A SPE-HPLC-MS/MS method for the simultaneous determination of pr ior itised pharmaceuticals and EDCs with high environmental risk potential in freshwater

This work describes the development,optimisation and validation of an analytical method for the rapid determination of 17 priority pharmaceutical compounds and endocrine disrupting chemicals(EDCs).Rather than studying compounds from the same therapeutic class,the analyses aimed to determine target compounds with the highest risk potential(with particular regard to Scotland),providing a tool for further monitoring in different water matrices.Prioritisation was based on a systematic environmental risk assessment approach,using consumption data;wastewater treatment removal efficiency;environmental occurrence;toxicological effects;and pre-existing regulatory indicators.This process highlighted 17 compounds across various therapeutic classes,which were then quantified,at environmentally relevant concentrations,by a single analytical methodology.Analytical determination was achieved using a single-step solid phase extraction(SPE)procedure followed by high-performance liquid chromatography with tandem mass spectrometry(HPLC-MS/MS).The fully optimised method performed well for the majority of target compounds,with recoveries>71%for 15 of 17 analytes.The limits of quantification for most target analytes(14 of 17)ranged from 0.07 ng/L to 1.88 ng/L in river waters.The utility of this method was then demonstrated using real water samples associated with a rural hospital/setting.Eight compounds were targeted and detected,with the highest levels found for the analgesic,paracetamol(at up to 105,910 ng/L in the hospital discharge).This method offers a robust tool to monitor high priority pharmaceutical and EDC levels in various aqueous sample matrices.

Occurrence, variations, and risk assessment of neonicotinoid insecticides in Harbin section of the Songhua River, northeast China

Neonicotinoid insecticides(NNIs)have been intensively used and exploited,resulting in their presence and accumulation in multiple environmental media.We herein investigated the current levels of eight major NNIs in the Harbin section of the Songhua River in northeast China,providing the first systematic report on NNIs in this region.At least four NNIs in water and three in sediment were detected,with total concentrations ranging from 30.8 to 135 ng L^(-1) and from 0.61 to 14.7 ng g^(-1) dw,respectively.Larger spatial variations in surface water NNIs concentrations were observed in tributary than mainstream(p<0.05)due to the intensive human activities(e.g.,horticulture,urban landscaping,and household pet flea control)and the discharge of wastewater from many treatment plants.There was a significant positive correlation(p<0.05)between the concentrations of residual imidacloprid(IMI),clothianidin(CLO),and S4NNIs in the sediment and total organic carbon(TOC).Due to its high solubility and low octanol-water partition coefficient(Kow),the sediment-water exchange behavior shows that NNIs in sediments can re-enter into the water body.Human exposure risk was assessed using the relative potency factor(RPF),which showed that infants have the highest exposure risk(estimated daily intake(SIMIeq EDI):31.9 ng kg^(-1) bw$d^(-1)).The concentration thresholds of NNIs for aquatic organisms in the Harbin section of the Songhua River were determined using the species sensitivity distribution(SSD)approach,resulting in a value of 355 ng L^(-1) for acute hazardous concentration for 5%of species(HC5)and 165 ng L^(-1) for chronic HC5.Aquatic organisms at low trophic levels were more vulnerable to potential harm from NNIs.