Biodegradation Of Pharmaceuticals Research Articles

Application of fungal-based microbial fuel cells for biodegradation of pharmaceuticals: Comparative study of individual vs. mixed contaminant solutions

The present study focuses on the application of fungal-based microbial fuel cells (FMFC) for the degradation of organic pollutants including Acetaminophen (APAP), Para-aminophenol (PAP), Sulfanilamide (SFA), and finally Methylene Blue (MB). The objective is to investigate the patterns of degradation (both individually and as a mixture solution) of the four compounds in response to fungal metabolic processes, with an emphasis on evaluating the possibility of generating energy. Linear Sweep Voltammetry (LSV) has been used for electrochemical analysis of the targeted compounds on a Glassy Carbon Electrode (GCE). A dual chamber MFC has been applied wherein the cathodic compartment, the reduction reaction of oxygen was catalyzed by an elaborated biofilm of Trametes trogii, and the anodic chamber consists of a mixed solution of 200 mg L−1 APAP, PAP, MB, and SFA in 0.1 M PBS and an elaborated biofilm of Trichoderma harzianum. The obtained results showed that all the tested molecules were degraded over time by the Trichoderma harzianum. The biodegradation kinetics of all the tested molecules were found to be in the pseudo-first-order. The results of half-lives and the degradation rate reveal that APAP in its individual form degrades relatively slower (0.0213 h−1) and has a half-life of 33 h compared to its degradation in a mixed solution with a half-life of 20 h. SFA showed the longest half-life in the mixed condition (98 h) which is the opposite of its degradation as individual molecules (20 h) as the fastest molecule compared to other pollutants. The maximum power density of the developed MFC dropped from 0.65 mW m−2 to 0.32 mW m−2 after 45.5 h, showing that the decrease of the residual concentration of molecules in the anodic compartment leads to the decrease of the MFC performance.

Anaerobic co-metabolic biodegradation of pharmaceuticals and personal care products driven by glycerol fermentation

Anaerobic digestion in two sequential phases, acidogenesis and methanogenesis, has been shown to be beneficial for enhancing the biomethane generation from wastewater. In this work, the application of glycerol (GOH) as a fermentation co-substrate during the wastewater treatment was evaluated on the biodegradation of different pharmaceuticals and personal care products (PPCPs). GOH co-digestion during acidogenesis led to a significant increase in the biodegradation of acetaminophen (from 78 to 89%), ciprofloxacin (from 25 to 46%), naproxen (from 73 to 86%), diclofenac (from 36 to 48%), ibuprofen (from 65 to 88%), metoprolol (from 45 to 59%), methylparaben (from 64 to 78%) and propylparaben (from 68 to 74%). The heterotrophic co-metabolism of PPCPs driven by glycerol was confirmed by the biodegradation kinetics, in which kbio (biodegradation kinetics constant) values increased from 0.18 to 2.11 to 0.27–3.60 L g−1-VSS d−1, for the operational phases without and with GOH, respectively. The assessment of metabolic pathways in each phase revealed that the prevalence of aromatic compounds degradation, metabolism of xenobiotics by cytochrome P450, and benzoate degradation routes during acidogenesis are key factors for the enzymatic mechanisms linked to the PPCPs co-metabolism. The phase separation of anaerobic digestion was effective in the PPCPs biodegradation, and the co-fermentation of glycerol provided an increase in the generation potential of biomethane in the system (energetic potential of 5.0 and 6.3 kJ g−1-CODremoved, without and with GOH, respectively). This study showed evidence that glycerol co-fermentation can exert a synergistic effect on the PPCPs removal during anaerobic digestion mediated by heterotrophic co-metabolism.

