A protocol for wide-scope non-target analysis of contaminants in small amounts of biota using bead beating tissuelyser extraction and LC-HRMS.

This work describes a robust and powerful method for wide-scope target and non-target analysis of xenobiotics in biota samples based on bead beating tissuelyser extraction, solid phase extraction (SPE) clean-up and further detection by liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS). Unlike target methodologies, non-target methods usually aim at determining a wide range of still unknown substances with different physicochemical properties. Therefore, losses during the extraction process were minimised. Apart from that, the reduction of possible interferences showed to be necessary to expand the number of compounds that can be detected. This was achieved with an additional SPE clean-up step carried out with mixed-bed multi-layered cartridges. The method was validated with a set of 27 compounds covering a wide range of physicochemical properties, and further applied to the analysis of krill and fish samples.•The bead beating extraction was efficient for a wide range of organic pollutants in small quantities of biota samples.•Multi-layered solid phase extraction clean-up yield a wide xenobiotics coverage reducing matrix effects.•Method validation with 27 compounds led to a suitable method for non-target analysis of organic pollutants in biota.

Showcasing the potential of wastewater-based epidemiology to track pharmaceuticals consumption in cities: Comparison against prescription data collected at fine spatial resolution.

While the extent of pharmaceutical consumption within a society/community is of high relevance to its health, economy and general wellbeing, this data is often not readily available. Herein, we strengthen a wastewater-based epidemiology (WBE) approach as a way to track the consumption of pharmaceuticals within the sampled community. This method is less laborious than established questionnaire or databases approaches and allows a higher temporal and spatial resolution. The WBE approach was conducted by sampling influent wastewater from two wastewater treatment plants of different size. A total of 39 targeted compounds were quantified by liquid chromatography coupled with tandem mass spectrometry. The number of prescriptions and the defined daily doses for each prescription was obtained from the reference database of The Catalan Health System to validate the wastewater-based approach. The wastewater sampling and the data inquiry were both executed during the same period (October 2019) and standardised for comparison to treatments per 1,000 inhabitants per day. The back-calculation parameters were improved from previous studies by including the faecal excretion rate of the pharmaceuticals. For prescription only pharmaceuticals, where prescription numbers are expected to be a good estimate of consumption, our WBE approach agreed with 27 out of 32 (<0.7 order of magnitude). Common over-the-counter pharmaceuticals such as acetaminophen, ibuprofen and naproxen showed much higher values for treatments per day per 1,000 inhabitant in wastewater than prescribed, reflecting the usefulness of WBE in obtaining an estimate of the total consumption i.e. with and without a prescription.

Contaminants of emerging concern in freshwater fish from four Spanish Rivers.

This study investigated the occurrence of 135 contaminants of emerging concern (CECs) - pharmaceuticals, pesticides, a set of endocrine disrupting compounds (EDCs) (parabens, bisphenols, hormones, triazoles, organophosphorus flame retardants and triclosan), UV-filters, perfluoroalkyl substances (PFASs) and halogenated flame retardants (HFRs) - in 59 fish samples, collected in 2010 in 4 Spanish Rivers (Guadalquivir, Júcar, Ebro and Llobregat). Of the 135 CECs, 76 including 8 pharmaceuticals, 25 pesticides, 10 EDCs, 5 UV-filters, 15 PFASs and 13 HFRs were detected. Pharmaceuticals were the less frequently found and at lower concentrations. Pesticides, EDCs, UV-filters, PFASs and HFRs were detected more frequently (>50% of the samples). The maximum concentrations were 15 ng/g dry weight (dw) for pharmaceuticals (diclofenac), 840 ng/g dw for pesticides (chlorpyrifos), 224 ng/g dw for EDCs (bisphenol A), 242 ng/g dw for UV-filters (EHMC), 1738 ng/g dw for PFASs (PFHxA) and 64 ng/g dw for HFRs (Dec 602). The contaminants detected in fish are commonly detected also in sediments. In light of current knowledge, the risk assessment revealed that there was no risk for humans related to the exposure to CECs via freshwater fish consumption. However, results provide detailed information on the mixtures of CECs accumulated that would be very useful to identify their effects on aquatic biota.