂ concentrations both increased by a factor of 2-3 during the course of the meet, while CHCl₃ concentration showed only a modest increase during this same period. Diurnal patterns of NCl₃, CH₃NCl₂ and CHCl₃ concentrations were observed, and these patterns appeared to depend on the Henry’s law constant of the compound.Urea concentration showed a diurnal pattern, superimposed on a trend of steady increase during each day of the competition; however, the diurnal pattern of urea behavior could not be explained by reactions with chlorine, as the urea-free chlorine reaction is relatively slow. It is more likely that the overnight decrease in urea concentration was attributable to mixing of surface water with water in the deeper parts of the pool. The findings of this study provide an indication of the changes in pool water chemistry that take place in a chlorinated, indoor pool under heavy use conditions.     

Evaluation on the impacts of predators on biomass components and oxygen uptake in sequencing batch reactor and continuous systems

An expanded unified model for the biomass fractions, soluble-organic fractions, and oxygen-uptake rates considering extracellular polymeric substances (EPS), intracellular storage products (X_STO), and predators for activated sludge is used to study the impacts of predators on biomass components and oxygen uptake. The new model is applied to evaluate how predation affects the oxygen-uptake rate (OUR) and the different forms of biomass: active bacteria (X_H), X_EPS, and X_STO, under dynamic feast-and-famine and continuous conditions. For the dynamic conditions of a sequencing batch reactor (SBR), eliminating predators from the model increases X_H and X_EPS fractions significantly, and this causes the substantial increases in OUR and MLVSS once the famine period begins. An analysis of how the OUR is distributed among the several respiration processes shows that the predation of X_H is the most significant oxygen utilization rate process in the system under famine conditions of an SBR. Application of the model to simulate the long-term operation of an SBR indicates that predators reach their maximum fraction in the MLVSS (∼4% of MLVSS) at a solids retention time of about 13 days, but they are washed out at a solids retention time less than ∼3 days. Simulation for a continuous system indicates that predators take more time (about 800 h) to reach steady state and reach their maximum fraction (∼5.5%) at an SRT of ∼14 days. Comparison of SBR and continuous systems reveals that the predators have greater impact in the continuous system because the permanent near-famine condition accentuates predation processes.     

Nitrification in porous media during rapid,unsaturated water flow

A substantial nitrification in rapid infiltration (RI) systems for wastewater treatment is a prerequisite for obtaining good N removal by denitrification. The purpose of this study is to investigate nitrification in porous media at conditions corresponding to RI treatment systems. Nitrification in six 50-cm porous media columns (98% weathered granite or sand and 2% field soil) during unsaturated leaching at constant flow rates of synthetic wastewater was investigated. Concentrations of NH₄-N between 20 and 60 mg l⁻¹ were applied and vertical concentration profiles of NO₃-N, NO₂-N and NH₄-N were measured for 54 d at 30°C (three columns) and for 140 d at 10°C (three columns). A time lag in nitrification of 20 d was found at 10°C. Complete nitrification was obtained after 3–5 at 30°C and after approximately 50 d at 10°C. Assuming first-order nitrification at steady-state, the corresponding first order reaction rate coefficients (k₁) for NO₃ production in the columns were estimated to be between 0.4 and 1 h⁻¹ at 10°C and between 6 and 9 h⁻¹ at 30°C. Steady-state NO₃ profiles were obtained between 1.5 and up to 9 weeks after the experiments were started. At the actual soil-air contents (0.10 cm³ air phase cm⁻³ soil), oxygen limitations were not observed during the experiments. Nitrogen loadings (water flow times N concentration) above 100 mg N 1⁻¹ cm h⁻¹ (1 g N m⁻² h⁻¹) caused NH₄ accumulation in the columns at 10°C and should probably be avoided during operation of RI system.     

Ferrate(VI) oxidation of glycine and glycylglycine: Kinetics and products

Amino acids and peptides may form potentially harmful disinfection byproducts during the conventional treatment of water and wastewater. Removal of these parent compounds by the use of the environmental-friendly oxidant, ferrate(VI) (Fe^VIO₄²⁻, Fe(VI)) was assessed by studying the kinetics of the oxidation of glycine (NH₃⁺CH₂COOH, Gly) and glycylglycine (NH₃⁺CH₂CONHCH₂COOH, Gly-Gly) as a function of pH (4.0-12.4) at 25 °C. This study with Gly-Gly represents an initial investigation of oxidation of peptides by Fe(VI). Generally, the second-order rate constant (k) increased with decreased pH in the basic pH region, but this trend was reversed in the acidic pH range. Consideration of the reactivity of three oxidants (H₂FeO₄, HFeO₄⁻, and FeO₄²⁻) with three species of Gly and Gly-Gly (positive, neutral, and negative) reasonably explained the pH dependence of the rates. At pH 9.0, the molar consumption of Fe(VI) was nearly equal to that of Gly. The reaction of Fe(VI) with Gly at molar ratios of 1.0 and 2.0 ([Fe(VI)]:[Gly]) produced ammonia, carbon dioxide, and acetate. A reaction scheme is proposed which explains the formation of these products. The values of k for oxidation of iminodiacetate and nitriloacetate at pH 7.0 were also determined in order to compare oxidation of amines by Fe(VI). The calculated half-lives at neutral pH for the oxidation of primary and secondary amines were in seconds while decomposition of tertiary amines would occur in minutes. Overall, the reactivity of Fe(VI) with Gly and Gly-Gly indicates the significant potential of Fe(VI) to remove amine- and peptide-containing pollutants in water and wastewater.