The microbial oxidation of pharmaceuticals in an anaerobic aqueous environment: Effect of dissolved organic matter fractions from different sources

Previous studies have demonstrated the importance of dissolved organic matter (DOM) on the biodegradation of trace organic contaminants occurred in the hyporheic zone. However, the role of diverse DOM fractions with distinct physicochemical properties on the biodegradation of pharmaceuticals under reducing conditions is scarcely known. To address this knowledge gap, DOMs derived from road-deposited sediment, soil, and active sludge (namely allochthonous DOM) and algae (namely autochthonous DOM) were collected and isolated into different fractions. Thereafter, the effect of DOM fractions on the anaerobic microbial oxidation of two typical pharmaceuticals, i.e., ritonavir (RTV) and tetracycline (TC) was explored by using simulated anaerobic microcosms. Mechanistic insights into how DOM fractions from different sources influence pharmaceutical biodegradation processes were provided by optical and electrochemical analyses. Results showed that humic acid and fulvic acid fractions from allochthonous DOM could enhance the biodegradation of TC (12.2 % per mgC/L) and RTV (14.5 % per mgC/L), while no significant impact was observed for that of hydrophilic fractions. However, autochthonous DOM promoted the biodegradation of TC (4.17 % per mgC/L) and inhibited that of RTV. Mechanistic analysis showed that the higher of humification and aromatization level of DOM components, the stronger their promotive effect on the biodegradation of TC and RTV. Further, the promotive mechanism could be attributed to the response of quinone moieties in DOM as extracellular electron acceptors that yields more energy to support microbial metabolism. These results provide a more comprehensive understanding of diverse DOM fractions mediating microbial anaerobic oxidation of trace organic pollutants, and extend our insights into contamination control and remediation technologies.

Analyzing microbial communities and their biodegradation of multiple pharmaceuticals in membrane bioreactors.

Pharmaceuticals are of concern to our planet and health as they can accumulate in the environment. The impact of these biologically active compounds on ecosystems is hard to predict, and information on their biodegradation is necessary to establish sound risk assessment. Microbial communities are promising candidates for the biodegradation of pharmaceuticals such as ibuprofen, but little is known yet about their degradation capacity of multiple micropollutants at higher concentrations (100mg/L). In this work, microbial communities were cultivated in lab-scale membrane bioreactors (MBRs) exposed to increasing concentrations of a mixture of six micropollutants (ibuprofen, diclofenac, enalapril, caffeine, atenolol, paracetamol). Key players of biodegradation were identified using a combinatorial approach of 16S rRNA sequencing and analytics. Microbial community structure changed with increasing pharmaceutical intake (from 1 to 100mg/L) and reached a steady-state during incubation for 7weeks on 100mg/L. HPLC analysis revealed a fluctuating but significant degradation (30-100%) of five pollutants (caffeine, paracetamol, ibuprofen, atenolol, enalapril) by an established and stable microbial community mainly composed of Achromobacter, Cupriavidus, Pseudomonas and Leucobacter. By using the microbial community from MBR1 as inoculum for further batch culture experiments on single micropollutants (400mg/L substrate, respectively), different active microbial consortia were obtained for each single micropollutant. Microbial genera potentially responsible for degradation of the respective micropollutant were identified, i.e. Pseudomonas sp. and Sphingobacterium sp. for ibuprofen, caffeine and paracetamol, Sphingomonas sp. for atenolol and Klebsiella sp. for enalapril. Our study demonstrates the feasibility of cultivating stable microbial communities capable of degrading simultaneously a mixture of highly concentrated pharmaceuticals in lab-scale MBRs and the identification of microbial genera potentially responsible for the degradation of specific pollutants. KEY POINTS: • Multiple pharmaceuticals were removed by stable microbial communities. • Microbial key players of five main pharmaceuticals were identified.

Selective enrichment, identification, and isolation of diclofenac, ibuprofen, and carbamazepine degrading bacteria from a groundwater biofilm

