Characterization of the organic contamination pattern of a hyper-saline ecosystem by rapid screening using gas chromatography coupled to high-resolution time-of-flight mass spectrometry

Abstract

In this paper, gas chromatography coupled to high-resolution time-of-flight mass spectrometry (GC–TOF MS) has been applied to evaluate organic pollution in a hyper-saline aquatic environment. Firstly, a target screening was made for a list of 150 GC-amenable organic micro-contaminants, including PAHs, octyl/nonyl phenols, PCBs, PBDEs, and a notable number of pesticides, such us insecticides (organochlorines, organophosphorus, carbamates and pyrethroids), herbicides (triazines and chloroacetanilides), fungicides and several transformation products. This methodology was applied to brine samples, with a salt content from 112 g/L to saturation, and to samples from Artemia populations (crustacean Anostraca) collected during 1 year from three sampling stations in saltworks bodies sited in the Ebro river delta. Around 50 target contaminants, belong to chemical families included in the list of priority substances within the framework on European water policy.

Additionally, a non-target analysis was performed in both types of samples with the objective of investigating the presence of other non-selected organic compounds taking advantage of the potential of GC–TOF MS (high sensitivity in full-spectrum acquisition mode, accurate mass measurements) for searching unknowns. Organophosphorus pesticides were the contaminants more frequently detected in brine samples. Other compounds usually present in urban and industrial wastewaters, like caffeine, methylparaben, butylated-hydroxytoluene and N-butylbenzenesulfonamide were also detected in brines. The herbicide simazine and the insecticide chlorpyrifos were among the contaminants detected in Artemia samples.

Results of this work reveal a potential threat to vulnerable populations inhabiting the hyper-saline ecosystem. The valuable contribution of GC–TOF MS in environmental analysis, allowing the rapid screening of a large number of organic contaminants, is also demonstrated in this paper.