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.

Simple analytical methodology based on solid phase extraction for monitoring pesticide residues in natural waters.

Pesticide contamination of natural waters due to agricultural activities has been a widely publicized topic over the past 30 years and will continue to be a problem in the future. The determination of pesticide residues in water samples is necessary for solving various environmental problems. The aim of this work was to develop an efficient method on the basis of solid phase extraction (SPE) technique for the determination of 34 multiclass pesticides in natural waters. SPE using C18 extraction disks followed by gas chromatography (GC-MS) and liquid chromatography (LC-MS) were used for the determination of various pesticides residues in environmental waters. The developed SPE method provided good repeatability and reproducibility range, high extraction efficiency and low LODs. The performance results confirm the usefulness of the proposed methodology for the analysis multiclass pesticides in natural waters. The key benefits of this methodology are:•It possesses the advantages of SPE (fast, simple, highly sensitive) and could be potentially extended to other classes of pesticides.•It can be used as a useful tool for monitoring purposes on natural waters.•The validated methodology meets regulatory requirements established by the EU [1] and other authorities of developed countries [2].

Environmental monitoring and risk assessment of pesticide residues in surface waters of the Louros River (N.W. Greece).

Estuarine environments are being constantly stressed by new sources of pollution (e.g. pesticides) derived from activities of industry and intensive agriculture. The present study aims at quantify pesticides of three different categories (fungicides, herbicides and insecticides) in the Louros River (Epirus region, North-Western Greece). A monitoring study of 34 compounds was carried out in surface river waters from June 2011 until May 2012. Seven water sampling stations were established and 35 water samples were collected. A solid-phase extraction (SPE) method coupled with gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS), depending on the compound, was developed and validated. During the monitoring study 25 pesticides were detected (13 herbicides, 9 insecticides, 3 fungicides). The most commonly encountered pesticides were quizalofop-ethyl, trifluralin and pendimethaline. Tebufenpyrad was found in all sampling stations and seasons, with the highest concentrations of 0.330 µg/L at Tsopeli Lagoon exceeding the rather low concentrations reported nationwide. Regarding the environmental risk due to the presence of target compounds in surface waters, this was estimated by calculating risk quotients (RQs) for different aquatic organisms (algae, zooplankton and fish). The results denoted a possible threat for the aquatic environment, rendering in this way the RQ method as a useful screening tool. In any case, further extensive study is needed for acetochlor, pirimiphos-methyl, endosulfan-a and azinphos-ethyl in order to better correlate their occurrence and potential toxic effects in aquatic life and humans.

Persistent and emerging pollutants assessment on aquaculture oysters (Crassostrea gigas) from NW Portuguese coast (Ria De Aveiro).

The study aim was to determine a range of relevant persistent and emerging pollutants in oysters produced in an aquaculture facility located in an important production area, to assure their safety for human consumption. Pollutants, including 16 PAHs, 3 butyltins (BTs), 29 flame retardants (FRs, including organophosphate and halogenated FRs), 35 pesticides (including 9 pyrethroid insecticides) and 13 personal care products (PCPs, including musks and UV filters), were determined in oysters' tissues collected during one year in four seasonal sampling surveys. The seasonal environmental pollution on the production site was evaluated by water and sediment analysis. Furthermore, oysters' nutritional quality was also assessed and related with the consumption of healthy seafood, showing that oysters are a rich source of protein with low fat content and with a high quality index all year around. Results showed that most analysed pollutants were not detected either in oyster tissues or in environmental matrixes (water and sediments). The few pollutants detected in oyster tissues, including both regulated and non-legislated pollutants, such as a few PAHs (fluorene, phenanthrene, anthracene, fluoranthene, pyrene and indenopyrene), FRs (TPPO, TDCPP, DCP, BDE-47, BDE-209 and Dec 602) and PCPs (galaxolide, galaxolidone, homosalate and octocrylene), were present at low levels (in the ng/g dw range) and did not represent a significant health risk to humans. The observed seasonal variations related to human activities (e.g. tourism in summer) highlights the need for environmental protection and sustainable resource exploration for safe seafood production.