Diclofenac, ibuprofen, and carbamazepine are three of the most widely detected and most concerning pharmaceutical residues in aquatic ecosystems. The aim of this study was to identify bacteria that may be involved in their degradation from a bacterial biofilm. Selective enrichment cultures in mineral salt solution containing pharmaceutical compounds as sole source of carbon and energy were set up, and population dynamics were monitored using shotgun metagenome sequencing. Bacterial genomes were reconstructed using genome-resolved metagenomics. Thirty bacterial isolates were obtained, identified at species level, and tested regarding pharmaceutical biodegradation at an initial concentration of 1.5 mg l−1. The results indicated that most probably diclofenac biodegrading cultures consisted of members of genera Ferrovibrio, Hydrocarboniphaga, Zavarzinia, and Sphingopyxis, while in ibuprofen biodegradation Nocardioides and Starkeya, and in carbamazepine biodegradation Nocardioides, Pseudonocardia, and Sphingopyxis might be involved. During the enrichments, compared to the initial state the percentage relative abundance of these genera increased up to three orders of magnitude. Except Starkeya, the genomes of these bacteria were reconstructed and annotated. Metabolic analyses of the annotated genomes indicated that these bacteria harbored genes associated with pharmaceutical biodegradation. Stenotrophomonas humi DIC_5 and Rhizobium daejeonense IBU_18 isolates eliminated diclofenac and ibuprofen during the tests in the presence of either glucose (3 g l−1) or in R2A broth. Higher than 90% concentration reduction was observed in the case of both compounds.

Microbial paracetamol degradation involves a high diversity of novel amidase enzyme candidates

Pharmaceuticals are relatively new to nature and often not completely removed in wastewater treatment plants (WWTPs). Consequently, these micropollutants end up in water bodies all around the world posing a great environmental risk. One exception to this recalcitrant conversion is paracetamol, whose full degradation has been linked to several microorganisms. However, the genes and corresponding proteins involved in microbial paracetamol degradation are still elusive. In order to improve our knowledge of the microbial paracetamol degradation pathway, we inoculated a bioreactor with sludge of a hospital WWTP (Pharmafilter, Delft, NL) and fed it with paracetamol as the sole carbon source. Paracetamol was fully degraded without any lag phase and the enriched microbial community was investigated by metagenomic and metatranscriptomic analyses, which demonstrated that the microbial community was very diverse. Dilution and plating on paracetamol-amended agar plates yielded two Pseudomonas sp. isolates: a fast-growing Pseudomonas sp. that degraded 200 mg/L of paracetamol in approximately 10 h while excreting 4-aminophenol, and a slow-growing Pseudomonas sp. that degraded paracetamol without obvious intermediates in more than 90 days. Each Pseudomonas sp. contained a different highly-expressed amidase (31% identity to each other). These amidase genes were not detected in the bioreactor metagenome suggesting that other as-yet uncharacterized amidases may be responsible for the first biodegradation step of paracetamol. Uncharacterized deaminase genes and genes encoding dioxygenase enzymes involved in the catabolism of aromatic compounds and amino acids were the most likely candidates responsible for the degradation of paracetamol intermediates based on their high expression levels in the bioreactor metagenome and the Pseudomonas spp. genomes. Furthermore, cross-feeding between different community members might have occurred to efficiently degrade paracetamol and its intermediates in the bioreactor. This study increases our knowledge about the ongoing microbial evolution towards biodegradation of pharmaceuticals and points to a large diversity of (amidase) enzymes that are likely involved in paracetamol metabolism in WWTPs.

Biodegradation of pharmaceuticals in photobioreactors – a systematic literature review

ABSTRACT This work is a systematic review that reports state-of-the-art in removal of pharmaceuticals from water and wastewater by photosynthetic organisms in photobioreactors. The PRISMA protocol-based review of the most recent literature data from the last 10 years (2011–2021) was reported. Articles were searched by the combination of the following keywords: photobioreactor, pharmaceuticals, drugs, hormones, antibiotics, biodegradation, removal, wastewater treatment. The review focuses on original research papers (not reviews), collected in 3 scientific databases: Scopus, Web of Knowledge, PubMed. The review considered the following factors: type of microorganisms, type of micropollutants removed, degradation efficiency and associated products, types of photosynthetic organisms and photobioreactor types. The conclusion from the systematic review is that the main factors that limit widespread pharmaceuticals removal in photobioreactors are high costs and the problem of low efficiency related with low concentrations of pharmaceuticals. The review indicated a need for further research in this area due to increasing amounts of metabolites in the food chain, such as p-aminophenol and estrone, which can cause harm to people and ichthyofauna. Pharmaceuticals removal can be improved by adapting the type of microorganism used to the type of contamination and implementing photoperiods, which increase the removal efficiency of e.g. sulfamethazine by up to 28%. In the future, it is necessary to search for new solutions in terms of the construction of photobioreactors, as well as for more effective species in terms of pharmaceuticals biodegradation that can survive the competition with other strains during water and wastewater treatment.

