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.     

Performance of conventional multi-barrier drinking water treatment plants for the removal of four artificial sweeteners

Due to incomplete removal of artificial sweeteners in wastewater treatment plants some of these compounds end up in receiving surface waters, which are used for drinking water production. The sum of removal efficiency of single treatment steps in multi-barrier treatment systems affects the concentrations of these compounds in the provided drinking water. This is the first systematic study revealing the effectiveness of single treatment steps in laboratory experiments and in waterworks. Six full-scale waterworks using surface water influenced raw water were sampled up to ten times to study the fate of acesulfame, saccharin, cyclamate and sucralose. For the most important treatment technologies the results were confirmed by laboratory batch experiments. Saccharin and cyclamate proved to play a minor role for drinking water treatment plants as they were eliminated by nearly 100% in all waterworks with biologically active treatment units like river bank filtration (RBF) or artificial groundwater recharge. Acesulfame and sucralose were not biodegraded during RBF and their suitability as wastewater tracers under aerobic conditions was confirmed. Sucralose proved to be persistent against ozone and its transformation was <20% in lab and field investigations. Remaining traces were completely removed by subsequent granular activated carbon (GAC) filters. Acesulfame readily reacts with ozone (pseudo first-order rate constant k = 1.3 × 10⁻³ s⁻¹ at 1 mg L⁻¹ ozone concentration). However, the applied ozone concentrations and contact times under typical waterworks conditions only led to an incomplete removal (18-60%) in the ozonation step. Acesulfame was efficiently removed by subsequent GAC filters with a low throughput of less than 30 m³ kg⁻¹, but removal strongly depended on the GAC preload. Thus, acesulfame was detected up to 0.76 μg L⁻¹ in finished water.     

Comparison of the ozonation and Fenton process performances for the treatment of antibiotic containing manure

An integrated treatment method based on magnesium salt extraction followed by chemical oxidation was used for the treatment of a veterinary antibiotic, oxytetracycline (OTC) contaminated cow manure since animal manure can be an important source for antibiotic pollution in the environment. Pretreatment with magnesium salt enhanced the efficiencies of subsequent oxidation processes by extracting 63.9% of OTC from the manure thereby making it more favorable for oxidation with the hydroxyl radicals produced by the Fenton and ozone oxidation processes. Both the 24 h Fenton oxidation process with 434 mM H₂O₂ and 43.4 mM Fe²⁺ doses and the 1-h ozonation process with an applied ozone dose of 2.5 mg min^− 1 provided more than 90% OTC removal from the manure slurry. However, the second-order OTC removal rate constant of Fenton process (119 M^− 1s^− 1) was remarkably lower than that obtained with the ozonation process (548 M^− 1s^− 1). The oxidant dose was a significant factor for the efficiency of the Fenton treatment but not for the ozone treatment. The efficiencies of both the Fenton and ozone oxidation processes were not affected by the pH adjustment of the manure slurry.     

Ozone oxidation of pharmaceuticals, endocrine disruptors and pesticides during drinking water treatment

This study investigates the oxidation of pharmaceuticals, endocrine disrupting compounds and pesticides during ozonation applied in drinking water treatment. In the first step, second-order rate constants for the reactions of selected compounds with molecular ozone (k_O3) were determined in bench-scale experiments at pH 8.10: caffeine (650 ± 22 M⁻¹ s⁻¹), progesterone (601 ± 9 M⁻¹ s⁻¹), medroxyprogesterone (558 ± 9 M⁻¹ s⁻¹), norethindrone (2215 ± 76 M⁻¹ s⁻¹) and levonorgestrel (1427 ± 62 M⁻¹ s⁻¹). Compared to phenolic estrogens (estrone, 17β-estradiol, estriol and 17α-ethinylestradiol), the selected progestogen endocrine disruptors reacted far slower with ozone. In the second part of the study, bench-scale experiments were conducted with surface waters spiked with 16 target compounds to assess their oxidative removal using ozone and determine if bench-scale results would accurately predict full-scale removal data. Overall, the data provided evidence that ozone is effective for removing trace organic contaminants from water with ozone doses typically applied in drinking water treatment. Ozonation removed over 80% of caffeine, pharmaceuticals and endocrine disruptors within the CT value of about 2 mg min L⁻¹. As expected, pesticides were found to be the most recalcitrant compounds to oxidize. Caffeine can be used as an indicator compound to gauge the efficacy of ozone treatment.     

