title: Congener specific determination of polychlorinated naphthalenes in sediment and biota by gas chromatography high resolution mass spectrometry.
abstract: An isotope dilution congener-specific method for the determination of the most abundant and most toxic polychlorinated naphthalenes (PCNs) was developed using gas chromatography with high resolution mass spectrometry (GC-HRMS). The method was used to determine the concentration of 24 target congeners and total PCN concentrations in fish and sediment samples. Tissue samples were extracted using pressurized liquid extraction (PLE) and sediment samples were extracted using Soxhlet extraction. Sample extracts were cleaned up using either a manual two-stage open column procedure or an automated FMS Power Prep System with multi-analyte and multi-sample capability using a three-column cleanup procedure. Sediment extracts were cleaned up with a dual open column cleanup technique involving the use of both a multi-layered silica (silver nitrate/acid/base/neutral silica) column followed by column containing carbon-activated silica. Fish tissue extracts were cleaned up on the automated system involving the use of a high capacity ABN (acid/base/neutral column), carbon celite column, and a basic alumina column. The method is capable of producing instrument detection limits (IDLs) between 0.06 and 0.13pg for each PCN (on column), with method detection limits (MDLs) for the fish extracts ranging from 1.3 to 3.4pg/g (wet weight) and 0.46 to 1.2pg/g (dry weight) for sediments. The average accuracy of 34 spiked fish samples analysed over a period of several months was 100% with a precision (%RSD) of 12%. Similarly, the average accuracy for 28 spiked sediment samples was 104% with a precision (%RSD) of 12%. The application of the method to environmental samples was demonstrated through the analysis of sediment and fish samples obtained from Lake Ontario, Canada. The method is used both for the determination of 24 PCNs and to perform non-targeted screening for the remaining 51 PCN congeners, which are included in the total PCN quantification result. It is currently one of the most comprehensive and accurate congener-specific methods available and was developed from the existing techniques used for the determination of polychlorinated dioxins and furans to produce high quality data with only minor modifications in the clean-up procedure. It can therefore be readily adopted by other laboratories performing dioxin and POP analyses.
authors.affiliation: Ontario Ministry of the Environment and Climate Change, Toronto, ON, M9P 3V6, Canada.
authors.forename: R
authors.initials: R
authors.lastname: Lega
authors.affiliation: University of Toronto, Department of Chemistry, Toronto, ON, M5S 3H6, Canada; Manchester Metropolitan University, School of Science and the Environment, Manchester, M1 5GD, UK. Electronic address: dpmegson@hotmail.co.uk.
authors.forename: D
authors.initials: D
authors.lastname: Megson
authors.affiliation: Ontario Ministry of the Environment and Climate Change, Toronto, ON, M9P 3V6, Canada.
authors.forename: C
authors.initials: C
authors.lastname: Hartley
authors.affiliation: Ontario Ministry of the Environment and Climate Change, Toronto, ON, M9P 3V6, Canada.
authors.forename: P
authors.initials: P
authors.lastname: Crozier
authors.affiliation: Ontario Ministry of the Environment and Climate Change, Toronto, ON, M9P 3V6, Canada.
authors.forename: K
authors.initials: K
authors.lastname: MacPherson
authors.affiliation: Ontario Ministry of the Environment and Climate Change, Toronto, ON, M9P 3V6, Canada.
authors.forename: T
authors.initials: T
authors.lastname: Kolic
authors.affiliation: Ontario Ministry of the Environment and Climate Change, Toronto, ON, M9P 3V6, Canada.
authors.forename: P A
authors.initials: PA
authors.lastname: Helm
authors.affiliation: Ontario Ministry of the Environment and Climate Change, Toronto, ON, M9P 3V6, Canada.
authors.forename: A
authors.initials: A
authors.lastname: Myers
authors.affiliation: Ontario Ministry of the Environment and Climate Change, Toronto, ON, M9P 3V6, Canada.
authors.forename: S P
authors.initials: SP
authors.lastname: Bhavsar
authors.affiliation: Ontario Ministry of the Environment and Climate Change, Toronto, ON, M9P 3V6, Canada; University of Toronto, Department of Chemistry, Toronto, ON, M5S 3H6, Canada.
authors.forename: E J
authors.initials: EJ
authors.lastname: Reiner
mesh_terms: D000818:Animals; D005399:Fishes / Q000378:metabolism; D008401:Gas Chromatography-Mass Spectrometry; D019015:Geologic Sediments / Q000737:chemistry; D057230:Limit of Detection; D059625:Liquid-Liquid Extraction; D009281:Naphthalenes / Q000032:analysis* / Q000737:chemistry / Q000302:isolation & purification; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000737:chemistry
chemical_list: D009281:Naphthalenes; D014874:Water Pollutants, Chemical
keywords: Biota; Gas chromatography; High resolution mass spectrometry; PCN; Polychlorinated naphthalenes; Sediment