Pathways of nitrobenzene degradation in horizontal subsurface flow constructed wetlands: Effect of intermittent aeration and glucose addition.

Intermittent aeration and addition of glucose were applied to horizontal subsurface flow constructed wetlands in order to investigate the effect on pathways of nitrobenzene (NB) degradation and interactions with microbial nitrogen and sulphur transformations. The experiment was carried out in three phases A, B and C consisting of different NB loading and glucose dosing. For each phase, the effect of aeration was assessed by intermittently aerating one wetland and leaving one unaerated. Regardless of whether or not the wetland was aerated, at an influent NB concentration of 140 mg/L, both wetlands significantly reduced NB to less than 2 mg/L, a reduction efficiency of 98%. However, once the influent NB concentration was increased to 280 mg/L, the aerated wetland had a higher removal performance 82% compared to that of the unaerated wetland 71%. Addition of glucose further intensified the NB removal to 95% in the aerated wetlands and 92% in the unaerated. Aeration of wetlands enhanced NB degradation, but also resulted in higher NB volatilization of 6 mg m(-2) d(-1). The detected high concentration of sulphide 20-60 mg/L in the unaerated wetland gave a strong indication that NB may act as an electron donor to sulphate-reducing bacteria, but this should be further investigated. Aeration positively improved NB removal in constructed wetlands, but resulted in higher NB volatilization. Glucose addition induced co-metabolism to enhance NB degradation.

Microbial density and diversity in constructed wetland systems and the relation to pollutant removal efficiency.

Microbes are believed to be at the core of the wastewater treatment processes in constructed wetlands (CWs). The aim of this study was to assess the microbial biomass carbon (MBC) and Shannon's diversity index (SDI) in the substrate of CWs planted with Phragmites australis, Hymenocallis littoralis, Canna indica and Cyperus flabelliformis, and to relate MBC and SDI to the pollutant removal in the systems. Significant higher MBC was observed in CWs with H. littoralis and C. indica than in CWs with P. australis, and the MBC differed with season and substrate depth. The microbial community in the wetlands included four phyla: Cyanobacteria, Proteobacteria, Chloroflexi, and Acidobacteria, with a more diverse community structure in wetlands with C. flabelliformis. The MBC in the substrate and the SDI of the 15-20 cm depth correlated with the removal of biochemical oxygen demand, NH4-N and NO3-N. Our results indicate that substrate SDI and MBC can both be regarded as bioindicators of the pollutant removal ability in CWs.

Stability of chlorophenols and their acetylated derivatives in water: sample storage procedures.

The determination of chlorophenols (CPs) in water samples is a subject of increasing interest. Reduction of sample storage space and the stability of CPs when present at very low levels are still problems that deserve research. The stability of CPs at ng/L levels at different temperatures and in the presence or absence of sodium carbonate and acetic anhydride was studied for up to 39 days. Stable and reproducible CP concentrations for about a month of storage in both river and wastewater were achieved in two storage conditions as follows: at -18 degrees C with addition of 10% sodium chloride; and at 4 degrees C with addition of both 10% sodium chloride and 10 mglmL sodium carbonate. These sample treatments are good alternatives to the immobilization of CPs on SPE cartridges in terms of both analyte stability and saving of storage space.

Cyanobacterial blooms in surface waters - Nature-based solutions, cyanotoxins and their biotransformation products.