Sorption and biodegradation parameters of selected pharmaceuticals in laboratory column experiments

Pharmaceutically active compounds have increasingly been detected in groundwater worldwide. Despite constituting a risk for human health and ecosystems, their fate in the environment has still not been exhaustively investigated. This study characterizes the transport behavior of five selected pharmaceutically active compounds (antipyrine, atenolol, caffeine, carbamazepine and sulfamethoxazole) in two sediments (coarse quartz sand and sandy loam) using column experiments with long-term injection of spiked groundwater. Transport parameters were estimated using an analytical reactive transport model. When five selected compounds were injected simultaneously, transport behavior of antipyrine, carbamazepine and the antibiotic sulfamethoxazole were similar to the conservative tracer in both sediments and under varying redox conditions. Atenolol and caffeine were retarded significantly stronger in the sandy loam sediment than in the coarse quartz sand. Biodegradation of caffeine was observed in both sediments after an adaption period and depended on dissolved oxygen. The identification of biodegradation processes was supported by monitoring of intracellular adenosine triphosphate (ATPitc) as a measure for microbial activity. ATPitc was present in varying concentrations in all sediments and was highest when biodegradation of pharmaceuticals, especially caffeine, was observed. When only caffeine and sulfamethoxazole were injected simultaneously, sulfamethoxazole was degraded while caffeine degradation was reduced. The latter seemed to be influenced by low concentrations in dissolved oxygen rather than the presence of the antibiotic sulfamethoxazole. Results of these experiments emphasize the impact on pharmaceutical sorption and (bio)degradation of sediment type and redox conditions, as well as available time for microbial adaption and the combination of pharmaceuticals that are released together into groundwater.

Improved biodegradation of pharmaceuticals after mild photocatalytic pretreatment

AbstractThe combination of photocatalysis and biodegradation was investigated for the removal of nine selected pharmaceuticals as a means to reduce loadings into the environment. The combined process, consisting of a resource‐efficient mild photocatalysis and a subsequent biological treatment, was compared to single processes of intensive photocatalysis and biological treatment. The UV‐TiO2 based photocatalysis effectively removed atorvastatin, atenolol and fluoxetine (>80%). Biological treatment after mild photocatalytic pretreatment removed diclofenac effectively (>99%), while it persisted during the single biological treatment (<50%). Moreover, the biodegradation of atorvastatin, caffeine, gemfibrozil and ibuprofen was enhanced after mild photocatalytic pretreatment compared to biological treatment alone. The enhanced biodegradation of these pharmaceuticals appeared to be triggered by the biodegradation of photocatalytic products. Mild photocatalysis followed by biological treatment is an effective and resource‐efficient combination for pharmaceutical removal that could substantially reduce the loading of pharmaceuticals into the environment.

Pharmaceuticals removal by immobilized laccase on polyvinylidene fluoride nanocomposite with multi-walled carbon nanotubes

The presence of pharmaceutical micropollutants in water and wastewater is considered a serious environmental issue. To eliminate these pollutants, biodegradation of pharmaceuticals using enzymes such as laccase, is proposed as a green method. In this study, immobilized laccase was used for the removal of two model pharmaceutical compounds, carbamazepine and diclofenac. Polyvinylidene fluoride (PVDF) membrane modified with multi-walled carbon nanotubes (MWCNTs) were synthesized as a tailor-made support for enzyme immobilization. Covalently immobilized laccase from Trametes hirsuta exhibited remarkable activity and activity recovery of 4.47 U/cm2 and 38.31%, respectively. The results also indicated improvement in the operational and thermal stability of the immobilized laccase compared to free laccase. Finally, by using immobilized laccase in a mini-membrane reactor, removal efficiencies of 27% in 48 h and 95% in 4 h were obtained for carbamazepine and diclofenac, respectively. The findings suggest that immobilized laccase on PVDF/MWCNT membranes is a promising catalyst for large-scale water and wastewater treatment which is also compatible with existing treatment facilities.

