Determination of pharmaceuticals and metabolites in sludge and hydrochar after hydrothermal carbonization using sonication-QuEChERS extraction method and UHPLC LTQ/Orbitrap MS.

Pharmaceuticals (PhACs) are an important group of emerging contaminants that are released continuously in the environment from wastewater treatments plants (WWTPs). They can produce biological effects even though at very low concentrations. Conventional WWTPs are not able to remove or degrade completely emerging pollutants resulting in the presence of PhACs in sewage sludge after wastewater treatment. PhACs are found in sludge at low ppb-ppt levels, and their analysis and detection is a difficult task due to the complexity of sewage sludge matrices. Hydrothermal carbonization is currently being proposed as a suitable conversion technology for sewage sludge management to recover valuable products and to be used for soil amendment. In this work, a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS)-based methodology with a dispersive solid-phase extraction (d-SPE) clean-up followed by ultra-high-performance liquid chromatography coupled with high-resolution linear ion trap-Orbitrap mass spectrometry (UHPLC-LTQ/Orbitrap MS), operated in positive ionization mode, was adopted to investigate 33 multiclass pharmaceuticals in sewage sludge and in hydrochar produced after hydrothermal carbonization. The analytical method was first optimized studying various extraction parameters and finally validated in terms of linearity, recovery, intra and inter-day precisions, expanded uncertainty (%U)/Horrat ratio at three spiking levels, matrix-effects (ME), process efficiency (PE), and limits of detection and quantification. The developed methodology fulfilled all analytical requirements and was finally applied to sludge samples from the WWTP of Ioannina city where a group of antibiotics was detected at concentrations up to 15 ng g-1 and psychiatric drugs such as amisulpride, clozapine, and citalopram were detected at higher concentration levels up to 205, 87.4 and 63.2 ng g-1, respectively. The method was also applied to hydrothermally treated sludge sample under different reaction conditions. Most of the antibiotic compounds were not detected, and several psychiatric drugs such as mirtazapine, bupropion, valsartan, diazepam, and caffeine were found at concentrations below the LOQ.

Simultaneous determination of pharmaceuticals and metabolites in fish tissue by QuEChERS extraction and UHPLC Q/Orbitrap MS analysis.

In recent years, the occurrence, fate, and adverse effects of pharmaceutically active compounds (PhACs) in aquatic organisms have become a noteworthy issue. In the present study, a rapid and sensitive multiresidue analytical method was developed for the determination of 18 parent PhACs and 5 metabolites in sea bream (Sparus aurata), by combining a modified QuEChERS (quick, easy, cheap, effective, rugged and safe) procedure with ultra-high performance liquid chromatography-Orbitrap-mass spectrometry (UHPLC-Orbitrap-MS). The method development involved optimization of extraction solvent, extraction salts, clean-up sorbents, and amount of sample evaluation, while identification on Orbitrap MS was based on accurate mass and further confirmation with MS/MS fragmentation. The developed method was validated, and linearity was higher than 0.99. Recoveries in all cases ranged between 62 and 107% (at 10, 50, and 100 ng g-1), while intra-day and inter-day precision, expressed as relative standard deviation, RSD, was lower than 4% and 7%, respectively. In addition, limits of quantification (LOQs) ranged between 0.5 and 19 ng g-1. The compounds presented a low matrix effect, between - 13 and 4%, while the expanded uncertainty U% estimated at the three spiking levels 10, 50, and 100 ng g-1 was found below 49% in all cases. Finally, the validated method was applied to sea bream samples from an aquaculture farm located in the Mediterranean Sea, with one positive finding for the antibiotic trimethoprim at a concentration of 26 ng g-1, presenting negligible human health risk.

Accurate mass screening of pesticide residues in wine by modified QuEChERS and LC-hybrid LTQ/Orbitrap-MS.

In this research, a quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction procedure and Ultra-High Performance Liquid Chromatography-Orbitrap-Mass Spectrometry (UHPLC-Orbitrap-MS), were combined to obtain a sensitive and rapid method for the determination of multiclass pesticides in white and red wines. The optimization strategy involved the selection of buffering conditions, by applying different QuEChERS procedures and sorbents for the cleanup step in order to achieve acceptably high recoveries and low co-extractives in the final extracts. Identification was based on both accurate mass and retention time, while further confirmation was achieved by MS fragmentation. The method was evaluated in terms of linearity, recovery, precision, limit of detection (LOD) and quantification (LOQ), matrix effects (ME) and expanded uncertainty. The validated method was successfully applied to real samples (home-made and commercial) revealing the presence of two selected fungicides, in relatively low levels compared to the MRLs defined by the EU for vinification grapes.