Cyanobacterial blooms are expected to become more frequent and severe in surface water reservoirs due to climate change and ecosystem degradation. It is an emerging challenge that especially countries relying on surface water supplies will face. Nature-based solutions (NBS) like constructed wetlands and biofilters can be used for cyanotoxin remediation. Both technologies are reviewed and critically assessed for different types of water resources. The available information on cyanotoxins (bio)transformation products (TPs) is reviewed to point out the potential research gaps and to disclose the most reliable enzymatic degradation pathways. Knowledge gaps were found, such as information on the performance of the revised NBS in pilot and full scales, the removal processes covering different cyanotoxins (besides the most widely studied microcystin-LR), and the difficulties for real-world implementation of technologies proposed in the literature. Also, most studies focus on bacterial degradation processes while fungi have been completely overlooked. This review also presents an up-to-date overview of the transformation of cyanotoxins, where degradation product data was compiled in a unified library of 22 metabolites for microcystins (MCs), 7 for cylindrospermopsin (CYN) and 10 for nodularin (NOD), most of them reported only in a single study. Major gaps are the lack of environmentally relevant studies with TPs in pilot and full- scale treatment systems, information on TP's toxicity, as well as limited knowledge of environmentally relevant degradation pathways. NBS have the potential to mitigate cyanotoxins in recreational and irrigation waters, enabling the water-energy-food nexus and avoiding the degradability of the ecosystems.

Eat seldom is better than eat frequently: Pharmaceuticals degradation kinetics, enantiomeric profiling and microorganisms in moving bed biofilm reactors are affected by feast famine cycle times.

Feast-famine (FF) regimes improved the removal of recalcitrant pharmaceuticals in moving bed biofilm reactors (MBBRs), but the optimal FF cycle remained unresolved. The effects of FF cycle time on the removal of bulk substrates (organic carbon and nitrogen) and trace pharmaceuticals by MBBR are systematically evaluated in this study. The feast to famine ratio was fixed to 1:2 to keep the same loading rate, but the time for the FF cycles varied from 18 h to 288 h. The MBBR adapted to the longest FF cycle time (288 h equaling 48 × HRT) resulted in significantly higher degradation rates (up to +183%) for 12 out of 28 pharmaceuticals than a continuously fed (non-FF) reactor. However, other FF cycle times (18, 36, 72 and 144 h) only showed a significant up-regulation for 2-3 pharmaceuticals compared to the non-FF reactor. Enantioselective degradation of metoprolol and propranolol occurred in the second phase of a two phase degradation, which was different for the longer FF cycle time. N-oxidation and N-demethylation pathways of tramadol and venlafaxine differed across the FF cycle time suggestin the FF cycle time varied the predominant transformation pathways of pharmaceuticals. The abundance of bacteria in the biofilms varied considerably between different FF cycle times, which possibly caused the biofilm to remove more recalcitrant bulk organic C and pharmaceuticals under long cycle times.

Fungal removal of cyanotoxins in constructed wetlands: The forgotten degraders.

Harmful cyanobacterial blooms have increased globally, releasing hazardous cyanotoxins that threaten the safety of water resources. Constructed wetlands (CWs) are a nature-based and low-cost solution to purify and remove cyanotoxins from water. However, bio-mechanistic understanding of the biotransformation processes expected to drive cyanotoxin removal in such systems is poor, and primarily focused on bacteria. Thus, the present study aimed at exploring the fungal contribution to microcystin-LR and cylindrospermopsin biodegradation in CWs. Based on CW mesocosms, two experimental approaches were taken: a) amplicon sequencing studies were conducted to investigate the involvement of the fungal community; and b) CW fungal isolates were tested for their microcystin-LR and cylindrospermopsin degradation capabilities. The data uncovered effects of seasonality (spring or summer), cyanotoxin exposure, vegetation (unplanted, Juncus effusus or Phragmites australis) and substratum (sand or gravel) on the fungal community structure. Additionally, the arbuscular mycorrhizal fungus Rhizophagus and the endophyte Myrmecridium showed positive correlations with cyanotoxin removal. Fungal isolates revealed microcystin-LR-removal potentials of approximately 25 % in in vitro biodegradation experiments, while the extracellular chemical fingerprint of the cultures suggested a potential intracellular metabolization. The results from this study may help us understand the fungal contribution to cyanotoxin removal, as well as their ecology in CWs.

Constructed wetland mesocosms improve the biodegradation of microcystin-LR and cylindrospermopsin by indigenous bacterial consortia.