Biodegradation of five pharmaceuticals: estimation by predictive models and comparison with activated sludge data

This study investigated the biodegradation potential of five pharmaceutical micropollutants, acetaminophen, ibuprofen, carbamazepine, sulfamethoxazole and erythromycin, under aerobic conditions. First, theoretical aerobic biodegradation potential of these pharmaceuticals was investigated using the BIOWIN models of the Estimation Programs Interface Suite. The results were then compared with data from activated sludge experiments. The main novelty of this work was that it showed why deviations occurred between theoretical and experimental results. For example, erythromycin was found as the least biodegradable compound in BIOWIN models. On the other hand, carbamazepine proved to be the least biodegradable under experimental conditions. To explain such deviations, biodegradation mechanisms, biodegradation rates and biosorption of pharmaceuticals were taken into consideration. One reason for deviation is that the predictive BIOWIN models consider the single pharmaceutical and relate biodegradability to molecular structure alone. These two points often lead to underestimation of biodegradation. On the other hand, the present study revealed that biodegradation of pharmaceuticals can be enhanced under the microbial and operating conditions of an activated sludge system. Pharmaceuticals can be used as secondary substrates if biodegradable substances are present in an activated sludge. More importantly, they can often be used as cometabolites in the presence of nitrifiers. Also, compared to predicted results, a poorer sorption is observed in activated sludge, indicating that these pharmaceuticals would degrade in liquid phase. Databases/predictive tools are very helpful to have an initial idea about biodegradability. But, in estimation of real biodegradability, there is a need to consider the factors highlighted in this work.

Probing the degradation of pharmaceuticals in urine using MFC and studying their removal efficiency by UPLC-MS/MS

Nutrient recovery from source-separated human urine has attracted interest as it is rich in nitrogen and phosphorus that can be utilized as fertilizer. However, urine also contains pharmaceuticals, steroid hormones, etc. and their removal is crucial as they have detrimental effects on the environment and human health. The current study focuses on investigating the degradation of pharmaceuticals using a double-chamber microbial fuel cell (MFC). Urine was spiked with four pharmaceuticals (trimethoprim, lamivudine, levofloxacin, and estrone) at a concentration of 2 μg/mL. The MFC was operated for 7 months in batch mode with this spiked urine as feed. The degradation efficiency of the MFC was studied, for which a selective liquid chromatography-tandem mass-spectrometric method was developed for the quantitation of compounds used in the spiking experiments and was validated with a lower limit of quantification of 0.39 ng/mL. The maximum removal rate achieved was 96% ± 2%. The degradation mechanism involved processes like sorption and anoxic biodegradation. The voltage curve obtained showed that the presence of pharmaceuticals had an initial negative impact on power generation along with increased organic content; however, after the reactor acclimatization, increased power output was achieved with maximum organics removal at 30 h of retention time. This work opens a new perspective for the anoxic biodegradation of pharmaceuticals and can be useful in future bioremediation studies.

The effect of combined cometabolism and gamma irradiation treatment on the biodegradability of diclofenac and sulfamethoxazole

Diclofenac and sulfamethoxazole are poorly degradable when using activated sludge or biofilm biomass in biological wastewater treatment. However, a biological phenomenon called cometabolism can improve the removal efficiency, especially in activated sludge treatment. In the case of cometabolism an easily degradable substrate is added to the wastewater under treatment. Such easily degradable molecules (e.g. methanol, acetic acid, ethylene glycol) also form in the anaerobic wastewater treatment steps and are utilized as substrates. The rate of oxidative biodegradation of pharmaceuticals (measured by using oxygen uptake rate) was shown to greatly increase in the presence of easily degradable substrates in activated sludge treatment. However, in biofilm treatment the rate of cometabolism remained low, because biofim biomass has much narrower bacterial diversity than activated sludge. The oxidation rate on biofilm was found to increase considerably by using an advanced oxidation process, ionizing radiation treatment, before cometabolism. This combined treatment, irradiation and cometabolism is recommended for the degradation of recalcitrant organic compounds on biofilm.

