title: Low-resolution mass spectrometric relative response factors (RRFs) and relative retention times (RRTs) on two common gas chromatographic stationary phases for 87 polychlorinated dibenzofurans.
abstract: All 87 tetra- to octa-chlorinated dibenzofurans (PCDFs) were analysed using high-resolution gas chromatography/low-resolution mass spectrometry (HRGC-LRMS). The mass spectrometer was operated in two different modes: electron ionisation (EI), and negative ion chemical ionisation (NCI) with methane as a reagent gas. Baseline separation and identification of all PCDF congeners was carried out using one non-polar (DB-5) and one polar (RT-2330) capillary GC column. Relative retention times (RRTs) on both columns, and relative response factors (RRFs) in both EI- and NCI-modes, were calculated for all 87 of the PCDFs. Comparison of the EI-RRFs and NCI-RRFs showed that the mass spectrometric NCI-responses varied to a higher degree than the EI-responses. The level of NCI-response was dependent on the substitution positions of the chlorine atoms on the dibenzofuran molecule skeleton. The ratio between the highest and lowest RRFs was 26 in the NCI-mode, but only 2.3 in the EI-mode. Thus, quantification of tetra- to octa-CDFs in environmental samples using the NCI-mode will result in incorrect estimates of PCDF concentrations unless 13C-labelled internal standards are used for each congener, or RRFs are taken into consideration. In contrast, the quantification of PCDFs in the EI-mode using a single internal 13C-labelled PCDF standard for each PCDF homologue is accurate according to the findings in this investigation. A flue gas sample from a municipal solid waste incinerator (MSWI) analysed in the NCI-mode was quantified with and without NCI-RRFs. When using NCI-RRFs the reported concentration of SigmaPCDFs in the flue gas sample increased by 40%. Furthermore, TCDF analysis was compared using two mass spectrometers (a VG 12-250 and a Finnigan 4500) operating in EI-mode. These quadrupole instruments performed equally well, giving similar EI-RRFs for the tested compounds.
authors.affiliation: Environmental Chemistry, Department of Chemistry, Umeå University, SE-90187 Umeå, Sweden. kjell.lundgren@chem.umu.se
authors.forename: Kjell
authors.initials: K
authors.lastname: Lundgren
authors.forename: Christoffer
authors.initials: C
authors.lastname: Rappe
authors.forename: Mats
authors.initials: M
authors.lastname: Tysklind
mesh_terms: D001572:Benzofurans / Q000032:analysis* / Q000737:chemistry*; D002247:Carbon Isotopes; D000072338:Dibenzofurans, Polychlorinated; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D008697:Methane; D013997:Time Factors
chemical_list: D001572:Benzofurans; D002247:Carbon Isotopes; D000072338:Dibenzofurans, Polychlorinated; D008697:Methane