Cyanobacterial blooms releasing harmful cyanotoxins, such as microcystin (MC) and cylindrospermopsin (CYN), are prominent threats to human and animal health. Constructed wetlands (CW) may be a nature-based solution for bioremediation of lake surface water containing cyanotoxins, due to its low-cost requirement of infrastructure and environmentally friendly operation. There is recent evidence that microcystin-LR (MC-LR) can efficiently be removed in CW microcosms where CYN degradation in CW is unknown. Likewise, the mechanistic background regarding cyanotoxins transformation in CW is not yet elucidated. In the present study, the objective was to compare MC-LR and CYN degradation efficiencies by two similar microbial communities obtained from CW mesocosms, by two different experiments setup: 1) in vitro batch experiment in serum bottles with an introduced CW community, and 2) degradation in CW mesocosms. In experiment 1) MC-LR and CYN were spiked at 100 µg L-1 and in experiment 2) 200 µg L-1 were spiked. Results showed that MC-LR was degraded to ≤1 µg L-1 within seven days in both experiments. However, with a markedly higher degradation rate constant in the CW mesocosms (0.18 day-1 and 0.75 day-1, respectively). No CYN removal was detected in the in vitro incubations, whereas around 50 % of the spiked CYN was removed in the CW mesocosms. The microbial community responded markedly to the cyanotoxin treatment, with the most prominent increase of bacteria affiliated with Methylophilaceae (order: Methylophilales, phylum: Proteobacteria). The results strongly indicate that CWs can develop an active microbial community capable of efficient removal of MC-LR and CYN. However, the CW operational conditions need to be optimized to achieve a full CYN degradation. To the best of our knowledge, this study is the first to report the ability of CW mesocosms to degrade CYN.

Potential of nature-based solutions to reduce antibiotics, antimicrobial resistance, and pathogens in aquatic ecosystems. a critical review.

This comprehensive scientific review evaluates the effectiveness of nature-based solutions (NBS) in reducing antibiotics (ABs), combating antimicrobial resistance (AMR), and controlling pathogens in various aquatic environments at different river catchment levels. It covers conventional and innovative treatment wetland configurations for wastewater treatment to reduce pollutant discharge into the aquatic ecosystems as well as exploring how river restoration and saltmarshes can enhance pollutant removal. Through the analysis of experimental studies and case examples, the review shows NBS's potential for providing sustainable and cost-effective solutions to improve the health of aquatic ecosystems. It also evaluates the use of diagnostic indicators to predict NBS effectiveness in removing specific pollutants such as ABs and AMR. The review concludes that NBS are feasible for addressing the new challenges stemming from human activities such as the presence of ABs, AMR and pathogens, contributing to a better understanding of NBS, highlighting success stories, addressing knowledge gaps, and providing recommendations for future research and implementation.

Mechanistic studies on the effect of easy degradable carbon on pharmaceuticals removal in intermittently fed moving bed biofilm reactors.

This study was conducted to provide for the first time systematic data on how intermittent feeding with carbon (ethanol) affects the kinetics of pharmaceuticals degradation in a moving bed biofilm reactor (MBBR). The relationship between the degradation rate constants (K) of 36 pharmaceuticals and the length of famine was tested with 12 different feast-famine ratios: For 17 pharmaceuticals, intermittent feeding increased K with a factor of 3-17, while for six other pharmaceuticals, it decreased K. Concerning intermittent loading, three dependencies were detected: 1) for some compounds (e.g., valsartan, ibuprofen, iohexol), the K decreased linearly with carbon loading, 2) for three compounds (2 sulfonamides and benzotriazole) K increased linearly with carbon loading 3) for most compounds (e.g., beta blockers, macrocyclic antibiotics, candesartan, citalopram, clindamycin, gabapentin) K had a maximum around 6 d famine (with 2 d feast). Optimizing processes on MBBRs need therefore be conducted based on a prioritization of compounds.