Advances in biodegradation of pharmaceuticals and personal care products

Pharmaceuticals and personal care products (PPCPs) are a group of emerging environmental micropollutants, including prescription drugs and over-the-counter drugs (e.g., antibiotics, synthetic musk, painkiller, depressor, contraceptive drugs, soporific and weight-loss drug), and personal care products (e.g., cosmetics, synthetic perfume, sunscreen, hair spray, tint and fungicide). Extensive attention has been paid to PPCPs because of their potential negative effects on the environments and human health. Abundant researches have focused on the biodegradation of PPCPs. This review summarizes and discusses the biodegradation method, the diversity of PPCPs-degrading microorganisms, the degradation ability, metabolites and proposed pathways as well as the mechanisms of PPCPs' biodegradation. In addition, prospects for further research on biodegradation of PPCPs are also discussed.

Photocatalysis and biodegradation of pharmaceuticals in wastewater: effect of abiotic and biotic factors

Pharmaceuticals (PhACs) are a class of emerging contaminants of global concern due to their ubiquitous nature, persistence and capability of affecting humans and aquatic lives negatively even at very low concentrations. Conventional wastewater treatment procedures are generally inadequate for removing these contaminants. Photocatalysis, an advance oxidation process (AOP), has been widely used in eliminating PhACs from wastewater. This is due to its low operational cost compared to other AOPs. However, the problem of complete mineralization of PhACs by photocatalysis remains a challenge. In this review, we discussed photocatalysis, biodegradation and mechanisms of action for the degradation of PhACs in wastewaters. The application of a combined photocatalytic biodegradation systems for the degradation of PhACs in wastewater was also presented. It is worthy of note that several operating parameters such as the biotic and abiotic factors are pivotal to an efficient photocatalytic and biodegradation treatment systems. Therefore, an integrated photocatalysis/biodegradation system is essential to achieving a complete mineralization of PhACs; other advantages of this treatment technique include low energy cost, effective degradation process, generation of non-toxic by-product and self-sustenance energy generation.

Robust biodegradation of naproxen and diclofenac by laccase immobilized using electrospun nanofibers with enhanced stability and reusability

Enzymatic biodegradation of pharmaceuticals, using enzymes such as laccase, is a green solution for the removal of toxic pollutants that has attracted growing interest over recent years. Moreover, the application of immobilized biocatalysts is relevant for industrial applications, due to the improved stability and reusability of the immobilized enzymes. Thus, in the present study, laccase was immobilized by adsorption and encapsulation using poly(l-lactic acid)-co-poly(ε-caprolactone) (PLCL) electrospun nanofibers as a tailor-made support. The produced biocatalytic systems were applied in the biodegradation of two commonly used anti-inflammatories, naproxen and diclofenac, which are present in wastewaters at environmentally relevant concentrations. The results showed that under optimal process conditions (temperature 25 °C, pH 5 and 3 for naproxen and diclofenac respectively), even from a solution at a concentration of 1 mg L−1, over 90% of both pharmaceuticals was removed by encapsulated laccase in batch mode. Both immobilized enzymes also exhibited high reusability: after five reaction cycles approximately 60% and 40% of naproxen and diclofenac were removed by encapsulated and adsorbed laccase respectively. In addition, a thorough analysis was made of the products of biodegradation of the two studied pollutants. Furthermore, toxicity study of the mixture after biodegradation of the pharmaceuticals showed that the solutions obtained after the process were approximately 65% less toxic than the initial naproxen and diclofenac solutions.

