Effects of dissolved organic matter and nitrification on biodegradation of pharmaceuticals in aerobic enrichment cultures

Natural dissolved organic matter (DOM) and nitrification can play an important role in biodegradation of pharmaceutically active compounds (PhACs) in aerobic zones of constructed wetlands (CWs). This study used an enrichment culture originating from CW sediment to study the effect of DOM and nitrification on aerobic biodegradation of seven PhACs. The enriched culture degraded caffeine (CAF), metoprolol (MET), naproxen (NAP), and ibuprofen (IBP) with a consistent biodegradability order of CAF > MET > NAP > IBP. Biodegradation of propranolol, carbamazepine, and diclofenac was insignificant (<15%). CAF biodegradation was inhibited by the easily biodegradable DOM. Conversely, DOM enhanced biodegradation of MET, NAP, and IBP, potentially by contributing more biomass capable of degrading PhACs. Nitrification enhanced biodegradation of NAP and IBP and mineralization of the PhAC mixture as well as less biodegradable DOM, which may result from co-metabolism of ammonia oxidizing bacteria or enhanced heterotrophic microbial activity under nitrification. MET biodegradation was inhibited in the presence of nitrification. DOM and nitrification effects on PhAC biodegradation in CWs gained from this study can be used in strategies to improve CW operation, namely: designing hydraulic retention times based on the biodegradability order of specific PhACs; applying DOM amendment; and introducing consistent ammonium streams to increase removal of PhACs of interest

Application of manganese oxides under anoxic conditions to remove diclofenac from water

This study focuses on the potential of applying manganese oxides (MnO2) under anoxic conditions (absence of oxygen) to remove diclofenac (DFC). By investigating parameters that are important for application, including temperature, MnO2: DFC molar ratio, and co-solutes, the DFC removal potential is evaluated in terms of efficiency and observed initial kinetics (kobs,init). Four commonly-used kinetic models are compared in this study and the best fitting one is employed. Overall, DFC removal and kobs,init both increase upon changing temperature from 10 to 30°C and both decrease after further increasing temperature to 40°C. Increasing the MnO2: DFC molar ratio improves degradation, as this provides more reactive surface sites for DFC conversions. However, DFC removal does not further increase when increasing the MnO2:DFC from 2200:1 to 8900:1. The presence of metal ions inhibits DFC removal, possibly because the ions adsorb onto the reactive sites at the MnO2 surface and compete with DFC. Phosphate has a diverse effect on DFC degradation: low concentrations inhibit and high concentrations promote removal. The presence of humic acids significantly promotes diclofenac removal. These findings are a first step towards further developing pharmaceutical removal technology using MnO2 under anoxic conditions.</p

Pharmaceutical biodegradation under three anaerobic redox conditions evaluated by chemical and toxicological analyses

Biodegradation of pharmaceutically active compounds (PhACs) in the subsurface layer of constructed wetlands (CWs) under various anaerobic redox conditions is rarely studied. In this study, CW sediment microbial populations were enriched for PhAC biodegrading organisms. Biodegradation effectivity of a mixture of six PhACs (caffeine, CAF; naproxen, NAP; metoprolol, MET; propranolol, PRO; ibuprofen, IBP; carbamazepine, CBZ) and single compounds (CAF, NAP) was investigated under nitrate reducing, sulfate reducing, and methanogenic conditions using chemical and toxicological analyses. Biodegradation efficiencies varied strongly among the six PhACs and three redox conditions chosen. CAF and NAP were completely biodegraded under sulfate reducing and methanogenic conditions whereas biodegradation efficiencies of the other PhACs were much less (MET, PRO <. 20%; IBP, CBZ, negligible). CAF and NAP showed significantly lower biodegradation under nitrate reducing conditions than under the other two redox conditions. No difference was found in biodegradation efficiencies of CAF and NAP when present as single compound, or as a mixture with other PhACs. Different intermediates were observed, indicating different biodegradation pathways under different redox conditions and when the PhACs were present as single compound or in a mixture. From toxicological perspective, toxicity of PhACs and/or their intermediates to Vibrio fischeri was attenuated during the biodegradation process. Chemical and toxicological data showed positive correlations in principle component analysis, by which potentially toxic PhACs and intermediates are indicated for further ecotoxicological hazard assessment

Biological regeneration of manganese (IV) and iron (III) for anaerobic metal oxide-mediated removal of pharmaceuticals from water

