Single injection LC-MS/MS analytical method for the quantification of diverse families of micropollutants, including PFAS and organotins, in Gammarus fossarum.

ABSTRACT

Since the last decades, light has been shed on the pollution of aquatic ecosystems. Considering apolar compounds in water, analysis of the dissolved phase is not sufficient due to their possible bioaccumulation. Additional analysis of sediments, biota, or sentinel species is necessary. Among sentinel species, Gammarus fossarum is a small shrimp of 30 mg that lives naturally in the river. Its ability to bioaccumulate makes it a good bioindicator of river pollution. Nevertheless, micropollutants are difficult to extract from gammarids due to their small size and their high level of lipids. Extracted interferences can lead to analytical difficulties. Targeted micropollutants in this work were organotins, personal and pharmaceutical care products (PPCPs), pesticides, flame retardants, and perfluorinated compounds. A sample preparation based on QuEChERS followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) was developed different salts (acetate and citrate) and purification (addition of hexane, dispersive SPE) were tested and validated. Targeted molecules used to be analyzed by LC-MS/MS, except organotins which are principally analyzed in gas chromatography. One of the main challenges was to quantify them also in LC-MS/MS to implement an original multi-residue method. The analysis of 40 compounds was finally validated according to ICH guidelines, with LOQs ranging from 0.04 ng.g-1 to 313.5 ng.g-1. Regarding Perfluorooctanesulfonic acid (PFOS) and the sum of hexabromocyclododecane, LOQs reached the environmental quality standards in biota which are respectively of 9.1 and 167 ng.g-1. Finally, the method was applied to 15 real samples. Many compounds were quantified perfluorinated compounds, drugs such as ketoprofen, and even cosmetics products such as octocrylene. This is the first study to quantify as many emerging compounds, especially organotins, in a sentinel species such as G. fossarum.