Oxygenated polycyclic aromatic hydrocarbons in mussels: analytical method development and occurrence in the Belgian...

An analytical method was developed for the trace quantification of oxygenated polycyclic aromatic hydrocarbons (oxyPAHs) in mussels. Compounds included were naphthalene-1-ol, 9H-fluoren-9-one, anthracene-9,10-dione, 7H-benz[de]anthracene-7-one, naphtacene-5,12-dione, and benzo[a]anthracene-7,12-dione. Pyrene-1-carboxaldehyde was applied as an internal standard. Sample extraction by pressurized liquid extraction was followed by cleanup on silica, separation by high performance liquid chromatography, and quantitative measurement by mass spectrometry with atmospheric pressure chemical ionization. The method was validated by the analysis of spiked mussel samples, resulting in trueness values of 90-124% and measurement uncertainties of 6-49%, except for naphthalene-1-ol. Quantification limits varied from 0.25 ng·g^-1 to 10.7 ng·g^-1. The developed analytical oxyPAH method was applied on mussel samples from groynes and quaysides along the Belgian coastline and oxyPAH data were compared to PAH concentration data. The sum of 14 US EPA priority PAHs reached maxima at the eastern side of the Belgian coastal zone, with on average 202 ng·g^-1 wet weight for quayside Zeebrugge and 38.4 ng·g^-1 wet weight for groyne Knokke mussels. Anthracene-9,10-dione concentrations reached maxima of 19.1 ng·g^-1 wet weight at the most industrialized quayside of Zeebrugge. For other oxyPAHs, no clear relationship could be made with direct PAH emissions. Concentrations of anthracene-9,10-dione and 9H-fluoren-9-one were found to exceed corresponding parent PAH concentrations.