Kinetic constants and transformation products of ornidazole during ozonation.

Ornidazole (ONZ), a nitroimidazole antibiotic detected in water bodies, may negatively impact the aquatic ecosystem. Its reaction kinetics during ozonation which is a feasible and applicable technology to control the contamination of emerging contaminants, however, has not been reported in literature. In this study, we measured the apparent second-order kinetic constant of ONZ with ozone molecules via the excessive ozone method and the competing method which led to an average value of 103.8 ± 2.7 M-1 s-1 at pH 7. The apparent second-order kinetic constant of ONZ with HO• was calculated to be 4.65 × 109 M-1 s-1 with the concept of Rct measured via para-chlorobenzoic acid as a probe. The transformation products (TPs) of ONZ during ozonation at pH 3 and pH 11 were separately analyzed with HPLC-MS/MS and some unique products were found at pH 11, reflecting the influence of HO•. The toxicity of individual TPs was predicted with the tool of T.E.S.T. It was found that 62% of 21 identified TPs could be more toxic than ONZ in terms of at least one acute toxicity endpoint, including chlorinated amines and N-oxides. The analysis with a respirometer further revealed that the toxicity of mixing TPs generated at HO• rich conditions was slightly lower than O3 dominated conditions. In general, this study provides the basic kinetic data for designing ozonation processes to eliminate ONZ and the important reference for understanding the toxicity evolution of ONZ during ozonation.

Non-Biological Slaughterhouse Wastewater Treatment with Membrane Processes-An Opportunity for Water Recycling.

The pressure-driven membrane separation processes ultrafiltration (UF) and reverse osmosis (RO) enable the effective purification of wastewater, in particular in combination, allowing organic and inorganic contaminants to be separated from the wastewater. Consequently, this work investigates the suitability of this technology for slaughterhouse wastewater (SWW) recycling. This was investigated by means of laboratory and bench-scale plant membrane experiments, whereby slaughterhouse wastewater (SWW) pre-treated by flotation was first treated with UF and then further purified with RO. Through the process combination UF + RO in the bench scale experiment, a reduction of the parameters total organic carbon (TOC), chemical oxygen demand (COD) of more than 98% and 97% for the parameter total nitrogen (TN) could be achieved. This means that wastewater reuse without product contact can be guaranteed. For direct process water reuse, only the concentration limit for ammonium could not be reached. In addition, scanning electron microscopy (SEM) images and energy dispersive X-ray spectroscopy (EDX) analyses of the RO membrane were carried out before and after the experiment, which did not indicate any scaling effects.

Long-term nitrite-oxidizing bacteria suppression in a continuous activated sludge system exposed to frequent changes in pH and oxygen set-points.

Research has proven the adaptation of nitrite-oxidizing bacteria to unfavorable environmental conditions, and this work presents a novel concept to prevent nitrite oxidation during partial nitrification in wastewater. The approach is based on the real-time updating of mathematical models of the process to search for optimal set-points of pH and oxygen concentration in a continuous activated sludge reactor with a high sludge age (20.3 days). A heuristic optimization technique by 13 optimum set-points simultaneously maximized the degree of ammonia oxidation (α) and nitrite accumulation (ß), achieving an (α + ß) = 190% per day. The activated sludge reactor was conducted for 780 days under three control schemes: open-loop control, fuzzy model supervisory control and phenomenological supervisory control. The phenomenological supervisory control system achieved the best results, simultaneously reaching 95% ammonium oxidation and 90% nitrite accumulation. The Haldane kinetics were analyzed using steady-state concentrations of all nitrogen species, concluding that the simultaneous maximization of α + ß led to selecting set-points at the extreme values of the following ranges: pH = 7.5-8.5 and DO = 0.8-1.0 mg O2/L, which enabled the inhibition of one nitrifier species. At the same time, the other one was relieved from inhibition. The 16sRNA assays indicated that the nitrite-oxidizing bacteria presence (genera Nitrobacter and Nitrospira) shifted from 32% to less than 8% after 280 days of continuous operation with optimal pH and oxygen set-points.

Optimizing the Extraction Conditions of Hydroxytyrosol from Olive Leaves Using a Modified Spherical Activated Carbon: A New Experimental Design.