Applying manganese(IV)- or iron(III)-(hydr)oxides to remove pharmaceuticals from water could be attractive, due to the capacity of these metal oxides to remove pharmaceuticals and be regenerated. As pharmaceutical removal under anaerobic conditions is foreseen, Mn(IV) or Fe(III) regeneration under anaerobic conditions, or with minimum oxygen dosage, is preferred. In this study, batch experiments are performed to investigate (1) Mn(IV) and Fe(III) regeneration from Mn(II) and Fe(II); (2) the pharmaceutical removal during biological Mn(IV) and Fe(III) regeneration; and (3) anaerobic abiotic pharmaceutical removal with different Mn(IV) or Fe(III) species. Results show that biological re-oxidation of reduced Mn(II) to Mn(IV) occurs under oxygen-limiting conditions. Biological re-oxidation of Fe(II) to Fe(III) is obtained with nitrate under anaerobic conditions. Both bio-regenerated Mn(IV)-oxides and Fe(III)-hydroxides are amorphous. The pharmaceutical removal is insignificant by Mn(II)- or Fe(II)-oxidizing bacteria during regeneration. Finally, pharmaceutical removal is investigated with various Mn(IV) and Fe(III) sources. Anaerobic abiotic removal using Mn(IV) produced from drinking water treatment plants results in 23% metoprolol and 44% propranolol removal, similar to chemically synthesized Mn(IV). In contrast, Fe(III) from drinking water treatment plants outperformed chemically or biologically synthesized Fe(III); Fe (III) from drinking water treatment can remove 31–43% of propranolol via anaerobic abiotic process. In addition, one of the Fe(III)-based sorbents tested, FerroSorp®RW, can also remove propranolol (20–25%). Biological regeneration of Mn(IV) and Fe(III) from the reduced species Mn(II) and Fe(II) could be more effective in terms of cost and treatment efficiency.</p

Anaerobic biodegradation of pharmaceutical compounds coupled to dissimilatory manganese (IV) or iron (III) reduction

Pharmaceuticals in water have adverse effects on aquatic environment. Anaerobic pharmaceutical biodegradation coupled to dissimilatory manganese(Mn) (IV)- or iron(Fe) (III)-oxides reduction is potentially efficient but unexplored. In this study, batch experiments were performed using different Mn(IV) and Fe(III) species with a microbial inoculum pre-cultivated with 15 mM chemically-synthesized Mn(IV) and 10 mg L−1 metoprolol. Results show 26% caffeine and 52% naproxen are degraded with Mn(IV) as terminal electron acceptor and insignificant biodegradation for other pharmaceuticals tested. Reduction of Mn(IV) from drinking water treatment is coupled to anaerobic biodegradation of metoprolol and propranolol, resulting in removal efficiencies of 96% and 31%, respectively. The results indicate that adsorption contributes to the pharmaceutical removal during the first 10 days of incubation, while biodegradation is the main removal mechanism in the whole period. Fe(III) can also be used as electron acceptor in anaerobic pharmaceutical biodegradation. Over half of the added metoprolol is degraded with both chemically-synthesized Fe(III) and Fe(III)-citrate as terminal electron acceptors. However, this process did not occur when using Fe(III) from drinking water treatment or Fe(III)-based sorbents. This study indicates that anaerobic pharmaceutical biodegradation coupled to dissimilatory Mn(IV) or Fe(III) reduction is possible, and promising for application to cleaning wastewater treatment plant effluents.</p

Anoxic conditions are beneficial for abiotic diclofenac removal from water with manganese oxide (MnO2)

This is the first study examining pharmaceutical removal under anoxic conditions with MnO2. This study compares the abiotic removal of seven pharmaceuticals with reactive MnO2 particles in the presence of oxygen (oxic conditions) and in the absence of oxygen (anoxic conditions). Due to the novelty of pharmaceutical removal under anoxic conditions, the influence of phosphate buffer, pH, and MnO2 morphologies is also examined. Results show that over 90% of diclofenac is removed under anoxic conditions. Additionally, we found that (1) anoxic conditions are beneficial for diclofenac removal with MnO2, (2) phosphate buffer affects the pharmaceutical removal efficiencies, (3) higher pharmaceutical removal is obtained at acidic pH compared to that at neutral or alkaline conditions, and (4) amorphous MnO2 removes pharmaceuticals better than crystalline MnO2. The pharmaceutical molecular structure and properties, MnO2 properties especially reactive sites of the MnO2 surface, are important for degradation kinetics. This study provides a fundamental basis towards understanding pharmaceutical degradation with MnO2 under anoxic conditions, and development of a cost-effective, sustainable technology for removal of pharmaceuticals from water

Fate and distribution of pharmaceutically active compounds in mesocosm constructed wetlands