Electrophilicity index as a critical indicator for the biodegradation of the pharmaceuticals in aerobic activated sludge processes

Improving biodegradation of pharmaceuticals during wastewater treatment is critical to control the release of emerging micropollutants to natural waters. In this study, biodegradation of six model pharmaceuticals was investigated at different initial concentrations in two discrete activated sludge systems, and moreover, the correlation was explored between the biodegradation rate and key molecular properties of the contaminants. First, the biodegradation rates of the pharmaceuticals were measured fitting a pseudo first−order kinetic model to the experimental kinetic data. The degradation rate constants (kbio) were found to negatively correlate to the initial concentration of the chemicals, indicating an inhibitory effect on the microorganisms by the pharmaceuticals. Further examinations of the rate data against the key molecular properties of the pharmaceuticals revealed, for the first time, that the electrophilicity index (ω), a measure of electrophilic power, served as a better indicator of the biodegradability and predictive parameter for the kbio than the conventional log KOW (a measure of hydrophobicity) in the two discrete aerobic activated sludge systems. However, the correlation strength (goodness‒of‒fit) between ω and kbio deteriorated when the reactor turned from aerobic to anoxic and anaerobic conditions, suggesting that electron transfer from pharmaceutical molecules to enzymes was inhibited when dissolved oxygen was deficit or absent. Our results show that ω can potentially serve as a straightforward and robust indicator for predicting the biodegradability of pharmaceutical in conventional activated sludge processes.

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 β-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 β-blockers and thus reveals a complex co-metabolism relationship between transformation pathways of pharmaceuticals and carbon source.

Biodegradation of pharmaceuticals and personal care products in the sequential combination of activated sludge treatment and soil aquifer treatment

ABSTRACTSoil aquifer treatment (SAT), applied after activated sludge treatment (AST), has been widely used for wastewater reclamation. AST and SAT show potential for removing micropollutants, including pharmaceuticals and personal care products (PPCPs). However, the role of sequential combination of AST and SAT on the biodegradation of PPCPs was not clear in previous studies. In this study, the removal characteristics of PPCPs in AST and SAT were evaluated to assess the legitimacy of sequential combination of AST and SAT. SAT showed effective removals of antibiotics (> 80%), including fluoroquinolones and macrolides by sorption, but poor removals of amide pharmaceuticals (i.e. carbamazepine and crotamiton) were observed in both AST and SAT. Additionally, biodegradation contributed to the effective removal of carboxylic PPCPs (i.e. ketoprofen and gemfibrozil) in both ASTs and SAT, but effective biodegradation of halogenated acid and polycyclic aromatic compounds (i.e. clofibric acid and naproxen) was observed only in SAT (82.1% and 81.8%, respectively). Furthermore, the microbial substrate metabolic patterns showed that amino acids, amines, and polymers were biodegradable in SAT, which was fit for the biodegradation characteristics of PPCPs in SAT. For microbial communities, Proteobacteria were dominant in AST and SAT, but Acidobacteria and Actinobacteria were more abundant in SAT than AST, which could contribute to the effective removals of halogenated acid in SAT. Considering PPCP biodegradation and substrate metabolism, SAT displays a wider range on the biodegradation than AST. Therefore, we conclude that these two processes can complement each other when used for controlling PPCPs.

Analysis of pharmaceutical biodegradation of WWTP sludge using composting and identification of certain microorganisms involved in the process

Pharmaceuticals (PhCs) are organic contaminants that have been detected in wastewater, surface water, and soils throughout the world. The presence of 10 commonly used PhCs in Spain (azithromycin, benzylpenicillin, citalopram, fluconazole, fluoxetine, ibuprofen, irbesartan, olanzapine, telmisartan, and venlafaxine) was analysed at four wastewater treatment plants, and the changes in their concentrations during treatment were assessed. Although certain some PhCs were degraded in the treated water, their presence in sewage sludge increased in all cases. The sewage sludge was composted using rice straw to degrade the PhCs, and the composting efficiency was modified by changes in the relative C/N ratio of the composting blend. Using a simple microbiological culture process for enrichment, 11 different strains of microorganisms that degraded specific PhCs were identified. Ibuprofen and azithromycin were metabolized by one and four strains, respectively, and both PhCs were used as a carbon source; in addition, six strains used irbesartan as a nitrogen source.