Ozonation of wastewater containing N-methylmorpholine-N-oxide

Ozonation of synthetic wastewater containing N-methylmorpholine-N-oxide (NMMO) was investigated in batch experiments at different pH-values. Increasing pH caused higher initial elimination rates of NMMO as well as higher formation rates of nitrate. In mass transfer limited experiments, the shortest time needed for NMMO removal was observed at pH 7. This could be explained on the one hand through the importance of ^·OH-radicals for the oxidation of NMMO and on the other hand through ozone decomposition reactions by ^·OH-radicals at high pH-values. Dissolved ozone increased rapidly after elimination of NMMO at pH 7 and 8.5. High oxygen uptake rates of biomass with ozonation products showed the increase of the biodegradability compared to the initial synthetic wastewater. An improvement of ozone efficiency for elimination of NMMO and organic carbon can be expected in a process using a bioreactor in a recycle system.     

Electrochemical oxidation of trace organic contaminants in reverse osmosis concentrate using RuO2/IrO2-coated titanium anodes

During membrane treatment of secondary effluent from wastewater treatment plants, a reverse osmosis concentrate (ROC) containing trace organic contaminants is generated. As the latter are of concern, effective and economic treatment methods are required. Here, we investigated electrochemical oxidation of ROC using Ti/Ru_0.7Ir_0.3O₂ electrodes, focussing on the removal of dissolved organic carbon (DOC), specific ultra-violet absorbance at 254 nm (SUVA₂₅₄), and 28 pharmaceuticals and pesticides frequently encountered in secondary treated effluents. The experiments were conducted in a continuously fed reactor at current densities (J) ranging from 1 to 250 A m⁻² anode, and a batch reactor at J = 250 A m⁻². Higher mineralization efficiency was observed during batch oxidation (e.g. 25.1 ± 2.7% DOC removal vs 0% removal in the continuous reactor after applying specific electrical charge, Q = 437.0 A h m⁻³ ROC), indicating that DOC removal is depending on indirect oxidation by electrogenerated oxidants that accumulate in the bulk liquid. An initial increase and subsequent slow decrease in SUVA₂₅₄ during batch mode suggests the introduction of auxochrome substituents (e.g. -Cl, NH₂Cl, -Br, and -OH) into the aromatic compounds. Contrarily, in the continuous reactor ring-cleaving oxidation products were generated, and SUVA₂₅₄ removal correlated with applied charge. Furthermore, 20 of the target pharmaceuticals and pesticides completely disappeared in both the continuous and batch experiments when applying J ≥ 150 A m⁻² (i.e. Q ≥ 461.5 A h m⁻³) and 437.0 A h m⁻³ (J = 250 A m⁻²), respectively. Compounds that were more persistent during continuous oxidation were characterized by the presence of electrophilic groups on the aromatic ring (e.g. triclopyr) or by the absence of stronger nucleophilic substituents (e.g. ibuprofen). These pollutants were oxidized when applying higher specific electrical charge in batch mode (i.e. 1.45 kA h m⁻³ ROC). However, baseline toxicity as determined by Vibrio fischeri bioluminescence inhibition tests (Microtox) was increasing with higher applied charge during batch and continuous oxidation, indicating the formation of toxic oxidation products, possibly chlorinated and brominated organic compounds.     

Global sensitivity analysis for model-based prediction of oxidative micropollutant transformation during drinking water treatment

This study quantifies the uncertainty involved in predicting micropollutant oxidation during drinking water ozonation in a pilot plant reactor. The analysis is conducted for geosmin, methyl tert-butyl ether (MTBE), isopropylmethoxypyrazine (IPMP), bezafibrate, β-cyclocitral and ciprofloxazin. These compounds are representative for a wide range of substances with second order rate constants between 0.1 and 1.9 × 10⁴ M⁻¹ s⁻¹ for the reaction with ozone and between 2 × 10⁹ and 8 × 10⁹ M⁻¹ s⁻¹ for the reaction with OH-radicals. Uncertainty ranges are derived for second order rate constants, hydraulic parameters, flow- and ozone concentration data, and water characteristic parameters. The uncertain model factors are propagated via Monte Carlo simulation and the resulting probability distributions of the relative residual micropollutant concentrations are assessed. The importance of factors in determining model output variance is quantified using Extended Fourier Amplitude Sensitivity Testing (Extended-FAST). For substances that react slowly with ozone (MTBE, IPMP, geosmin) the water characteristic R_ct-value (ratio of ozone- to OH-radical concentration) is the most influential factor explaining 80% of the output variance. In the case of bezafibrate the R_ct-value and the second order rate constant for the reaction with ozone each contribute about 30% to the output variance. For β-cyclocitral and ciprofloxazin (fast reacting with ozone) the second order rate constant for the reaction with ozone and the hydraulic model structure become the dominating sources of uncertainty.     