Removal of pharmaceutically active compounds (PhACs) in constructed wetlands (CWs) is a complex interplay of different processes. We studied fate and distribution of seven PhACs (caffeine, CAF; naproxen, NAP; metoprolol, MET; propranolol, PRO; ibuprofen, IBP; carbamazepine, CBZ; diclofenac, DFC) in mesocosm CWs and effects of irradiation via pre-photocatalysis, substrate composition (mainly sediment) through addition of litter (dead plant biomass), and plants. CWs showed high removal of CAF, NAP, MET, PRO, and IBP (79–99%). All seven PhACs were detected in substrate and plant tissues as well as IBP intermediates. Estimated PhAC mass balance showed that sorption dominated PRO removal in CWs while other PhACs were mainly removed by biodegradation and/or phytodegradation. Pre-photocatalysis significantly increased removal of PhACs except for CAF and IBP, and decreased accumulation of PhACs in substrate and plant tissues of the following wetland compartment. Litter addition in CW significantly enhanced removal of PRO and CBZ via biodegradation and/or phytodegradation. Plants played an essential and positive role in removing PhACs, resulting from direct phytoremediation and indirectly enhancing sorption and biodegradation. Our study provides knowledge to understand removal mechanisms of PhACs in CWs and to potentially enhance PhAC removal by developing pre-photocatalysis, adding dead plant biomass, and optimizing vegetation.</p

Retention soil filter as post-treatment step to remove micropollutants from sewage treatment plant effluent

Retention soil filters (RSFs) are a specific form of vertical flow constructed wetlands for the treatment of rain water and/or wastewater. We have tested 3 pilot RSFs to investigate removal of dissolved organic carbon (DOC) and 14 different organic micropollutants (OMPs) from the effluent of a large scale sewage treatment plant (STP). Two of them were operated as conventional RSF with material (sand with CaCO3 and organic matter) from two different full-scale RSFs. The third pilot RSF contained filter material (sand with CaCO3) with additional biochar in the upper layer (0–10 cm) and granulated activated carbon (GAC) in the lower layer (60–90 cm). The filters were planted with Phragmites australis. The RSFs were operated and monitored for 3 years, and water samples were taken regularly at inflow, outflows and in 3 depths within the filters. In total 523 samples were taken. In the conventional RSF, best median removal was detected for galaxolide, diclofenac 4-hydroxy, metoprolol and clarithromycin (75–79%). No removal was seen for sulfamethoxazole and carbamazepine. The DOC and OMP removal in the conventional RSFs was best in the upper layer with highest organic matter content, increased in time over the three years of operation and also with extended contact time. In the effluent of the RSF with GAC, 10 out of the 14 OMPs could not be detected; 4 OMPs were detected, but only metformin with removal 88% to 60%) over the 2.5 years of operation. Biochar was most effective in OMP removal in the first operational year. It can be concluded that the increasing removal efficiency of the conventional RSF material – also present in the RSF with biochar and GAC – might mitigate the reduced efficiency of the sorbent additives biochar and GAC. This enables to extend the operational lifetime of the filters with acceptable removal rates. Finally, our study demonstrates that an RSF with GAC shows an enhanced removal of OMPs, which is a suitable post-treatment step for STPs.</p

In situ removal of four organic micropollutants in a small river determined by monitoring and modelling

Organic micropollutants (OMPs) are widely detected in surface waters. So far, the removal processes of these compounds in situ in river systems are not yet totally revealed. In this study, a combined monitoring and modelling approach was applied to determine the behaviour of 1-H benzotriazole, carbamazepine, diclofenac and galaxolide in a small river system. Sewage treatment plant effluents and the receiving waters of the river Swist were monitored in 9 dry weather sampling campaigns (precipitation < 1 mm on the sampling day itself and <5 mm total precipitation two days before the sampling) during different seasons over a period of 3 years. With the results gained through monitoring, mass balances have been calculated to assess fate in the river. With the DWA Water Quality Model, OMP concentrations in the river were successfully simulated with OMP characteristics gained through literature studies. No removal was determined for 1-H benzotriazole and carbamazepine, whereas diclofenac showed removal that coincided with light intensity. Moreover, modelling based on light sensitivity of diclofenac also suggested relevant degradation at natural light conditions. These two approaches suggest removal by photodegradation. The highest removal in the river was detected for galaxolide, presumably due to volatilisation, sorption and biodegradation. Furthermore, short-term concentration variability in the river was determined, showing that daily concentration patterns are influenced by dynamics of sewage treatment plant effluent volumes and removal processes in the river.</p