A critical review on the pathways of carbamazepine transformation products in oxidative wastewater treatment processes.

Carbamazepine (CBZ) is an anticonvulsant drug, released in domestic and hospital wastewater, and one of the drugs most commonly detected in surface water. Conventional secondary processes do a very poor job of removing it (<25 %), but its concentrations are significantly reduced by polishing oxidation processes. However, there are still many unknowns regarding the transformation products generated and their fate. This review first presents the journey of CBZ and its transformation products (TPs) in wastewater, from human consumption to discharge in water bodies. It then goes on to detail the diversity of mechanisms responsible for CBZ degradation and the generation of multiple TPs, laying the emphasis on the different types of advanced oxidation processes (AOP). 135 TPs were reported and a map describing their formation/degradation pathways was drawn up. This work highlights the wide range of physicochemical properties and toxicity effects of TPs on aquatic organisms and provides information about TPs of interest for future research. Finally, this review concludes on the importance of quantifying TPs and of determining kinetic characteristics to produce more accurate reaction schemes and computer-based fate predictions.

Modeling, simulation and control of biological and chemical P-removal processes for membrane bioreactors (MBRs) from lab to full-scale applications: State of the art.

Phosphorus (P) removal from the domestic wastewater is required to counter the eutrophication in receiving water bodies and is mandated by the regulatory frameworks in several countries with discharge limits within 1-2mgPL-1. Operating at higher sludge retention time (SRT) and higher biomass concentration than the conventional activated sludge process (CASP), membrane bioreactors (MBRs) are able to remove 70-98% phosphorus without addition of coagulant. In full-scale facilities, enhanced biological phosphorus removal (EBPR) is assisted by the addition of metal coagulant to ensure >95% P-removal. MBRs are successfully used for super-large-scale wastewater treatment facilities (capacity >100,000 m3d-1). This paper documents the knowledge of P-removal modeling from lab to full-scale submerged MBRs and assesses the existing mathematical models for P-removal from domestic wastewater. There are still limited studies involving integrated modeling of the MBRs (full/super large-scale), considering the complex interactions among biology, chemical addition, filtration, and fouling. This paper analyses the design configurations and the parameters affecting the biological and chemical P-removal in MBRs to understand the P-removal process sensitivity and their implications for the modeling studies. Furthermore, it thoroughly reviews the applications of bio-kinetic and chemical precipitation models to MBRs for assessing their effectiveness with default stoichiometric and kinetic parameters and the extent to which these parameters have been calibrated/adjusted to simulate the P-removal successfully. It also presents a brief overview and comparison of seven (7) chemical precipitation models, along with a quick comparison of commercially available simulators. In addition to advantages associated with chemical precipitation for P-removal, its role in changing the relative abundance of the microbial community responsible for P-removal and denitrification and the controversial role in fouling mitigation/increase are discussed. Lastly, it encompasses several coagulant dosing control systems and their applications in the pilot to full-scale facilities to save coagulants and optimize the P-removal performance.

Micropollutants removal in tertiary moving bed biofilm reactors (MBBRs): Contribution of the biofilm and suspended biomass.

The performance of tertiary moving bed biofilm reactors (MBBRs) was evaluated in terms of micropollutants (MPs) removal from secondary-treated municipal wastewater. After stepwise establishment of a mature biofilm, monitored by scanning electron and confocal microscopies, abiotic and biotic removals of MPs were deeply studied. Since no MPs reduction was observed by the both photodegradation and volatilization, abiotic removal of MPs was ascribed to the sorption onto the biomass. Target MPs i.e. Naproxen, Diclofenac, 17ß-Estradiol and 4n-Nonylphenol, arranged in the ascending order of hydrophobicity, abiotically declined up to 2.8%, 4%, 9.5% and 15%, respectively. MPs sorption onto the suspended biomass was found around two times more than the biofilm, in line with MPs' higher sorption kinetic constants (ksor) found for the suspended biomass. When comparing abiotic and biotic aspects, we found that biotic removal outperformed its counterpart for all compounds as Diclofenac, Naproxen, 17ß-Estradiol and 4n-Nonylphenol were biodegraded by 72.8, 80.6, 84.7 and 84.4%, respectively. The effect of the changes in organic loading rates (OLRs) was investigated on the pseudo-first order degradation constants (kbiol), revealing the dominant biodegradation mechanism of co-metabolism for the removal of Diclofenac, Naproxen, and 4n-Nonylphenol, while 17ß-Estradiol obeyed the biodegradation mechanism of competitive inhibition. Biotic removals and kbiol values of all MPs were also seen higher in the biofilm as compared to the suspended biomass. To draw a conclusion, a quite high removal of recalcitrant MPs is achievable in tertiary MBBRs, making them a promising technology that supports both pathways of co-metabolism and competitive inhibition, next to the abiotic attenuation of MPs.

Optimization of pressurized liquid extraction using a multivariate chemometric approach for the determination of anticancer drugs in sludge by ultra high performance liquid chromatography-tandem mass spectrometry.