Simultaneous determination of several veterinary pharmaceuticals in effluents from urban, livestock and slaughterhouse wastewater treatment plants using a simple chromatographic method.

Minocycline, oxytetracycline, tetracycline, enrofloxacin and ceftiofur, commonly used veterinary pharmaceuticals, were searched in four urban, two livestock and two slaughterhouse effluents from wastewater treatment plants (WWTPs) in the north of Portugal. A simple method that includes solid-phase extraction followed with analysis by high-performance liquid chromatography with diode array detector was established and applied to the simultaneous determination of the five pharmaceuticals in WWTP effluents. This method, which is expeditious, inexpensive and available in most laboratories, showed to be useful for screening for problematic levels of drugs in WWTP effluents. It is known that several livestock and slaughterhouse effluents (pre-treated or treated) are discharged to the urban network before discharge into the environment. The presence of these drugs in such effluents can constitute a significant environmental problem that should be addressed, by the monitoring of these drugs and by implementation of methodologies that contribute to their decrease/elimination from wastewaters. Minocycline (≤6 µg L(-1)), oxytetracycline (≤7 µg L(-1)), tetracycline (≤6 µg L(-1)) and enrofloxacin (<2 µg L(-1)) could be detected and/or quantified in three urban effluents. Detectable levels of enrofloxacin (<2 µg L(-1)) and quantifiable levels of tetracycline (≤15 µg L(-1)) were found in the slaughterhouse effluents.

Effects of substrate loading on co-metabolic transformation pathways and removal rates of pharmaceuticals in biofilm reactors.

This study focused on the effects of substrate (raw wastewater) on the biological removal of 20 pharmaceuticals in moving bed biofilm reactors. This is the first study discriminating experimentally between effects of adaptation (45 d) and stimulation (100 h) on the removal of micropollutants. The results presented in this paper show: i) Tramadol and venlafaxine are subject to microbial N-oxidation (besides the known demethylation). ii) Changes in substrate loading, changed the preferential degradation pathways, e.g., from N-oxidation (under starvation) to N-demethylation of both model compounds: tramadol and venlafaxine, during adaptation and stimulation to high substrate supply. iii) In starving biofilms, the effects of stimulation on removal rates are minor (-100 to +150 %) in comparison to those caused by adaptation (-100 to +700 %). iv) Adaptation to high loadings resulted in increased removal rates (up to 700 % in selected cases) v) Adaptation to high loadings followed by high loading of stimulation, resulted in the highest increase of removal rates (+49 % to +1800 %) for hard-to-degrade compounds (e.g., diclofenac). All in all, this study shows that the efficiency of biofilm reactors is heavily dependent on their adaptation to substrate.

A headspace SPME-GC-ECD method suitable for determination of chlorophenols in water samples.

A headspace solid phase microextraction coupled to gas chromatography with electron capture detector (HS-SPME-GC-ECD) method was optimized for the determination of seven chlorophenols (CPs) with different levels of chlorination. This is the first time that HS-SPME-GC-ECD with acetylation of the analytes is used for the simultaneous determination of CPs in water samples. The influence of fibre type, derivatization conditions, salt addition, temperature and time of extraction and temperature of desorption was checked. Possible sources of contamination and analyte losses were considered. The best results were obtained with the polydimethylsiloxane/divinylbenzene fibre, derivatization by acetylation using 100 µL of acetic anhydride and 0.1 g of anhydrous sodium carbonate per 10 mL of sample, salt addition of 100 g L(-1) sodium chloride, extraction at 70 °C for 60 min and desorption in the GC injector at 260 °C for 6 min. The limits of detection (LOD) for monochlorophenols were 12 and 122 ng L(-1) for 2-chlorophenol and 4-chlorophenol, respectively. For polychlorinated CPs, the LODs were lower than 6 ng L(-1), values similar to the existing methods that use SPME with derivatization for CPs determination in water samples. The method is suitable for the determination of CPs in most environmental aqueous samples. Repeatability and reproducibility were less than 16.8% and 11.7%, respectively. The optimized method was successfully applied for the analysis of waters with complex matrices such as river and estuarine water samples.