Kinetic of benzotriazole oxidation by ozone and hydroxyl radical

Ozonation experiments were performed in batch reactors in order to determine the rate constants for the reaction of molecular ozone and OH radicals with benzotriazole (BT) at different pHs. The first group of ozonation experiments was carried out for the determination of the rate constant for the direct reactions between ozone and BT. Two different kinetic models were used for the determination of kinetic rate constants: (i) the log-reduction of BT with ozone in excess, (ii) the competition kinetic model. The second-order rate constants for BT with molecular ozone were determined to be 36.4 ± 3.8 M⁻¹ s⁻¹ and 18.4 ± 0.8 M⁻¹ s⁻¹ at pH 2 from the two methods respectively. With the competition method, the value at pH 5 was found to be 22.0 ± 2.0 M⁻¹ s⁻¹. In a following stage, the reaction of BT with OH radicals was investigated at pH values ranging from 2 to 10.2. Using a method involving two probe compounds during the ozonation, the second-order rate constants of the BT reaction with hydroxyl radicals were determined. The rate constants were found to vary from 6.2 × 10⁹ M⁻¹ s⁻¹ at pH 10.2 to 1.7 × 10¹⁰ M⁻¹ s⁻¹ at pH 2.     

Kinetics of electro-oxidation of ammonia-N, nitrites and COD from a recirculating aquaculture saline water system using BDD anodes

The viability of the electro-oxidation technology provided with boron doped diamond (BDD) electrodes for the treatment and reuse of the seawater used in a Recirculating Aquaculture System (RAS) was evaluated in this work.The influence of the applied current density (5-50 A m⁻²) in the removal of Total Ammonia Nitrogen (TAN), nitrite and chemical oxygen demand (COD) was analyzed observing that complete TAN removal together with important reductions of the other considered contaminants could be achieved, thus meeting the requirements for reuse of seawater in RAS systems.TAN removal, mainly due to an indirect oxidation mechanism was described by a second order kinetics while COD and nitrite removal followed zero-th order kinetics. The values of the kinetic constants for the anodic oxidation of each compound were obtained as a function of the applied current density (k_TAN = 7.86 × 10⁻⁵·exp(6.30 × 10⁻² J); k₂NO = 3.43 × 10⁻² J; k_COD = 1.35 × 10⁻² J). The formation of free chlorine and oxidation by-products, i.e., trihalomethanes (THMs) was followed along the electro-oxidation process. Although a maximum concentration of 1.7 mg l⁻¹ of total trihalomethanes was detected an integrated process combining electrochemical oxidation in order to eliminate TAN, nitrite and COD and adsorption onto activated carbon to remove the residual chlorine and THMs is proposed, as an efficient alternative to treat and reuse the seawater in fish culture systems. Finally, the energy consumption of the treatment has been evaluated.     

Microbial community distribution and activity dynamics of granular biomass in a CANON reactor

The application of microelectrodes to measure oxygen and nitrite concentrations inside granules operated at 20 °C in a CANON (Complete Autotrophic Nitrogen-removal Over Nitrite) reactor and the application of the FISH (Fluorescent In Situ Hybridization) technique to cryosectioned slices of these granules showed the presence of two differentiated zones inside of them: an external nitrification zone and an internal anammox zone. The FISH analysis of these layers allowed the identification of Nitrosomonas spp. and Candidatus Kuenenia Stutgartiensis as the main populations carrying out aerobic and anaerobic ammonia oxidation, respectively.Concentration microprofiles measured at different oxygen concentrations in the bulk liquid (from 1.5 to 35.2 mg O₂ L⁻¹) revealed that oxygen was consumed in a surface layer of 100-350 μm width. The obtained consumption rate of the most active layers was of 80 g O₂ (L_granule)⁻¹ d⁻¹. Anammox activity was registered between 400 and 1000 μm depth inside the granules. The nitrogen removal capacity of the studied sequencing batch reactor containing the granular biomass was of 0.5 g N L⁻¹ d⁻¹. This value is similar to the mean nitrogen removal rate obtained from calculations based on in- and outflow concentrations.Information obtained in the present work allowed the establishment of a simple control strategy based on the measurements of NH₄⁺ and NO₂⁻ in the bulk liquid and acting over the dissolved oxygen concentration in the bulk liquid and the hydraulic retention time of the reactor.     

