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.

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.

Sartan blood pressure regulators in classical and biofilm wastewater treatment - Concentrations and metabolism.

Sartans are a group of pharmaceuticals widely used to regulate blood pressure. Their concentration levels were monitored in 80 wastewater treatment plants (WWTP) in the Baltic Sea Region, reached from limit of detection up to 6 µg/L. The concentrations were significantly different in different countries, but consistent within the respective country. The degradation of sartans (losartan, valsartan, irbesartan) in moving bed biofilm reactors (MBBRs) that utilize biofilms grown on mobile carriers to treat wastewater was investigated for the first time, and compared with the degradation in a conventional activated sludge (CAS) treatment plant. The results showed the formation of six microbial transformation products (TPs) of losartan, four of valsartan, and four of irbesartan in biological wastewater treatment. Four of these metabolites have not been described in the literature before. Chemical structures were suggested and selected TPs were verified and quantified depending on availability of true standards. Valsartan acid was a common TP of losartan, valsartan, and irbesartan. Losartan and irbesartan also shared one TP: losartan/irbesartan TP335. Based on the mass balance analysis, losartan carboxylic acid is the main TP of losartan, and valsartan acid is the main TP of valsartan during the biotransformation process. For irbesartan, TP447 is likely to be the main TP, as its peak areas were two orders of magnitude higher than those of all the other detected TPs of this compound. The effects of adapting biofilms to different biological oxygen demand (BOD) loading on the degradation of sartans as well as the formation of their TPs were investigated. Compared to feeding a poor substrate (pure effluent wastewater from a CAS), feeding with richer substrate (1/3 raw and 2/3 effluent wastewater) promoted the metabolism of most compounds (co-metabolization). However, the addition of raw wastewater inhibited some metabolic pathways of other compounds, such as from losartan/irbesartan to TP335 (competitive inhibition). The formation of irbesartan TP447 did not change with or without raw wastewater. Finally, the sartans and their TPs were investigated in a full-scale CAS wastewater treatment plant (WWTP). The removal of losartan, valsartan, and irbesartan ranged from 3.0 % to 72% and some of the transformation products (TPs) from human metabolism were also removed in the WWTP. However, some of the sartan TPs, i.e., valsartan acid, losartan carboxylic acid, irbesartan TP443 and losartan TP453, were formed in the WWTP. Relative high amounts of especially losartan carboxylic acid, which was detected with concentrations up to 2.27 µg/L were found in the effluent.

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.

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.