Kinetics and biotransformation products of bisphenol F and S during aerobic degradation with activated sludge.

Bisphenol F (BPF) and bisphenol S (BPS) are becoming widespread in the environment despite the lack of information regarding their fate during wastewater treatment and in the environment. This study assessed the biodegradation kinetics of BPF and BPS during biological wastewater treatment with activated sludge using GC-MS/MS, and the identification of biotransformation products (BTPs) using LC-QTOF-MS. The results showed that BPF and BPS degrade readily and unlikely accumulate in biosolids or wastewater effluent (ci = 0.1 mg L-1, half-lives <4.3 days). The first-order kinetic model revealed that BPF (kt = 0.20-0.38) degraded faster than BPS (kt = 0.04-0.16) and that degradation rate decreases with an increasing initial concentration of BPS (half-lives 17.3 days). The absence of any additional organic carbon source significantly slowed down degradation, in particular, that of BPS (lag phase on day 18 instead of day 7). The machine-learning algorithm adopted as part of the non-targeted workflow identified three known BTPs and one novel BTP of BPF, and one known and ten new BTPs of BPS. The data from this study support possible new biodegradation pathways, namely sulphation, methylation, cleavage and the coupling of smaller bisphenol moieties.

Biotransformation study of antidepressant sertraline and its removal during biological wastewater treatment.

Sertraline is one of the most commonly prescribed antidepressants in the last few years. Therefore, it is not surprising that it is regularly detected in wastewaters, surface waters, sediments, biosolids and biota. Effluents from wastewater treatment plants are the main contributors to its presence in the environment. The presented study aims to elucidate the processes involved in its removal, concentrating mainly on sorption and biodegradation during wastewater treatment. We performed our laboratory scale experiments in two sets of experiments: 1) batch biodegradation and sorption experiments and 2) flow-through laboratory scale pilot wastewater treatment bioreactors. The batch experiments revealed that sorption to activated sludge was the leading removal process, eliminating up to 90% of sertraline present in the batches. Biodegradation was however the secondary removal process, influenced by the presence of alternative easily biodegradable carbon sources. We postulated chemical structures of ten detected biotransformation products. Among these, we propose the previously recognized metabolite norsertraline, sertraline ketone and hydroxy-sertraline. All the remaining biotransformation products are herein reported for the first time. The removal efficiency of approximately 94% was determined after the treatment in the flow-through bioreactors. To support our findings, we sampled influents and effluents from two wastewater treatment plants and untreated wastewater from a psychiatric hospital. Removal efficiencies of 81% and 77% were determined, and along with the parent compound sertraline, the presence of eight transformation products was confirmed in the actual wastewaters.

Molecularly Imprinted Polymers for the Removal of Antidepressants from Contaminated Wastewater.

Selective serotonin reuptake inhibitors (SSRIs) are a class of antidepressants regularly detected in the environment. This indicates that the existing wastewater treatment techniques are not successfully removing them beforehand. This study investigated the potential of molecularly imprinted polymers (MIPs) to serve as sorbents for removal of SSRIs in water treatment. Sertraline was chosen as the template for imprinting. We optimized the composition of MIPs in order to obtain materials with highest capacity, affinity, and selectivity for sertraline. We report the maximum capacity of MIP for sertraline in water at 72.6 mg g-1, and the maximum imprinting factor at 3.7. The MIPs were cross-reactive towards other SSRIs and the metabolite norsertraline. They showed a stable performance in wastewater-relevant pH range between 6 and 8, and were reusable after a short washing cycle. Despite having a smaller surface area between 27.4 and 193.8 m2·g-1, as compared to that of the activated carbon at 1400 m2·g-1, their sorption capabilities in wastewaters were generally superior. The MIPs with higher surface area and pore volume that formed more non-specific interactions with the targets considerably contributed to the overall removal efficiency, which made them better suited for use in wastewater treatment.

Determination and photodegradation of sertraline residues in aqueous environment.

Sertraline is an antidepressant drug that has been frequently reported in the aquatic environment and biota. While the research has mostly dealt with its occurrence and toxicity, there is a lack of information pertaining to its environmental transformation. The present study aimed to fill in these gaps by giving an insight into mechanisms of sertraline phototransformation in surface waters, which was recognized as the main transformation pathway for this contaminant. We performed photodegradation experiments in presence of photosensitizers or reaction quenchers to determine rate constants and used them to predict sertraline phototransformation kinetics by "Aqueous Photochemistry of Environmentally occurring Xenobiotics" (APEX) software. It was established that sertraline degrades by pseudo-first order kinetics mostly dominated by direct photolysis, while the presence of certain reactive species including •OH, CO3-• and 3CDOM* further accelerate the compound's breakdown rate. To validate the predicted results, sertraline-spiked surface water was irradiated by sunlight, where the half-life of sertraline at around 1.4 days was estimated. While following the photodegradation kinetics, we also identified five transformation products, of which three were determined in Slovenian surface waters. According to the ECOSAR toxicity prediction, these transformation products will either have comparable or lower toxicity than their parent compound.

Identification and quantification of bleomycin in serum and tumor tissue by liquid chromatography coupled to high resolution mass spectrometry.

Bleomycin is a cytotoxic antibiotic available as a compost of structurally strongly related glycopeptides, which is in vivo found chelated with several metals. Its pharmacotherapy has merely been based on experimental dose - response data, whereas its biodistribution and pharmacokinetics remain fundamentally unknown. This is reasoned by an absence of a specific and sensitive mass spectrometry-based analytical method for its determination in biological tissues. We herein reveal the results of our study on the mass spectrometric behavior of two main bleomycin fractions A2 and B2, including their metal complexes, particularly the predominant copper chelates. In the electrospray ion source bleomycin forms double charged species, where for the metal-free fraction A2 and its copper complex m/z 707.76 and m/z 707.21 are seen, respectively. Hence, the second isotopic ion of the chelate (m/z 707.71) nearly coincides with the first isotopic ion of the metal-free fraction. This phenomenon can only be followed by high-resolution mass spectrometry, and is considered the plausible reason, why the attempts to determine bleomycin with mass spectrometry have been so scarce. The presented paper further describes a sensitive and selective liquid chromatography - mass spectrometry analytical method for determination of bleomycin in serum and tumor tissues. This newly developed method was employed for bleomycin pharmacokinetic studies in serum and tumors of laboratory animals. Additionally, the method was employed for determination of bleomycin pharmacokinetic parameters in elderly patients in order to determine the effective therapeutic window of electrochemotherapy with bleomycin.