Identification of more than 100 new compounds in the wastewater: Fate of polyethylene/polypropylene oxide copolymers and their metabolites in the aquatic environment.

100 ethylene oxide (EO)/propylene oxide (PO) copolymer precursor and metabolites were detected in wastewater effluents. The homopolymers of EO and PO as well as the EO/PO copolymers are widely used as surfactants, e.g., for the production of cosmetics, pharmaceuticals and lubricants. Concomitantly, these compounds are discharged into the wastewater and the environmental fate of the PO homopolymers, also called polypropylene glycols (PPGs), and EO/PO copolymers is mostly unknown. In the present study, we identified hitherto unknown copolymer EO/PO homologous series and their metabolites in wastewater effluent. The identified compounds occur in homologous series and consist of PPGs and EO/PO copolymers, and their carbonylated, carboxylated and dicarboxylated metabolites. MBBR lab incubations of PPGs and EO/PO copolymers showed the successive degradation by cleavage of individual PO and EO groups, with high removal (>90%) in the initial 8 h for most of the copolymers. Carbonylated and carboxylated metabolites were degraded within 40 h. EO/PO copolymers with a higher number of EO and PO units showed a higher removal in MBBR and conventional activated sludge wastewater treatment plants. Polymers with lower molecular weight were initially formed by degradation of the EO/PO polymers. The mono-carboxylated metabolites were also detected in surface waters. Overall, our results provide new knowledge about degradation pathways of PO containing compounds and show the hitherto unnoticed occurrence of EO/PO copolymers and metabolites in the water cycle.

Concentration dependent degradation of pharmaceuticals in WWTP effluent by biofilm reactors.

Conventional wastewater treatment lacks the ability to remove many pharmaceuticals. This is leading to emissions to the natural aquatic environment, where these compounds pose a risk to the aquatic organisms. An advanced wastewater treatment technique that has shown promising results is Moving Bed Biofilm Reactors (MBBR). Initial degradation velocity and degradation rate constants of the pharmaceuticals are important parameters for designing an optimal MBBR system; however, the degradation efficiency varies across studies and one of the most plausible causes might be initial concentration. Thus, to verify the effect of initial concentration, the degradation of a mixture of 18 pharmaceuticals at different initial concentrations was studied. For this study MBBR's with very low BOD loading were used as they were conditioned with effluent water. The experiment was set up as a MBBR batch incubation, using effluent wastewater as medium, spiked with the 18 pharmaceuticals in seven different concentration levels (approximately 0-300 µg L-1). The degradation of 14 out of 18 pharmaceuticals was concentration-dependent. The initial degradation velocity of the pharmaceuticals was either proportional to the initial concentration or was following a typical Michaelis-Menten kinetic. The degradation velocity of one compound, i.e., sulfamethizole might have been inhibited at high concentrations. The degradation rate constants from single first-order fittings (KSFO) for some compounds deviated from the expected behavior at low concentrations (below 10 µg L-1). This is suggested to be caused by simplicity of the Michaelis-Menten model, not taking possible occurrence of co-metabolism and mass-transfer limitations into account at low concentrations. This study underlines the fact that K values cannot be interpreted without paying attention to the tested concentration level. Furthermore, it shows that the used MBBRs was able to handle high concentrations of pharmaceuticals, and that the most efficient removal occurs at concentrations above 100 µg L-1.

Leaching of herbicidal residues from gravel surfaces - A lysimeter-based study comparing gravels with agricultural topsoil.

