Conny Danielsson

Evaluation of modulators and electron-capture detectors for comprehensive two-dimensional GC of halogenated organic compounds

Different cryogenic and a heated GC x GC modulator(s) were evaluated and compared for the analysis of high-boiling halogenated compounds. The cryogenic modulators investigated were: (i) the longitudinally modulated cryogenic system; (ii) the liquid-nitrogen-cooled jet modulator (KT2001); (iii) a dual-jet CO2 modulator (made in-house); (iv) a semi-rotating cryogenic modulator (made in-house) and (v) a CO2 loop modulator (KT2003); the heated modulator was the slotted heater system (sweeper). Each modulator was optimised with respect to analyte peak widths at half height in the second-dimension. n-Alkanes, chlorinated alkanes, polychlorinated biphenyls (PCBs) and fluorinated polycyclic aromatic hydrocarbons (F-PAHs) were used as test analytes. The flow rate of the coolant was found to be an important parameter, i.e. the flow rate of the gaseous nitrogen in the KT2001, and of the liquid CO2 in the other cryogenic modulators. For the slotted heater the stroke velocity and pause time were important parameters. This modulator had a limited application range in terms of temperature due to a necessary 100 degrees C difference between sweeper and oven temperature. All cryogenic modulators were found to be suitable for the GC x GC analysis of high-boiling compounds, but the CO2 modulators are to be preferred to the KT2001 due to a wider application range and slightly narrower peaks. As regards the performance of three commercially available electron-capture detectors (ECDs), the aim was to obtain narrow peak widths in GC x GC, i.e. to avoid band broadening caused by the cell volume. The most important parameters were the flow rate of the make-up gas and the detector temperature which both should be as high as possible. Comparison of analyte peak widths obtained with ECD mode and flame ionisation detection (FID) showed that all ECDs exhibited band broadening compared to the FID. The narrowest peaks were obtained with the Agilent micro-ECD, which has a cell volume of only 150 microl.

Accumulation of Polybrominated Diphenyl Ethers, Hexabromobenzene, and 1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane in Earthworm (Eisenia fetida). Effects of Soil Type and Aging

In the present study the accumulation potentials in earthworms (Eisenia fetida) of selected brominated flame retardants (BFRs) were investigated. The tested BFRs, including polybrominated diphenyl ethers (PBDEs), hexabromobenzene (HBB), and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), were found to be bioavailable to Eisenia fetida, and they accumulated in the earthworms. To our knowledge, this is the first published study to address the bioaccumulation potential of TBECH in terrestrial biota. Aging the soil resulted in decreased accumulation of TBECH, HBB, and PBDEs with six or less bromine atoms. However, no effect of soil aging was seen for BDEs 183 or 209, possibly due to their low mobility in soil. The use of different soils (artificial OECD soil and two natural Swedish soils) also affected the degree of accumulation in the worms. The results indicate that use of the generally accepted standard OECD soil may overestimate accumulation of organic contaminants by earthworms, due to high bioavailability of the contaminants and/or weight loss of the worms in it. Further, the accumulation of selected PBDEs and HBB was compared to the accumulation of their chlorinated analogues. Brominated compounds accumulated to the same or a lesser extent than their chlorinated counterparts.