Evaluating membrane bioreactor treatment for the elimination of emerging contaminants using different analytical methods.

Since wastewater treatment plants (WWTPs) were not originally designed to eliminate contaminants of emerging concern (CECs), alternative strategies like membrane bioreactor (MBR) technology are gaining importance in achieving effective CEC removal and minimising their environmental impact. In this study, composite wastewater samples were collected from the biggest WWTP in the Basque Country (Galindo, Biscay) and the performance of two secondary treatments (i.e. conventional activated sludge treatment, CAS, and MBR) was assessed. The combination of a suspect screening approach using liquid chromatography tandem high-resolution mass spectrometry (LC-HRMS) and multitarget analysis by gas chromatography-mass spectrometry (GC-MS) allowed the detection of approximately 200 compounds in the WWTP effluents. The estimated removal efficiencies (REs) revealed that only 16 micropollutants exhibited enhanced removal by MBR treatment (RE > 70% or 40 - 60%). The environmental risk posed by the non-eliminated compounds after both treatments remained similar, being anthracene, clarithromycin, bis(2-ethylhexyl) phthalate (DEHP) and dilantin the most concerning pollutants (RQ > 1). The Microtox® bioassay confirmed the MBR's efficiency in removing baseline toxicity, while suggesting a similar performance of CAS treatment. These minimal differences between treatments call into question the worthiness of MBR treatment and emphasise the need to seek more efficient alternative treatment methods.

Suspect and non-target screening: the last frontier in environmental analysis.

Suspect and non-target screening (SNTS) techniques are arising as new analytical strategies useful to disentangle the environmental occurrence of the thousands of exogenous chemicals present in our ecosystems. The unbiased discovery of the wide number of substances present over environmental analysis needs to find a consensus with powerful technical and computational requirements, as well as with the time-consuming unequivocal identification of discovered analytes. Within these boundaries, the potential applications of SNTS include the studies of environmental pollution in aquatic, atmospheric, solid and biological samples, the assessment of new compounds, transformation products and metabolites, contaminant prioritization, bioremediation or soil/water treatment evaluation, and retrospective data analysis, among many others. In this review, we evaluate the state of the art of SNTS techniques going over the normalized workflow from sampling and sample treatment to instrumental analysis, data processing and a brief review of the more recent applications of SNTS in environmental occurrence and exposure to xenobiotics. The main issues related to harmonization and knowledge gaps are critically evaluated and the challenges of their implementation are assessed in order to ensure a proper use of these promising techniques in the near future.

Uptake of perfluorooctanoic acid, perfluorooctane sulfonate and perfluorooctane sulfonamide by carrot and lettuce from compost amended soil.

Sewage sludge, which acts like a sink for many pollutants, including metals, pathogens and organic pollutants, that are not completely removed in waste water treatment plants (WWTPs), is applied as a nutrient rich organic fertilizer in many agricultural applications. In the present work, carrot and lettuce crops were grown in two different compost amended soils fortified with perfluorooctanoic acid (PFOA), perfluorosulfonate acid (PFOS) and perfluorosulfonamide (FOSA) and cultivated in a greenhouse. The plants were harvested and divided into root core, root peel and leaves in the case of carrots and into heart and leaves for lettuces. Concentrations for all the different compartments were determined to assess the bioconcentration factors (BCFs) and the plant distribution of the target analytes. The highest carrot BCFs for PFOA and PFOS were determined in the leaves (0.6-3.4), while lower values were calculated in the core (0.05-0.6) and the peel (0.05-1.9) compartments. However, PFOA was taken up in the translocation stream and accumulated more than PFOS in the edible part of lettuce. FOSA was totally degraded in the presence of carrot; however, a lower FOSA degradation was observed in presence of the lettuce, which was dependent on the total organic carbon (TOC) content of the soil. The higher the TOC value, the higher the FOSA degradation observed. No degradation was observed in the crop absence. In the case of the carrot experiments, different polymeric materials (polyethersulfone, PES, polyoxymethylene, and silicone rod) were tested to predict the concentration in the cultivation media. A high correlation (r(2)>0.63) was observed for the BCFs in the PES and in the carrot core and peel for PFOA and PFOS. It could be, concluded that the PES can be used as a first approach for the determination of the uptake of compounds such as PFOS and PFOA in carrot.

Simultaneous determination of a variety of endocrine disrupting compounds in carrot, lettuce and amended soil by means of focused ultrasonic solid-liquid extraction and dispersive solid-phase extraction as simplified clean-up strategy.

The present study is focused on the development of an analytical method based on focused ultrasonic solid-liquid extraction (FUSLE) followed by dispersive solid-phase extraction (dSPE) clean-up and liquid chromatography-triple quadrupole tandem mass spectrometry (LC-MS/MS) optimised for the simultaneous analysis of certain endocrine disrupting compounds (EDCs), including alkylphenols (APs), bisphenol A (BPA), triclosan (TCS) and several hormones and sterols in vegetables (lettuce and carrot) and amended soil samples. Different variables affecting the chromatographic separation, the electrospray ionisation and mass spectrometric detection were optimised in order to improve the sensitivity of the separation and detection steps. Under the optimised extraction conditions (sonication of 5min at 33% of power with pulse times on of 0.8s and pulse times off of 0.2s in 10mL of n-hexane:acetone (30:70, v:v) mixture using an ice bath), different dSPE clean-up sorbents, such as Florisil, Envi-Carb, primary-secondary amine bonded silica (PSA) and C18, or combinations of them were evaluated for FUSLE extracts before LC-MS/MS. Apparent recoveries and precision in terms of relative standard deviation (RSDs %) of the method were determined at two different fortification levels (according to the matrix and the analyte) and values in the 70-130% and 2-27% ranges, respectively, were obtained for most of the target analytes and matrices. Matrix-matched calibration approach and the use of labelled standards as surrogates were needed for the properly quantification of most analytes and matrices. Method detection limits (MDLs), estimated with fortified samples, in the ranges of 0.1-100ng/g for carrot, 0.2-152ng/g for lettuce and 0.9-31ng/g for amended soil were obtained. The developed methodology was applied to the analysis of 11 EDCs in both real vegetable bought in a local market and in compost (from a local wastewater treatment plant, WWTP) amended soil samples.