Evidence from the past shows that pesticide use in populated areas may impact groundwater quality. The approval of herbicides such as diflufenican and glyphosate for use on paved and unpaved gravel surfaces in the European Union is based on their behaviour and fate in agricultural soils. However, this might be very different from their fate in gravel surfaces. We therefore conducted an outdoor study with 21 small lysimeters containing different gravel types and a sandy arable topsoil as control. The lysimeters were sprayed with a commercial product for gardening, containing diflufenican and glyphosate. The concentrations of the herbicides and their relevant degradation products in the outlet was followed for 19 months. Diflufenican, glyphosate and AMPA did not leach from any of the lysimeters. However, one diflufenican degradation product (AE-0) leached from two of the gravel types for more than a year and a second degradation product (AE-B) leached from all gravels for up to one year. Concentrations in the leachate peaked at 0.5-3 µg/L, with highest concentrations over the longest periods observed with rock chippings on top of the gravel. We conclude, that the different properties of gravel compared to those of agricultural soils may lead to very different herbicide leaching patterns but also that the leaching depends highly on the type of gravel and type of herbicide.

Hydrothermal liquefaction of sewage sludge; energy considerations and fate of micropollutants during pilot scale processing.

The beneficial use of sewage sludge for valorization of carbon and nutrients is of increasing interest while micropollutants in sludge are of concern to the environment and human health. This study investigates the hydrothermal liquefaction (HTL) of sewage sludge in a continuous flow pilot scale reactor at conditions expected to reflect future industrial installations. The processing is evaluated in terms of energy efficiency, bio-crude yields and quality. The raw sludge and post-HTL process water and solid residues were analyzed extensively for micropollutants via HPLC-MS/MS for target pharmaceuticals including antibiotics, blood pressure medicine, antidepressants, analgesics, x-ray contrast media, angiotensin II receptor blockers, immunosuppressant drugs and biocides including triazines, triazoles, carbamates, a carboxamide, an organophosphate and a cationic surfactant. The results show that a positive energy return on investment was achieved for all three HTL processing temperatures of 300, 325 and 350 °C with the most beneficial temperature identified as 325 °C. The analysis of the HTL by-products, process water and solids, indicates that HTL is indeed a suitable technology for the destruction of micropollutants. However, due to the large matrix effect of the HTL process water it can only be stated with certainty that 9 out of 30 pharmaceuticals and 5 out of 7 biocides products were destroyed successfully (over 98% removal). One compound, the antidepressant citalopram, was shown to be moderately recalcitrant at 300 °C with 87% removal and was only destroyed at temperatures ≥325 °C (>99% removal). Overall, the results suggest that HTL is a suitable technology for energy efficient and value added sewage sludge treatment enabling destruction of micropollutants.

A comparison of the fate of diflufenican in agricultural sandy soil and gravel used in urban areas.

Diflufenican is used in both agricultural and urban areas to control weeds. However, in Europe pesticides are regulated using agricultural soil data only. Urban soils where the top layer is replaced by gravel (e.g. driveways, outdoor tiled areas) can evidently differ from agricultural soils in many biotic and physical properties. In the present study, we compared the degradation, mineralization, sorption and aging of diflufenican between an agricultural sandy soil to a gravel used in urban areas. Both diflufenican and its two main aerobic metabolites were investigated. Diflufenican and the metabolites degraded slower in gravel than in agricultural soil. One of the metabolites, 2-[3-(Trifluoromethyl)phenoxy]nicotinic acid (AE B107137 as identified by EFSA; further abbreviated as AE-B), was formed from the incubation of diflufenican in both soil and gravel, however, showing different formation patterns in the two materials: No accumulation of AE-B was determined in the soil, whereas in gravel, an accumulation of AE-B was determined over the full study period of 150 days. After 150 days, approximately 10% of the applied diflufenican was mineralised in the soil (cumulative), while it was not mineralised in the gravel. Diflufenican showed much stronger sorption to the soil than to the gravel, while the sorption of the metabolites was weaker than diflufenican in both soil and gravel. Within the experimental period, the influence of aging on the fate of diflufenican in soil and gravel is limited (<0.9 and <1.4%, respectively) when compared to the amount of compound still present in the soil. Overall, the results imply shortcomings in the risk assessment procedures requested for the registration of pesticides for urban areas.

