BIOMEDICAL AND ENVIRONMENTAL MASS SPECTROMETRY, VOL. 14, 375-381 (1987) A Comparison of Chromatographic and Chromatographic/Mass Spectrometric Techniques for the Determination of Polycyclic Aromatic Hydrocarbons in Marine Sediments* P. G. Sim'F, R. K. Boyd, R. M. Gersheyf, R. Guevremont and W. D. Jamieson zyxw Marine Analytical Chemistry Standards Program, Atlantic Research Laboratory, National Research Council of Canada, 1411 Oxford St., Halifax, Nova Scotia, Canada, B3H 321 M. A. Quilliam and R. J. Gergely Department of Chemistry, McMaster University, Hamilton, Ontario, Canada, L8S 4M1 The establishment of reliable values for concentrations of 16 priority pollutant polycyclic aromatic hydrocarbons (PAH) in a suite of marine sediment reference materials included an examination of the methods used to determine such compounds. Results from the five techniques zyxwvut used indicate large method biases. The biases arise from chemical interferences in methods which use non-selective measuring systems with separation techniques which do not first completely resolve the analytes; e.g., single-parameter optical detectors with high performance liquid chromato- graphic (HPLC) techniques or a flame ionisation detector (FID) with capillary column gas chromatographic (GC) methods. Measurement by a mass spectrometer with HPLC and GC removes much of the method bias. Results for a representative sediment are discussed to illustrate these conclusions. INTRODUCTION The increasing use of coastal marine resources requires that adequate programs be in place for the monitoring of hazardous pollutants. Sediments are of particular concern since a large portion of contaminants adsorb on particulate matter which settle to the sea floor, and since a strong correlation exists between sediment levels of some pollutants and organism concentrations.' Poly- cyclic aromatic hydrocarbons (PAH) are members of a very important class of pollutants because of their mutagenic and carcinogenic properties.273Sources of PAH in marine sediments include combustion emissions deposited by atmospheric precipitation and fallout, industrial waste dumping, sewage effluents and petroleum spills. The assessment of possible hazards to the fishery or aquaculture operations requires the accur- ate assessment of both the identities and quantities of PAH present. For the routine analysis of PAH mixtures as complex as those found in marine sediments, it is essential to have available well characterised standard reference materials (SRM). As an aid for analysts involved in such work, the Marine Analytical Chemistry Standards Pro- zyxwvu * NRCC No. 26728. t Author to whom correspondence should be addressed. $ Present address: Seakem Oceanography Ltd., Argo Building, Bed- ford Institute of Oceanography, P.O. Box 696, Dartmouth, Nova Scotia, Canada, B2Y 3Y9 zyxwvutsrqpo Abbreviations: FID, flame ionisation detector; FLD, fluorescence detector; GC, capillary column gas chromatography; HPLC, high performance liquid chromatography; HPLC/O, HPLC with single- parameter optical detection; HPLC/MS, directly-coupled liquid chromatography/MS; MACSP, Marine Analytical Chemistry Stan- dards Program; MS, mass spectrometry; MS/MS, tandem mass spec- trometry; NBS, United States National Bureau of Standards; PAH polycyclic aromatic hydrocarbons(s); SRM, standard reference material(s); UVD, ultraviolet absorption detector. 0887-6134/87/080375-07 $05.00 @ 1987 by John Wiley & Sons Ltd gram (MACSP) of the National Research Council of Canada is preparing a suite of reference materials for the determination of PAH in marine sediments. This MACSP work is designed to meet the need for such materials over the next few years. The members of the suite of sediments are to be certified for the concentra- tions of 16 PAH which have been designated priority pollutants by the United States Environmental Protec- tion Agency (see Table 2 for list). A necessary condition for the certification of com- pound concentrations in reference materials is that determinations must be made by at least two indepen- dent, complementary methods of analysis in order to avoid systematic errors associated with any one par- ticular technique. It is important in such work to have a high degree of confidence that the analytical signal being measured is attributed to only one specific target compound before attempting any quantification. With complex mixtures the analytical procedure must provide a high overall resolution through a combination of pre- parative fractionation methods to isolate compound classes and high column efficiency and separation selec- tivity in the final chromatographic analysis. Selective detectors can be very important for further reducing interferences but are not so useful for 'broad-spectrum' screening of samples. Spectroscopic detectors such as mass spectrometers offer both universal and selective detection capabilities as well as a high degree of confidence in compound identification. As part of the certification process, samples of a suite of dried, homogenised candidate sediment reference materials were analysed for PAH by various techniques in a number of laboratories. In this paper we examine results from these analyses for just one of these sedi- ments. The techniques used were capillary column gas chromatography (GC) with flame ionisation detection (FID), combined GC/MS, reversed phase high perform-