Guidelines for routine mercury speciation analysis in seafood by gas chromatography coupled to a home-modified AFS detector. Application to the Andalusian coast (south Spain)

Abstract

A home-modified atomic fluorescence detector (mAFS) has been employed for mercury and methylmercury determination in bivalves from the Andalusian coast (south Spain). This modification consists on the inclusion of a quartz flow cell into the detector, which increases the concentration of mercury atoms in the detector and therefore enhances sensitivity about two fold. Two analytical approaches for mercury speciation based on the coupling of gas chromatography on-line pyrolysis and mAFS (GC–Pyro–mAFS) have been tested. The first approach ( Method 1) is based on aqueous ethylation followed by extraction into an organic solvent, and the second one ( Method 2) in the extraction of monoalkylated mercury as chloride. Method 1 is a rapid procedure but not sensitive enough for the analysis of methylmercury in non-polluted sites (detection limit: 20 ng g −1 as mercury, wet basis). The second one is quite more sensitive (detection limit: 0.2 ng g −1, wet weight), but sample treatment is cumbersome and time-consuming. The optimum range for mercury determination for both methods are complementary and exhibit an overlapping measurable concentration range (OMCR) in which methylmercury can be indistinctly determined (75–100 ng g −1 as mercury, wet basis). The suitability of both methods has been assayed with spiking experiences at levels within the OMCR with good recoveries. Both approaches have been validated with two certified reference materials (BCR-463, mercury and methylmercury in tuna fish; and NIST-2977, organic contaminants and trace metals in mussel tissue). Both procedures have been used for the analysis of three species of bivalve molluscs collected along the Andalusian coast (south Spain), all of them employed for human consumption ( Chamelea gallina, Donax trunculus and Scrobicularia plana), and their potential use in routine analysis has been established.