Phthalate esters (PEs) are a group of widely used commercial chemicals consisting of many different congeners. Concentrations of di(2-ethylhexyl) phthalate ester in the parts per million range have been observed in sediments from locations in North America and Europe. However, sediment and biota concentrations of other widely used PEs (i.e., dibutyl phthalate, dusononyl phthalate, and dusodecyl phthalate) are rare and often in doubt because of analytical difficulties. One of the problems is that commercial formulations predominantly consist of PEs with a specific molecular weight but include many isomers within each molecular weight class. Currently there are no analytical methods or required standards to fully separate PEs into the different molecular weight classes corresponding to the formulations from which they originate. Hence, ambient total and mixture-specific PE concentrations do not exist. This study presents a new method based on reversed-phase liquid chromatography/ electrospray ionization mass spectrometry (LC/ESI-MS) for the quantitative determination of individual PEs, including six congeners on the U.S. EPA Priority pollutant list and several commercial PE isomeric mixtures, in complex environmental matrixes. The method is applied to determine the composition of PE concentrations in sediments and fish in an urbanized marine ecosystem. PE fingerprints in sediments show a predominance of high molecular weight PEs and match per capita consumption levels of PEs. Fingerprints in fish tissue show a predominance of low molecular weight PEs and do not match per capita consumption levels. The findings indicate that the higher molecular weight PEs are less biologically available than the lower molecular weight ones.
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