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.     

Effectiveness of different oxidizing agents for removing sodium dodecylbenzenesulphonate in aqueous systems

The present study investigates the efficacy of various oxidizing treatments (ClO⁻, ClO₂, KMnO₄, O₃, O₃/H₂O₂, O₃/activated carbon) to remove from waters sodium dodecylbenzenesulphonate (SDBS), considered as model surfactant. Results obtained show that the use of ClO⁻ and ClO₂ does not cause appreciable SDBS degradation. Additionally, in the case of ClO⁻, trihalomethanes are generated, increasing system toxicity. Because the reaction kinetics between SDBS and KMnO₄ is very slow, a decrease in contaminant concentration is not observed, even at very acid pH values. SDBS reactivity with ozone is very low, with a kinetic constant (kO3) of 3.68 M⁻¹ s⁻¹, but its reactivity with HO radicals is very high (k_OH = 1.16 × 10¹⁰ M⁻¹ s⁻¹), therefore O₃/H₂O₂ and O₃/activated carbon, which can also generate HO, appear as promising advanced oxidation processes to remove this contaminant from waters. The method based on ozone and activated carbon was the only process studied that produced both an increase in SDBS removal rate (due to the generation of HO radicals in the O₃-PAC or O₃-GAC interaction) and a considerable reduction in the concentration of dissolved organic carbon in the system due to the PAC adsorbent properties.     

Efficiency of phenol biodegradation by planktonic Pseudomonas pseudoalcaligenes (a constructed wetland isolate) vs. root and gravel biofilm

In the last two decades, constructed wetland systems gained increasing interest in wastewater treatment and as such have been intensively studied around the world. While most of the studies showed excellent removal of various pollutants, the exact contribution, in kinetic terms, of its particular components (such as: root, gravel and water) combined with bacteria is almost nonexistent.In the present study, a phenol degrader bacterium identified as Pseudomonas pseudoalcaligenes was isolated from a constructed wetland, and used in an experimental set-up containing: plants and gravel. Phenol removal rate by planktonic and biofilm bacteria (on sterile Zea mays roots and gravel surfaces) was studied. Specific phenol removal rates revealed significant advantage of planktonic cells (1.04 × 10⁻⁹ mg phenol/CFU/h) compared to root and gravel biofilms: 4.59 × 10⁻¹¹-2.04 × 10⁻¹⁰ and 8.04 × 10⁻¹¹-4.39 × 10⁻¹⁰ (mg phenol/CFU/h), respectively.In batch cultures, phenol biodegradation kinetic parameters were determined by biomass growth rates and phenol removal as a function of time. Based on Haldane equation, kinetic constants such as μ_max = 1.15/h, K_s = 35.4 mg/L and K_i = 198.6 mg/L fit well phenol removal by P. pseudoalcaligenes.Although P. pseudoalcaligenes planktonic cells showed the highest phenol removal rate, in constructed wetland systems and especially in those with sub-surface flow, it is expected that surface associated microorganisms (biofilms) will provide a much higher contribution in phenol and other organics removal, due to greater bacterial biomass.Factors affecting the performance of planktonic vs. biofilm bacteria in sub-surface flow constructed wetlands are further discussed.     

Evaluation of nanoscale zerovalent iron particles for trichloroethene degradation in clayey soils

