Ultra-trace determination of phthalate ester metabolites in seawater, sediments, and biota from an urbanized marine inlet by LC/ESI-MS/MS

Abstract

This study presents results of an analytical method developed for the quantification of monoalkyl phthalate esters (MPEs) in seawater, sediments, and biota. The method uses accelerated solvent extraction, solid-phase extraction, and liquid chromatography electrospray ionization tandem mass spectrometry (LC/ ESI-MS/MS). Results show the method is robust and can provide trace measurement of several MPE analytes at low parts per trillion levels in water and low parts per billion levels in sediments and biological tissues. Analyte recoveries varied between 70% and 110%. Method detection limits (MDLs) varied between 0.19 and 3.98 ng/L in seawater and between 0.024 and 0.99 ng/g in sediment and biota, which is approximately 10-50 times lower than previously reported MDLs using gas chromatography mass spectrometry. We applied the method to field collected samples of seawater, sediments, and tissues of mussels, crabs, and fish from False Creek an urbanized marine inlet near Vancouver, Canada. The results indicate residues of several MPEs can be found in surface waters, sediments, and organism tissues of this marine system. Monoethyl phthalate (MEP), mono-n-butyl phthalate (MnBP), and mono-(2-ethylhexyl)-phthalate (MEHP) were frequently detected in all matrices. MnBP generally exhibited the highest concentrations among MPEs analyzed. Detectable concentrations of MPEs varied from 1 to 600 ng/L in seawater, 0.1 to 20 ng/g dry wt in sediments, and 0.1 to 600 ng/g wet wt in biota. Observed concentrations of low molecular weight MPEs in mussels were found to be significantly higher (P < 0.05) than those of corresponding parent DPEs (e.g., MnBP > DBP). Mono-iso-nonyl-phthalate (MoC9) and mono-iso-decyl phthalate (MoC10), which were routinely detected in water and sediments, were not detected in False Creek biota, indicating negligible uptake and/or in vivo bioformation of these high molecular weight MPEs. The ability to measure MPEs in complex environmental samples provided by this LC/ESI-MS/MS method expands the capability for future biomonitoring and risk assessment of phthalate plasticizers.