The occurrence of chemical and biological contaminants of emerging concern (CECs) was investigated in treated wastewater intended for reuse in agriculture. An agarose hydrogel diffusion-based passive sampler was exposed to the outlet of a wastewater treatment plant (WWTP) located in Cyprus, which is equipped with membrane bioreactor (MBR). Passive samplers in triplicate were exposed according to a time-series exposure plan with maximum exposure duration of 28 days. Composite flow-proportional wastewater samples were collected in parallel with the passive sampling exposure plan and were processed by solid phase extraction using HORIZON SPE-DEX 4790 and the same sorbent material (Oasis HLB) as in the passive sampler. The analysis of passive samplers and wastewater samples enabled (i) the field-scale calibration of the passive sampler prototype by the calculation of in situ sampling rates of target substances, and (ii) the investigation of in silico predicted transformation products of the four most ecotoxicologically hazardous antibiotics (azithromycin, clarithromycin, erythromycin, ofloxacin). Additionally, the wastewater samples were subjected to the analysis of seven preselected antibiotic resistant genes (ARGs) and one mobile resistant element (int1). All extracts were analyzed for chemicals in a single batch using a highly sensitive method for pharmaceuticals, antibiotics and illicit drugs by liquid chromatography tandem MS/MS (LC-QQQ) and for various other target compounds (2316 compounds in total) by liquid chromatography high-resolution mass spectrometry (LC-HRMS). 279 CECs and all investigated ARGs (except for blaCTX-M-32) were detected, highlighting potential chemical and biological hazards related to wastewater reuse practices. 16 CECs were prioritized following ecotoxicological risk assessment, whereas sul1 and the mobile resistant element (int1) showed the highest abundance. Comprehensive monitoring efforts using novel sampling methods such as passive sampling, wide-scope target screening and molecular analysis are required to assure safe application of wastewater reuse and avoid spread and crop uptake of potentially hazardous chemicals.
Passive samplers based on diffusive gradients in thin hydrogel films (DGT) were recently modified for sampling of polar organic compounds in water. However, since the sampling rates of the commonly used DGT design with the surface area of 3.1 cm2 are low, we propose to increase them by applying a two-sided design with a larger sampling surface area of 22.7 cm2. The sampler design consists of two sorptive hydrogel disks compressed between two diffusive hydrogel disk layers strengthened by nylon netting and held together by two stainless steel rings. Sorbent/water distribution coefficients (KSW) were determined, and the sampler was calibrated for monitoring 11 perfluoroalkyl substances and 12 pharmaceuticals and personal care products in water at laboratory conditions using a closed system with artificial flow generated by submersible pumps. A field performance test was conducted at five locations in the Morava River basin in Czech Republic. The median value of laboratory-derived sampling rates was 43 mL day-1 with extreme values of 2 mL day-1 and 90 mL day-1 for perfluorotridecanoic and perfluoroheptanoic acids, respectively. The log KSW values of tested compounds ranged from 3.18 to 5.47 L kg-1, and the estimated halftime to attain sampler-water equilibrium ranged from 2 days to more than 28 days, which is the maximum recommended exposure period, considering potential issues with the stability of hydrogel. The sampler can be used for assessment of spatial trends as well as estimation of aqueous concentration of investigated polar compounds.
- MeSH
- Water Pollutants, Chemical analysis MeSH
- Diffusion MeSH
- Fluorocarbons chemistry MeSH
- Hydrogels chemistry MeSH
- Heptanoic Acids chemistry MeSH
- Organic Chemicals chemistry MeSH
- Rivers chemistry MeSH
- Sepharose chemistry MeSH
- Water MeSH
- Publication type
- Journal Article MeSH
- Geographicals
- Czech Republic MeSH