Butyltin levels in several Portuguese coastal areas.

This work aimed to report present levels (2007-2008 sampling) of tri- (TBT), di- (DBT), and monobutyltin (MBT) in surface sediments from 11 Portuguese coastal sites and discuss the evolution of BTs contamination in the last two decades. All the samples revealed quantifiable values of TBT, DBT, and MBT with total butyltin concentrations between 1 and 565 ng/g (of Sn in dry sediment). Maximum level of TBT, 66 ng/g, was observed in Sado estuary, at Lisnave site, in the proximity of a big shipyard. MBT decreased site by site by the same order as DBT and TBT did, but its concentrations were much higher in many cases, denoting that TBT contamination was much higher in the past. A comparison with the available previous data confirmed a marked decrease of TBT contamination all over the last years, indicating that the main sources of TBT in Portuguese coastwise stopped effectively.

Dose-dependent effects of acetate on the biodegradation of pharmaceuticals in moving bed biofilm reactors.

Moving bed biofilm reactors (MBBR) are promising as a post-treatment for removing pharmaceuticals from wastewater. However, the effect of easily degradable carbon sources on the degradation of pharmaceuticals is unclear. This study shows the influence of acetate on the degradation of 26 pharmaceuticals in an MBBR was dose- and compound-dependent: while the degradation of venlafaxine, tramadol and ciprofloxacin was promoted (increase of reaction rate constant (k) by 133%, 212%, 55%) by acetate, its presence caused negative effects on the removal of ibuprofen, citalopram and diclofenac (decrease of k by 76%, 57%, 44%). The deconjugation of acetyl-sulfadiazine was clearly slowed down (decrease of k by 75%) by the dosed acetate, probably due to feedback inhibition by abundant acetate. 17 out of 25 tested compounds were found to be independent of the acetate dosage, which suggested dosing acetate induced minor effects on most of pharmaceuticals' removal. Enrichment of S- or first eluted enantiomer of 4 ß-blockers and the metabolite metoprolol acid was observed. Both non-enantioselective (rapid at elevated compound concentration) and enantioselective enzymes (slower and predominant at lower compound concentration) played a part in the biodegradation. High doses of acetate slowed down the enantiomeric enrichment of atenolol, metoprolol, propranolol and metoprolol acid, which demonstrated that the acetate is able to up- or down-regulate enzymes involved in the enantioselective degradation of ß-blockers and thus reveals a complex co-metabolism relationship between transformation pathways of pharmaceuticals and carbon source.

Enhanced removal of pharmaceuticals in a biofilter: Effects of manipulating co-degradation by carbon feeding.

Biofilm reactors are a promising biotechnology to eliminate pharmaceuticals from wastewater during tertiary treatment or in water works for drinking water production. This study aimed at investigating the effects of pulsed carbon feeding for promoting the co-degradation of indigenous pharmaceuticals from pre-treated wastewater in a fixed-bed porous biofilm reactor (slow sand filter). The addition of acetate (carbon source) resulted in three different enhancement/limitation effects, which were compound dependent: 1) atenolol and iohexol experienced enhanced co-degradation followed by constant (acetate independent) degradation; 2) metoprolol, iomeprol, diclofenac, propranolol and sulfamethizole co-degradation dependent on aerobic turnover, but inhibited at higher acetate concentrations (60-300 mg C/L); 3) sulfadiazine, sulfamethoxazole and trimethoprim were removed independently of oxygen and acetate concentration. Carbamazepine, ditriazoic acid, iopromide; tramadol and venlavaxine were not removed at any acetate dosage. Biofilm reactors can be employed for polishing treated wastewater, and the addition of a primary carbon source can enhance the performance of the bioreactor.