The present paper describes an analytical method for the determination of 2 widely administered anticancer drugs, ifosfamide and cyclophosphamide, contained in sewage sludge. The method relies on the extraction from the solid matrix by pressurized liquid extraction, sample purification by solid-phase extraction and analysis by ultra high performance liquid chromatography coupled with tandem mass spectrometry. The different parameters affecting the extraction efficiency were optimized using an experimental design. Solvent nature was the most decisive factor for the extraction but interactions between some parameters also appeared very influent. The method was applied to seven different types of sludge for validation. The performances of the analytical method displayed high variability between sludges with limits of detection spanning more than one order of magnitude and confirming the relevance of multi-sample validation. Matrix effect has been determined as the most limiting analytical step for quantification with different extent depending on analyte and sludge nature. For each analyte, the use of deuterated standard spiked at the very beginning ensured the complete compensation of losses regardless of the sample nature. The suitability of the method between freshly spiked and aged samples has also been verified. The optimized method was applied to different sludge samples to determine the environmental levels of anticancer drugs. The compounds were detected in some samples reaching 42.5µg/kgDM in ifosfamide for the most contaminated sample.

Cytotoxicity micropollutant removal in a crossflow membrane bioreactor.

The application of membrane bioreactor (MBR) technology was investigated with the aim of evaluating its potential for cytostatic drug and cytotoxicity bioremoval. The toxicity removal was assessed from biomarker test. CP removal of up to 80% was achieved under the operating conditions studied (HRT of 48 h and a SRT of 50 days). The increase of TMP was associated with an increase of supernatant toxicity as if fouling led to retention of the toxicity. Peaks of supernatant cytotoxicity were correlated with peaks in supernatant humic acid contents. It may suggest that molecules with a toxic effect may be adsorbed or entrapped in humic acids substances. Our study then points out that advances in wastewater treatment using an MBR can provide a suitable process for lowering CP concentrations before discharge into the aqueous environment. However, a tertiary treatment is necessary if complete elimination of toxicity is targeted.

Effect of cytostatic drugs on microbial behaviour in membrane bioreactor system.

The aim of this work is to evaluate the influence of cyclophosphamide and its principal metabolites (CPs) on microbial behaviour in a membrane bioreactor system. Two laboratory-scale membrane bioreactors (MBR) were run in parallel with a sludge retention time of 70 days (one with the cytostatic drugs, MBR-CPs, the second without, MBR-control). The microbial activity was measured by respirometric analysis. The endogenous and exogenous respirations of heterotrophic micro-organisms were evaluated. Micro-organisms exposed to CPs showed higher endogenous respiration rates and lower exogenous respiration rates than micro-organisms present in MBR-control. The effects were observed several days after adding the cocktail. Reduced sludge production was observed in MBR-CPs compared to MBR-control. This reduction of sludge production and the increase in the endogenous respiration rate in relation to MBR-control suggest that the chemical stress caused by CPs led to a diversion of carbon and/or energy from growth to adaptive responses and protection. In addition, the inhibitory effect on the assimilation of exogenous substrate (reduced exogenous respiration rate) suggests an inhibition of catabolism and anabolism despite the low CPs concentration studied (microg/L). However, this inhibitory effect can be offset by the biomass still active under low ratio (substrate/biomass) conditions in the bioreactor (due to complete retention of biomass and high sludge age), which helped to maintain high overall performance in the removal of conventional pollution.

Decolorization of synthetic melanoidins-containing wastewater by a bacterial consortium.

The presence of melanoidins in molasses wastewater leads to water pollution both due to its dark brown color and its COD contents. In this study, a bacterial consortium isolated from waterfall sediment was tested for its decolorization. The identification of culturable bacteria by 16S rDNA based approach showed that the consortium composed of Klebsiella oxytoca, Serratia mercescens, Citrobacter sp. and unknown bacterium. In the context of academic study, prevention on the difficulties of providing effluent as well as its variations in compositions, several synthetic media prepared with respect to color and COD contents based on analysis of molasses wastewater, i.e., Viandox sauce (13.5% v/v), caramel (30% w/v), beet molasses wastewater (41.5% v/v) and sugarcane molasses wastewater (20% v/v) were used for decolorization using consortium with color removal 9.5, 1.13, 8.02 and 17.5%, respectively, within 2 days. However, Viandox sauce was retained for further study. The effect of initial pH and Viandox concentration on decolorization and growth of bacterial consortium were further determined. The highest decolorization of 18.3% was achieved at pH 4 after 2 day of incubation. Experiments on fresh or used medium and used or fresh bacterial cells, led to conclusion that the limitation of decolorization was due to nutritional deficiency. The effect of aeration on decolorization was also carried out in 2 L laboratory-scale suspended cell bioreactor. The maximum decolorization was 19.3% with aeration at KLa=2.5836 h(-1) (0.1 vvm).

Oil removal from water by sorption on hydrophobic cotton fibers. 2. Study of sorption properties in dynamic mode.

The recovery of oil from an oil-in-water emulsion, during a flow through a bed of cotton rendered hydrophobic by acylation of cellulose was defined by sorption and coalescence phenomena. During percolation, the column "hold-up" (difference between injected and rejected oil) became constant at the equilibrium volume, i.e., as soon as the instant oil concentration in the effluent (C) was equal to the oil concentration in the initial emulsion (C0). This equilibrium permitted the measurement of the cotton sorption capacity (SC), which increased with C0 up to the cotton saturation. The oil-water separation improved at a lower temperature, lower flow, a deeper medium, and larger oil drops. The system was modeled as a piston flow-through in order to generalize the results.