An overview of homogeneous and heterogeneous photocatalysis applications for the removal of pharmaceutical compounds from real or synthetic hospital wastewaters under lab or pilot scale.

The last few decades, Pharmaceutical Active Compounds (PhACs) have been considered as emerging contaminants due to their continuous release and persistence to aquatic environment even at low concentrations. A growing number of research articles have shown the occurrence of numerous PhACs in various wastewater treatment plant influents, hospital effluents, and surface waters all over the world. The rising concern regarding PhACs, which present high recalcitrance towards conventional treatment methods, has provoked extensive research in the field of their effective remediation. This review provides a comprehensive assessment of homogeneous and heterogeneous photocatalytic applications for the removal of PhACs, from real or artificial hospital wastewater effluents. These two representative advanced oxidation processes (AOPs) are assessed in terms of their efficiency to remove PhACs, reduce the COD and toxicity as well as increase the biodegradability of the effluent. Simultaneously with their efficiency the operational costs of the processes are considered. Their potential combination with other processes is critically discussed, as this option seems to enhance the treatment efficiency and simultaneously overcome the limitations of each individual process. Moreover, the type of reactors as well as the main parameters that should be considered for the design and the development of photoreactors for wastewater treatment are reviewed. Finally, based on the literature survey, indications for future work are provided.

Assessment of multiclass pharmaceutical active compounds (PhACs) in hospital WWTP influent and effluent samples by UHPLC-Orbitrap MS: Temporal variation, removals and environmental risk assessment.

Nowadays the occurrence and associated risks of Pharmaceutical Active Compounds (PhACs) in the aquatic environment comprises a major issue. In the present study, a comprehensive survey on contamination profiles, occurrence, removals, temporal variation and ecological risk of multiclass multiresidue PhACs, such as antibiotics, non-steroidal anti-inflammatories, lipid regulators and phsychiatrics, (including past and newly monitored PhACs as well as some of their metabolites) was performed in wastewaters from the WWTP of Ioannina University hospital along one year period on a monthly sampling basis. WWTP influent and effluent samples were analyzed for physicochemical quality parameters and PhACs concentration levels using Ultra High Performance Liquid Chromatography-Orbitrap-Mass Spectrometry (UHPLC-Orbitrap-MS), after Solid Phase Extraction (SPE) through Oasis HLB cartridges. Influent concentrations ranged between < LOQ (Limit of Quantification) for diclofenac and tolfenamic acid and 48586 ng/L for caffeine, while effluent concentrations between < LOQ for tolfenamic acid and simvastatin and 3361 ng/L for caffeine. Removal efficiencies ranged between -132.6% for venlafaxine and 100% for caffeine. Environmental risk assessment by means of Risk Quotient (RQ) for maximum and minimum concentration levels as well as optimized by the frequency of exceeding toxicity threshold values, RQf, was applied revealing that up to 12 PhACs posed acute toxicity (clofibric acid, fenofibrate, sulfadiazine, sulfamethoxazole, trimethoprim, amitryptiline, fluoxetine, fluvoxamine, norfluoxetine, sertraline, venlafaxine, caffeine) while up to 4 compounds exerted long-term toxicity (sulfamethoxazole, fluoxetine, sertraline, caffeine) at least for one of the studied organisms. Furthermore, mixture RQMEC/PNEC and RQSTU effect of multiple compounds showed high potential risks of the target groups in some cases, although some contaminants were not included due to lack of available data. Results can be used to prioritization of PhACs and their metabolites for surveillance in receiving water bodies as well as development of knowledge on toxicity and mechanism(s) of action.

Psychiatrics and selected metabolites in hospital and urban wastewaters: Occurrence, removal, mass loading, seasonal influence and risk assessment.

The occurrence, removal, mass loading, seasonal influence and environmental risk assessment of nine psychiatric pharmaceuticals and four of their selected metabolites, were studied in one hospital and one urban wastewater treatment plant (WWTP) in Ioannina city, in northwestern Greece, providing information about the efficiency of the plants and their contribution into the final receiver's flow. Samples were collected from the influents and the effluents of the plants in different sampling campaigns, from July to December 2016. Analytical methodology was based on ultra-high performance liquid chromatography-Orbitrap high-resolution mass spectrometry, after solid-phase extraction through Oasis HLB cartridges. Concentrations in both WWTPs ranged between

Photochemical transformation and wastewater fate and occurrence of omeprazole: HRMS for elucidation of transformation products and target and suspect screening analysis in wastewaters.