The purification of hydroxytyrosol from olive leaves extract by modified activated carbon was studied experimentally in a batch system and a column by adsorption and desorption processes. The extraction yield reached 90% of hydroxytyrosol, which is the major compound found in the extract. Despite the abundance of research on extracts of hydroxytyrosol from olive leaves, it seems that the applied methods can be further improved. In this study, several approaches were applied to optimize the extraction conditions of this molecule. Hence, the response surface method and the Box-Behnken design (BBD) were used to evaluate the effect of the temperature, time, and adsorbent dose on the hydroxytyrosol recovery. Moreover, adsorption isotherm, kinetics, and thermodynamic studies were also performed to clarify the nature of the process. The main finding was the obtainment of a maximum adsorption yield of 97.5% at an adsorbent/adsorbate ratio of 1 : 20, after a 6 h cycle and at a temperature of 30°C. Furthermore, adsorption process seemed to fit best with Freundlich model. In addition, the thermodynamic study describes a spontaneous and endothermic process. Desorption assay using ethanol helped to recover 73% of hydroxytyrosol. Furthermore, the HPLC analysis of fractions after column adsorption showed a simple peak of hydroxytyrosol with purity higher than 97% and a flavonoids-rich fraction. These findings would indicate that this separation method for the recovery of phenolic compounds with high antioxidant activity can be a very promising one.

Dynamic and equilibrium precipitation of struvite from the concentrated cellulosic ethanol stillage.

The phosphate rock mineral is the main source of P-fertilizer production. It is estimated to become depleted in next century. Thus, the recovery of phosphorus from waste streams has attracted great interest. The cellulosic ethanol production is seen as more and more important in future. During the production of cellulosic ethanol, the phosphorus element is released from lignocellulosic biomasses and ends up dissolved as phosphate ions in the stillage stream. In this study, the struvite (MgNH4PO4 · 6 H2O) recovery from the concentrated cellulosic ethanol stillage (ES) was conducted under room conditions with an initial pH at 7-9. The effect of Mg2+, PO43-, NH4+ and Ca2+ during struvite precipitation tests was investigated. The optimized pH value for struvite recovery is estimated at 8.5, by which 85% of PO43- and 46% of Mg2+ are removed from the liquid stream. The mass fraction of struvite in recovered crystal sample reaches 82 wt.%. The economic evaluation of struvite recovery from ES was also investigated. This work proves that the struvite is potentially to be recovered with high purity from the concentrated cellulosic ethanol stillage.

Steady-state modeling of the biodegradation performance of a multistage moving bed biofilm reactor (MBBR) used for on-site greywater treatment.

In this study, the Activated Sludge Model No. 3 (ASM3) was applied for the simulation of the removal of organics and nitrogen in a multistage moving bed biofilm reactor (MBBR) used for biological greywater treatment. The data related to the characterization of the greywater were collected over a period of 5 months to be investigated in the model. The reactor showed a high performance for the removal of chemical oxygen demand (COD), dissolved organic carbon (DOC), biological oxygen demand (BOD5), ammonia (NH4-N), and total nitrogen (TN) with a removal efficiency of 93%, 80.7%, 99%, 89%, and 77%, respectively. The results of modeling showed a good correlation between simulated and experimental concentrations of COD issued from different reactors of the MBBR system. The adaptability of the ASM3 model to fit other parameters such as TN, NH4-N, total suspended solids (TSS), and the dissolved oxygen (DO) was also investigated for two selected reactors: reactor (R1) and the reactor (R5). The simulation results showed an acceptable correlation regarding the evolution of the investigated parameters in R1 and R5 and in the effluent except for total nitrogen TN. The adjustment of the stoichiometric parameters led to a satisfactory simulation of TN concentrations.

A comparative study on ozone, hydrogen peroxide and UV based advanced oxidation processes for efficient removal of diethyl phthalate in water.

Several Advanced Oxidation Processes (AOPs) including O3/H2O2, O3/TiO2, O3/activated carbon (AC), O3/Al2O3, O3/Fe2+/H2O2 and UV/TiO2 have been investigated and compared for the removal of diethyl phthalate (DEP), an endocrine disrupting compound, in aqueous solutions. Hydroxyl radicals were the main species responsible for DEP degradation and this was supported by computational chemistry calculation, scavenger experiments, and LC/MS/MS analysis. The change of the abundance of reaction products over time was determined. Organic acids as well as anhydride and hydroxylated products were found to accumulate in solution even after long reaction time (2 h). Careful choice of the operating parameters (pH, ozone concentration and catalyst dosage) was crucial to achieve enhanced performance of the combined processes above what each oxidant and catalyst can achieve alone. O3/AC process was found to reduce the oxidation efficiency of O3 at high ozone concentrations. Heterogeneous catalytic ozonation with Al2O3 was the most effective process for DEP removal (∼100% removal in about 15 min) and based on pseudo-first-order kinetics at pH7, the studied oxidation processes followed the order: O3/Al2O3(0.093 min-1)>O3/H2O2/Fe2+(0.076 min-1)>O3/AC(0.069 min-1)>O3/H2O2(0.053 min-1)>O3/TiO2(0.050 min-1)> O3 alone (0.039 min-1)>UV/TiO2(0.009 min-1).

