Determination of biogenic halogenated methyl-phenyl ethers (halogenated anisoles) in the picogram m -3 range in air

Abstract

Halogenated anisoles (methyl-phenyl ethers) appear to be ubiquitous organic trace compounds in the environment. An analytical method is presented for analyzing the altogether 134 congeners of chloro-, bromo- and mixed bromochloro-anisoles on an isomer-specific basis in air. High volume sampling (20 m(3) per hour) is carried out by adsorption, using a mixture of silica gel 60 and ENVI-Carb. The preseparation of the anisoles is achieved by NP-LC on Florisil (a magnesium silicate). The interference by volatile n-alkyl nitrates in the electron-capture detection can be avoided by a LC-preseparation on a carboneous phase. The isomer-specific separation and detection is performed by HRGC-ECD and HRGC-MS-SIM. A structure-specific systematic numbering of the 134 congeners of the chloro-, bromo- and bromochloro-anisoles is suggested. The retention data are given of 16 chloroanisoles, 10 bromoanisoles and 27 bromo-chloroanisoles on three stationary phases with different polarity.

Northern Rivers Ecosystem Initiative: Distribution and Effects of Contaminants

“…Spatial trends of PCBs and toxaphene in burbot liver (ng/g ww; lipid adjusted) in the PeaceAthabasca River basin from this study and comparison with results from Great Slave Lake/Slave River from Evans et al (1996). (Führer et al, 1996). Pentachloroanisole (PCA), a methylated derivative of pentachlorophenol, was included as a marker of old wood preservation facilities.…”

QSPR models for the physicochemical properties of halogenated methyl-phenyl ethers

“…The inclusion of E HOMO in the model (1) indicates that there is probably electron-transfer process in the interaction between molecules. The parameter has a negative sign, which means that the larger E HOMO , the lower the p L value.…”

“…The experimentally determined physicochemical properties of halogenated anisoles were taken from previous publications [1,10], including sub-cooled liquid vapor pressures (lg p L ), noctanol/water partition coefficient (lg K ow ) and water solubilities (Àlg S w,L ). These data, together with the chemical names and the predicted properties from QSPR models for all 134 halogenated anisoles, are collected in Table S1 of the supplementary materials.…”

“…There are 134 possible congeners consisting of 19 chloroanisoles, 19 bromoanisoles and 96 bromo-chloroanisoles. Although they are not produced in industrial quantities, various members of the halogenated methyl-phenyl ethers have been detected in the air, water, sediments, food, marine algae and fish [1][2][3][4][5][6][7][8]. The musty odors of drinking water are among the major causes of complaints by consumers.…”

“…It has been shown in a recent study that they are linearly correlated to the gas-chromatographic relative retention time (RRT) for the halogenated methyl-phenyl ethers [10]. Ballschmiter et al [1,10] measured systematically the RRT of about 60 possible halogenated anisoles in environmental samples by GC, then they further determined vapor pressures ( p L ), water solubilities (S w,L ), and n-octanol/water partition coefficients (K ow ) by capillary HR-GC (high resolution gas chromatography) on a non-polar phase and by RP-HPLC (reversed phase high performance liquid chromatography) on a C 18 phase with chlorobenzenes as reference standards. From these experimental data the Henry's law constants (H), and the gas/water (K gw ) and gas/n-octanol (K go ) partition coefficients were calculated.…”