Omeprazole is one of the world-wide most frequently prescribed and administered pharmaceuticals in humans for the relief of gastro-intestinal disorders. Despite its high worldwide consumption, omeprazole is rarely detected in urban wastewaters and environmental waters. On the other hand, its human urinary metabolites and transformation products formed through abiotic processes in the environment have been recently documented. Despite these available data, however, there is still a lack of information on the extent of environmental fate and occurrence, on elimination mechanisms and efficiencies in waste water treatment plants. In this study, the relevance of photodegradation processes on the environmental persistence of omeprazole under simulated and solar irradiation was investigated. Photodegradation experiments were performed in distilled water, lake, river and seawater, and revealed that the different matrix in natural waters significantly affect the photolytic behavior of the investigated compound. Overall, the results highlight that photodegradation process by solar irradiation significantly contributes to omeprazole degradation and elimination from the aquatic environment. TPs formed through the process were identified and elucidated by using liquid chromatography high resolution mass spectrometry. In total seven TPs were identified, among of which four were also detected as hydrolysis TPs. The Microtox bioassay showed that solar photolysis is efficient to detoxify omeprazole and its TPs in aqueous solutions. Finally, a systematic investigation was conducted in order to provide information on removal efficiency and occurrence of omeprazole and its metabolites/TPs in 8 WWTPs in North West Greece by performing target and suspect screening analysis. The findings revealed the presence of both parent compound and metabolites/TPs in wastewaters. Given, however, the scarce detection of omeprazole at fairly low concentration levels, from analytical and environmental point of view, further attention should be given to metabolites/TPs instead of the parent compound.

Analysis, occurrence, fate and risks of proton pump inhibitors, their metabolites and transformation products in aquatic environment: A review.

Proton pump inhibitors (PPIs) which include omeprazole, esomeprazole, lansoprazole, pantoprazole and rabeprazole, are extensively used for the relief of gastro-intestinal disorders. Despite their high worldwide consumption, PPIs are extensively metabolized in human bodies and therefore are not regularly detected in monitoring studies. Very recently, however, it has been shown that some omeprazole metabolites may enter and are likely to persist in aquatic environment. Hence, to fully assess the environmental exposures and risks associated with PPIs, it is important to better understand and evaluate the fate and behavior not only of the parent compound but also of their metabolites and their transformation products arising from biotic and abiotic processes (hydrolysis, photodegradation, biodegradation etc.) in the environment. In this light, the purpose of this review is to summarize the present state of knowledge on the introduction and behavior of these chemicals in natural and engineering systems and highlight research needs and gaps. It draws attention to their transformation, the increase contamination by their metabolites/TPs in different environmental matrices and their potential adverse effects in the environment. Furthermore, existing research on analytical developments with respect to sample treatment, separation and detection of PPIs and their metabolites/TPs is provided.

Seasonal occurrence, removal, mass loading and environmental risk assessment of 55 pharmaceuticals and personal care products in a municipal wastewater treatment plant in Central Greece.

A comprehensive study, which contains the seasonal occurrence, removal, mass loading and environmental risk assessment of 55 multi-class pharmaceuticals and personal care products (PPCPs), took place in the wastewater treatment plant (WWTP) of Volos, Greece. A one year monitoring study was performed and the samples were collected from the influent and the effluent of the WWTP. Solid phase extraction was used for the pre-concentration of the samples followed by an LC-DAD-ESI/MS analysis. Positive samples were further confirmed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The maximum concentrations of the PPCPs varied between 21 ng/L and 15,320 ng/L in the influents and between 18 ng/L and 9965 ng/L in the effluents. The most commonly detected PPCPs were the diuretic furosemide, the beta-blockers atenolol and metoprolol, the analgesics paracetamol, nimesulide, salicylic acid and diclofenac and the psychomotor stimulant caffeine. The removal efficiencies ranged between negative and high removal rates, demonstrating that the WWTP is not able to efficiently remove the complex mixture of PPCPs. The estimated mass loads ranged between 5.1 and 3513 mg/day/1000 inhabitants for WWTP influent and between 4.1 to 2141 mg/day/1000 inhabitants for WWTP effluent. Finally, environmental risk assessment has been regarded a necessary part of the general research. According to the results produced from the calculation of the risk quotient on three trophic levels, the anti-inflammatory drug diclofenac and the antibiotics, trimethoprim and ciprofloxacin, identified to be of high potential environmental risk for acute toxicity, while diclofenac also for chronic toxicity.