Application of direct contact membrane distillation for saline dairy effluent treatment: performance and fouling analysis.

Membrane distillation is getting increasing attention thanks to its advantages in terms of energy consumption and final permeate quality in addition to its resistance against highly corrosive media which forms an appealing solution for industrial wastewater treatment. Despite its advantages, one of the most challenging issues in direct contact membrane distillation (DCMD) is membrane fouling and wetting. In the present research work, saline dairy effluent discharged from hard cheese industry was pretreated by macrofiltration (MAF) and ultrafiltration (UF) and processed by DCMD to investigate the extent of the aforementioned issues. Effluents pretreated by UF have led the best process performance with stable flux values at different operating conditions. Fouling has occurred in all the experiments, though their effect on the flux behavior and membrane wetting was different from one feed to the other. Changing the flow rate and the temperature difference have affected slightly the membrane wettability for all feed qualities. In all experiments, the permeate has maintained a good quality with low electrical conductivity that did not exceed 70 µS/cm and low total organic carbon < 2 mg/L.

Direct contact membrane distillation applied to saline wastewater: parameter optimization.

Freshwater availability is increasingly under pressure from growing demand, resource depletion and environmental pollution. Desalination of saline wastewater is an option for supplying households, industry and agriculture with water, but technologies such as reverse osmosis, evaporation or electrodialysis are energy intensive. By contrast, membrane distillation (MD) is a competitive technology for water desalination. In our study, response surface methodology was applied to optimize the direct contact membrane distillation (DCMD) treatment of synthetic saline wastewater. The aim was to enhance the process performance and the permeate flux Jp (L/m2·h) by optimizing the operating parameters: temperature difference ΔT, feed velocity Vf, salt concentration [NaCl], and glucose concentration [Gluc]. The results are a high permeate quality, with 99.9% electrical conductivity reduction and more than 99.9% chemical oxygen demand (COD) removal rate. The predicted optimum permeate flux Jp was 34.1 L/m2·h at ΔT = 55.2 °C and Vf = 0.086 m/s, the two most significant parameters. The model created showed a high degree of correlation between the experimental and the predicted responses, with high statistical significance.

Model-based performance and energy analyses of reverse osmosis to reuse wastewater in a PVC production site.

A pilot-scale reverse osmosis (RO) followed behind a membrane bioreactor (MBR) was developed for the desalination to reuse wastewater in a PVC production site. The solution-diffusion-film model (SDFM) based on the solution-diffusion model (SDM) and the film theory was proposed to describe rejections of electrolyte mixtures in the MBR effluent which consists of dominant ions (Na+ and Cl-) and several trace ions (Ca2+, Mg2+, K+ and SO42-). The universal global optimisation method was used to estimate the ion permeability coefficients (B) and mass transfer coefficients (K) in SDFM. Then, the membrane performance was evaluated based on the estimated parameters which demonstrated that the theoretical simulations were in line with the experimental results for the dominant ions. Moreover, an energy analysis model with the consideration of limitation imposed by the thermodynamic restriction was proposed to analyse the specific energy consumption of the pilot-scale RO system in various scenarios.

Adsorption and regenerative oxidation of trichlorophenol with synthetic zeolite: Ozone dosage and its influence on adsorption performance.

Regeneration of loaded adsorbents is a key step for the sustainability of an adsorption process. In this study, ozone was applied to regenerate a synthetic zeolite for the adsorption of trichlorophenol (TCP) as an organic model pollutant. Three initial concentrations of TCP in water phase were used in adsorption tests. After the equilibrium, zeolite loaded different amounts of TCP was dried and then regenerated with ozone gas. It was found that the adsorption capacity of zeolite was increased through three regeneration cycles. However, the adsorption kinetics was compromised after the regeneration with slightly declined 2nd order reaction constants. The ozone demand for the regeneration was highly dependent on the TCP mass loaded onto the zeolite. It was estimated that the mass ratio of ozone to TCP was 1.2 ± 0.3 g O3/g TCP.