The longevity and reactivity of nanoscale zerovalent iron (nZVI) and palladized bimetallic particles (BNP) were evaluated in batch and column experiments for remediation of a trichloroethene (TCE)-contaminated plume within a clayey soil from Oak Ridge Reservation (ORR). Comparative studies assessing the viability of BNP and nZVI confirmed that particle behavior is severely affected by clay sediments. Surface morphology and composition analyses using SEM and SEM-energy-dispersive spectroscopy spectrum revealed particle agglomeration through the formation of clay-iron aggregates of greater mass during the early phase of the experiment. Batch study results suggest that TCE degradation in ORR clayey soil follows a pseudo-first-order kinetic model exhibiting reaction rate constants (k) of 0.05-0.24 day^− 1 at varied iron-to-soil ratios. Despite high reactivity in water, BNP were less effective in the site-derived clay sediment with calculated TCE removal efficiencies of 98.7% and 19.59%, respectively.A column experiment was conducted to investigate particle longevity and indicator parameters of the TCE degradation process under flow conditions. It revealed that the TCE removal efficiency gradually declined over the course of the experiment from 86-93% to 51-52%, correlating to a progressive increase in oxidation-reduction potential (ORP) from − 485 to − 250 mV and pH drop from 8.2-8.6 to 7.4-7.5. The rate of nZVI deactivation reaction was found to be a first order with a k_d value of 0.0058 day^− 1. SEM images of residual nZVI revealed heavily agglomerated particles. However, despite widespread oxidation and agglomeration, particles managed to maintain some capacity for oxidation. A quantitative analysis of nZVI deactivation has the potential of predicting nZVI longevity in order to improve the design strategy of TCE remediation.     

Removal of micropollutants from aerobically treated grey water via ozone and activated carbon

Ozonation and adsorption onto activated carbon were tested for the removal micropollutants of personal care products from aerobically treated grey water. MilliQ water spiked with micropollutants (100-1600 μgL⁻¹) was ozonated at a dosing rate of 1.22. In 45 min, this effectively removed (>99%): Four parabens, bisphenol-A, hexylcinnamic aldehyde, 4-methylbenzylidene-camphor (4MBC), benzophenone-3 (BP3), triclosan, galaxolide and ethylhexyl methoxycinnamate. After 60 min, the removal efficiency of benzalkonium chloride was 98%, tonalide and nonylphenol 95%, octocrylene 92% and 2-phenyl-5-benzimidazolesulfonic acid (PBSA) 84%. Ozonation of aerobically treated grey water at an applied ozone dose of 15 mgL⁻¹, reduced the concentrations of octocrylene, nonylphenol, triclosan, galaxolide, tonalide and 4-methylbenzylidene-camphor to below limits of quantification, with removal efficiencies of at least 79%. Complete adsorption of all studied micropollutants onto powdered activated carbon (PAC) was observed in batch tests with milliQ water spiked with 100-1600 μgL⁻¹ at a PAC dose of 1.25 gL⁻¹ and a contact time of 5 min. Three granular activated carbon (GAC) column experiments were operated to treat aerobically treated grey water. The operation of a GAC column with aerobically treated grey water spiked with micropollutants in the range of 0.1-10 μgL⁻¹ at a flow of 0.5 bed volumes (BV)h⁻¹ showed micropollutant removal efficiencies higher than 72%. During the operation time of 1728 BV, no breakthrough of TOC or micropollutants was observed. Removal of micropollutants from aerobically treated grey water was tested in a GAC column at a flow of 2 BVh⁻¹. Bisphenol-A, triclosan, tonalide, BP3, galaxolide, nonylphenol and PBSA were effectively removed even after a stable TOC breakthrough of 65% had been reached. After spiking the aerobically treated effluent with micropollutants to concentrations of 10-100 μgL⁻¹, efficient removal to below limits of quantification continued for at least 1440 BV. Both ozonation and adsorption are suitable techniques for the removal of micropollutants from aerobically treated grey water.     

A sustainable, carbon neutral methane oxidation by a partnership of methane oxidizing communities and microalgae

Effluents of anaerobic wastewater treatment plants are saturated with methane, an effective greenhouse gas. We propose a novel approach to treat such effluents using a coculture of methane oxidizing communities and microalgae, further indicated as methalgae, which would allow microbial methane oxidation with minimal CO₂ emissions. Coculturing a methane oxidizing community with microalgae in sequence batch reactors under continuous lightning yielded a factor of about 1.6 more biomass relative to the control without microalgae. Moreover, 55% less external oxygen supply was needed to maintain the methane oxidation, as oxygen was produced in situ by the microalgae. An overall methane oxidation rate of 171 ± 27 mg CH₄ L⁻¹ liquid phase d⁻¹ was accomplished in a semi-batch setup, while the excess CO₂ production was lower than 1 mg CO₂ L⁻¹ d⁻¹. Both nitrate and ammonium were feasible nitrogen sources for the methalgae. These results show that a coculture of microalgae and methane oxidizing communities can be used to oxidize dissolved methane under O₂-limiting conditions, which could lead to a novel treatment for dissolved methane in anaerobic effluents.     