Comprehensive study of the antidiabetic drug metformin and its transformation product guanylurea in Greek wastewaters.

Many pollutants such as pharmaceuticals and their transformation products (TPs) are not efficiently removed from wastewater treatment plants and enter into surface waters. The aim of this study was to investigate the occurrence and behavior of metformin, one of the most prescribed drugs worldwide, and its biological transformation product guanylurea, in eight wastewater treatment plants (WWTPs) of Greece. All WWTPs were equipped with conventional activated sludge treatment and the samples were taken from the influents and the effluents, over the four seasons of one year. The analytical method developed based on SPE followed by LC-UV/Vis-ESI/MS analysis, while positive findings were confirmed also by means of LTQ Orbitrap mass spectrometer. High polarity of both compounds led to the extraction with Oasis HLB and the use of the anionic surfactant SDS. The results showed that metformin dominated in the influents (bql-1167 ng/L), while guanylurea in the effluents (bql-627 ng/L) of the wastewater treatment plants, with Metformin/Guanylurea ratio ranging between 0.88 and 81.3 in the influents and between 0.005 and 0.78 in the effluents. Lack of a clear seasonal tendency in the occurrence and removal or formation was observed. Finally, an ecotoxicological risk assessment of metformin in effluent wastewaters took place by calculating the ratio between the environmental concentrations (MEC) and the predicted no effect concentrations (PNEC). Despite the fact that metformin presented low risk in all cases, an environmental concern is suspected for guanylurea since it is continuously released into the aquatic environment.

Investigation of PPCPs in wastewater treatment plants in Greece: occurrence, removal and environmental risk assessment.

In the present work, an extensive study on the presence of eighteen pharmaceuticals and personal care products (PPCPs) in eight wastewater treatment plants (WWTPs) of Greece has been conducted. The study covered four sampling periods over 1-year, where samples (influents; effluents) from eight WWTPs of various cities in Greece were taken. All WWTPs investigated are equipped with conventional activated sludge treatment. A common pre-concentration step based on SPE was applied, followed by LC-UV/Vis-ESI-MS. Further confirmation of positive findings was accomplished by using LC coupled to a high resolution Orbitrap mass spectrometer. The results showed the occurrence of all target compounds in the wastewater samples with concentrations up to 96.65 µg/L. Paracetamol, caffeine, trimethoprim, sulfamethoxazole, carbamazepine, diclofenac and salicylic acid were the dominant compounds, while tolfenamic acid, fenofibrate and simvastatin were the less frequently detected compounds with concentrations in effluents below the LOQ. The removal efficiencies showed that many WWTPs were unable to effectively remove most of the PPCPs investigated. Finally, the study provides an assessment of the environmental risk posed by their presence in wastewaters by means of the risk quotient (RQ). RQs were more than unity for various compounds in the effluents expressing possible threat for the aquatic environment. Triclosan was found to be the most critical compound in terms of contribution and environmental risk, concluding that it should be seriously considered as a candidate for regulatory monitoring and prioritization on a European scale on the basis of realistic PNECs. The results of the extensive monitoring study contributed to a better insight on PPCPs in Greece and their presence in influent and effluent wastewaters. Furthermore, the unequivocal identification of two transformation products of trimethoprim in real wastewaters by using the advantages of the LTQ Orbitrap capabilities provides information that should be taken into consideration in future PPCP monitoring studies in wastewaters.

Occurrence and removal of PPCPs in municipal and hospital wastewaters in Greece.

A monitoring study was carried out for the four seasons over 1-year monitoring period (March 2006-March 2007) to investigate the residues of 11 pharmaceuticals and personal care products (PPCPs) belonging to various therapeutic categories. The selected areas of the study were the municipal and hospital wastewater treatment plants (WWTPs) of Ioannina city, located in Western Greece. The most common pre-treatment technique for pharmaceuticals, solid-phase extraction (SPE), was used for the isolation and pre-concentration of the target analytes. The samples were screened using gas chromatography mass spectrometry (GC-MS). The results of the monitoring study, showed the occurrence of all target compounds in the wastewater samples. Concentrations in the municipal WWTP ranged between 0.3 and 164.4 microg/L in the influent and between 0.5 and 13.9 microg/L in the effluent. In the hospital WWTP concentrations ranged between 0.6 and 70.1 microg/L in the influent and between 0.5 and 14.6 microg/L in the effluent. Mean removal efficiencies ranged between 13% and 97% and between 9% and 87% for municipal and hospital WWTPs, respectively. Removal efficiencies were higher in the municipal WWTP than in the hospital WWTP.