Reuse of recalcitrant-rich anaerobic effluent as dilution water after enhancement of biodegradability by Fenton processes.

Anaerobic digestion is used to treat effluents with a lot of organics, such as molasses distillery wastewater (MDW) which is the effluent of bioethanol production from molasses. The raw MDW requires a lot of dilution water before biodigestion, while the digested MDW has high level of recalcitrants which are problematic for its discharge. This study investigated ferric coagulation, Fenton, Fenton-like (with ferric ions as catalyst) processes and their combinations on the biodegradability of digested MDW. The Fenton and Fenton-like processes after coagulation increased the MDW biodegradability defined by (BOD5/COD) from 0.07 to (0.4-0.6) and saved 50% of H2O2 consumed in the classic Fenton process. The effluent from coagulation coupled to a Fenton-like process was used as dilution water for the raw MDW before the anaerobic digestion. The process was stable with volumetric loading of approx. 2.7 g COD/L/d. It resulted in increased overall biogas recovery and significantly decreased the demand for the dilution water.

Treatment of melanoidin wastewater by anaerobic digestion and coagulation.

Melanoidins are dark-coloured recalcitrant pollutants found in many industrial wastewaters including coffee-manufacturing effluent, molasses distillery wastewater (MDWW) and other wastewater with molasses as the raw material. The wastewaters are mostly treated with anaerobic digestion after some dilution to minimize the inhibition effect. However, the dark colour and recalcitrant dissolved organic carbon (DOC) mainly caused by melanoidin are not effectively removed. The aim of this study was to investigate the removal of colour and remnant DOC by different coagulants from anaerobically digested MDWW. From the six coagulants tested, ferric chloride had the highest melanoidin (48%), colour (92.7%) and DOC (63.3%) removal at pH 5 and a dosage of 1.6 g/l. Both polymer and inorganic salt coagulants tested had optimal colour, melanoidin and DOC removal at acidic pH. The molecular size distribution of synthetic melanoidins by liquid chromatography-organic carbon detection indicated a preferential removal of high-molecular-weight melanoidins over low weight melanoidins by the coagulation. Further studies should focus on how to improve biodegradability of the treated effluent for it to be reused as dilution water for anaerobic digestion.

Removal of pharmaceuticals in aerated biofilters with manganese feeding.

A tertiary treatment step is required in current wastewater treatment plants to remove trace pollutants and thus to prevent their extensive occurrence in the aquatic environment. In this study, natural MnOx ore and natural zeolite were separately used to pack two lab-scale aerated biofilters, which were operated in approximately 1.5 years for the removal of frequently occurring pharmaceuticals, including carbamazepine (CBZ), diclofenac (DFC), and sulfamethoxazole (SMX), out of synthetic and real secondary effluents. Mn(2+) was added in the feeds to promote the growth of iron/manganese oxidizing bacteria which were recently found to be capable of degrading recalcitrant pollutants. An effective removal (80-90%) of DFC and SMX was observed in both biofilters after adaptation while a significant removal of CBZ was not found. Both biofilters also achieved an effective removal of spiked Mn(2+), but a limited removal of carbon and nitrogen contents. Additionally, MnOx biofilter removed 50% of UV254 from real secondary effluent, indicating a high potential on the removal of aromatic compounds.

Catalysed ozonation for removal of an endocrine-disrupting compound using the O3/Fenton reagents system.

Aqueous solutions of diethyl phthalate (DEP) were oxidized by using ozone combined with Fenton reagents. The effects of operating parameters such as initial pH; initial concentration of DEP, H2O2 and Fe2+; [H2O2]0/[Fe2+]0 ratio and O3 dosage on the degradation rates of DEP were investigated. The results showed that DEP degradation is strongly dependant on the pH; initial concentrations of the phthalate, H2O2 and Fe2+; [H2O2]0/[Fe2+]0 ratio and O3 dosage. The addition of H2O2 and Fe2+ ions was effective to achieve almost 98% degradation of 200 mg L(-1) of DEP in about 40 min using a dose of O3=45 g m(-3) NTP; [H2O2]0=2.5×10(-2) mol L(-1) and [Fe(II)]0=5×10(-3) mol L(-1), as compared to over 60 min by using O3 and Fenton processes applied separately. DEP degradation followed apparent pseudo-first-order kinetics under ozonation, Fenton's reagents oxidation and the combined ozonation/Fenton reagents oxidation process. The overall reaction rates were significantly enhanced in the O3/Fe2+/H2O2 oxidation system, and allows achieving 100% degradation of DEP (100 mg L(-1)) in 30 min of reaction time. The notable decrease in DEP removal rate observed in the presence of a radical scavenger indicates that there was an obvious synergetic effect in the combined ozonation/Fenton reagent process most likely because ozonation could accelerate Fenton reagents to generate hydroxyl radical HO•. Thus, the reaction between DEP and HO• proceeds mainly in the bulk of the aqueous phase. Under optimal conditions, the O3/Fe2+/H2O2 system oxidation was the most effective in DEP removal in water.