High-rate denitrification using polyethylene glycol gel carriers entrapping heterotrophic denitrifying bacteria

This study evaluated the nitrogen removal performance of polyethylene glycol (PEG) gel carriers containing entrapped heterotrophic denitrifying bacteria. A laboratory-scale denitrification reactor was operated for treatment of synthetic nitrate wastewater. The nitrogen removal activity gradually increased in continuous feed experiments, reaching 4.4 kg N m⁻³ d⁻¹ on day 16 (30 °C). A maximum nitrogen removal rate of 5.1 kg N m⁻³ d⁻¹ was observed. A high nitrogen removal efficiency of 92% on average was observed at a high loading rate. In batch experiments, the denitrifying gel carriers were characterized by temperature. Nitrate and total nitrogen removal activities both increased with increasing temperature, reaching a maximum at 37 and 43 °C, respectively. Apparent activation energies for nitrate and nitrite reduction were 52.1 and 71.9 kJ mol⁻¹, respectively. Clone library analysis performed on the basis of the 16S rRNA gene revealed that Hyphomicrobium was mainly involved in denitrification in the methanol-fed denitrification reactors.     

Influences of humic acid, bicarbonate and calcium on Cr(VI) reductive removal by zero-valent iron

The influences of various geochemical constituents, such as humic acid, HCO₃⁻, and Ca²⁺, on Cr(VI) removal by zero-valent iron (Fe⁰) were investigated in a batch setting. The collective impacts of humic acid, HCO₃⁻, and Ca²⁺ on the Cr(VI) reduction process by Fe⁰ appeared to significantly differ from their individual impacts. Humic acid introduced a marginal influence on Fe⁰ reactivity toward Cr(VI) reduction, whereas HCO₃⁻ greatly enhanced Cr(VI) removal by maintaining the solution pH near neutral. The Cr(VI) reduction rate constants (k_obs) were increased by 37.8% and 78.3%, respectively, with 2 mM and 6 mM HCO₃⁻ in solutions where humic acid and Ca²⁺ were absent. Singly present Ca²⁺ did not show a significant impact to Cr(VI) reduction. However, probably due to the formation of passivating CaCO₃, further addition of Ca²⁺ to HCO₃⁻ containing solutions resulted in a decrease of k_obs compared to solutions containing HCO₃⁻ alone. Ca²⁺ enhanced humic acid adsorption led to a minor decrease of Cr(VI) reduction rates. In Ca²⁺-free solutions, humic acid increased the amount of total dissolved iron to 25 mg/l due to the formation of soluble Fe-humate complexes and stably dispersed fine Fe (oxy)hydroxide colloids, which appeared to suppress iron precipitation. In contrast, the coexistence of humic acid and Ca²⁺ significantly promoted the aggregation of Fe (oxy)hydroxides, with which humic acid co-aggregated and co-precipitated. These aggregates would progressively be deposited on Fe⁰ surfaces and impose long-term impacts on the permeability of PRBs.     

Reactions of tetracycline antibiotics with chlorine dioxide and free chlorine

Tetracyclines (TCs) are a group of widely used antibiotics that have been frequently found in the aquatic environment. The potential reactions of TCs with common water disinfection oxidants such as chlorine dioxide (ClO₂) and free available chlorine (FAC) have not been studied in depth and are the focus of this study. The oxidation kinetics of tetracycline, oxytetracycline, chlorotetracycline and iso-chlorotetracycline by ClO₂ and FAC are very rapid (with large apparent second-order rate constants k_app = 2.24 × 10⁵-1.26 × 10⁶ M⁻¹ s⁻¹ with ClO₂ and k_app = 1.12 × 10⁴-1.78 × 10⁶ M⁻¹ s⁻¹ with FAC at pH 7.0) and highly dependent on pH. Species-specific rate constants are obtained by kinetic modeling that incorporates pH-speciation of TCs and the oxidants (for FAC), and reveal that TCs primarily react with ClO₂ and FAC by their unprotonated dimethylamino group and deprotonated phenolic-diketone group. The modest difference in reactivity among the four TCs toward the oxidants is consistent with expectation and can be explained by structural influences on the two reactive moieties. Product evaluation shows that oxidation of TCs by ClO₂ leads to (hydr)oxylation and breakage of TC molecules, while oxidation of TCs by FAC leads to chlorinated and (hydr)oxylated products without any substantial ring breakage. Results of this study indicate that rapid transformation of TCs by oxidants such as ClO₂ and FAC under water and wastewater treatment conditions can be expected.