Adsorption of trichlorophenol on zeolite and adsorbent regeneration with ozone.

A FAU-type zeolite was studied as an adsorbent to remove 2,4,6-trichlorophenol (TCP), a frequently detected recalcitrant pollutant in water bodies. Both adsorption isotherm and kinetics were studied with TCP concentrations from 10 to 100mg/L. It was observed that TCP was effectively adsorbed onto the zeolite with a high adsorption capacity and a high kinetic rate. Freundlich model and pseudo-second-order kinetics were successfully applied to describe the experimental data. The influence of solution pH was also studied. Furthermore, ozone was applied to regenerate the loaded zeolite. It was found that an effective adsorption of TCP was kept for at least 8 cycles of adsorption and regeneration. The ozonation also increased the BET specific surface of zeolite by over 60% and consequently enhanced the adsorption capacity.

Modelling of integrated anoxic-anaerobic-aerobic treatment for salmon fishery wastewater in an upflow fixed-bed biofilm reactor.

Literature has paid scarce attention to the modelling of the integrated anoxic-anaerobic-aerobic process in upflow fixed-bed biofilm reactors used to treat wastewater. The present study developed a model for industrial salmon fishery wastewater treatment in an integrated anoxic-anaerobic-aerobic upflow fixed-bed biofilm reactor. The model successfully predicted the removal efficiency of both Chemical Oxygen Demand (COD) and nitrogen for two recycle ratios at steady state. The simulation study shows that the COD removal efficiency is not affected by any parameter under the studied conditions, while the nitrogen removal efficiency is affected by the hydraulic retention time (HRT) and the inlet COD concentration, where Total Ammonia Nitrogen (TAN) is the most sensitive variable of the anoxic-anaerobic-aerobic system. The conditions that best obtained removal efficiencies above 70% are: recycle rate between 1 and 2; HRT between 1.4 and 2.2 days and inlet COD concentrations lower than 2500 mg COD L(-1). Analysis of the model's sensitivity indicated that the parameters that exert most influence on the model for the system were micro(max,M), k(h), micro(max,H), eta(NO3-), micro(NOB), K(DO)NOB and D(DO).

Elimination of carbamazepine in a non-sterile fungal bioreactor.

A properly configured bioreactor is in need to transfer the fungal biodegradation of recalcitrant pollutants into real applications. In this study, a novel plate bioreactor was designed to eliminate carbamazepine (CBZ), a widely concerned pharmaceutical, with the white rot fungus Phanerochaete chrysosporium grown on polyether foam under non-sterile conditions. The bioreactor was operated in both sequence batch and continuous modes. It was found that the sufficient supply with nutrients is crucial for an effective elimination of CBZ. Given the conditions, a high elimination of CBZ (60-80%) was achieved. The effective elimination was stable in a continuous operation for a long term (around 100 days). The high elimination of CBZ could also be achieved under real conditions with the effluent from a municipal wastewater treatment plant.

Selective removal of diclofenac from contaminated water using molecularly imprinted polymer microspheres.

A molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using diclofenac (DFC) as a template. Binding characteristics of the MIP were evaluated using equilibrium binding experiments. Compared to the non-imprinted polymer (NIP), the MIP showed an outstanding affinity towards DFC in an aqueous solution with a binding site capacity (Q(max)) of 324.8 mg/g and a dissociation constant (K(d)) of 3.99 mg/L. The feasibility of removing DFC from natural water by the MIP was demonstrated by using river water spiked with DFC. Effects of pH and humic acid on the selectivity and adsorption capacity of MIP were evaluated in detail. MIP had better selectivity and higher adsorption efficiency for DFC as compared to that of powdered activated carbon (PAC). In addition, MIP reusability was demonstrated for at least 12 repeated cycles without significant loss in performance, which is a definite advantage over single-use activated carbon.