Separation of 26 toxaphene congeners and measurement in air particulate matter SRMs compared to technical toxaphene SRM 3067

Abstract

Toxaphene is a complex technical mixture that has been found ubiquitously in the environment but has caused issues for analysis, especially of individual congeners. This paper reports the elution order of 26 major toxaphene congeners on three gas chromatographic columns. The three different stationary phases generally had similar elution orders for the toxaphene congeners, but fewer co-elutions occurred on a low-bleed, low-polarity column. These congeners (except for two that co-eluted and were not added to the calibration mixture) were examined in air particulate matter standard reference materials (SRMs), 1648a, 1649a, and 1649b as well as SRM 3067 toxaphene in methanol for assignment of reference values. SRM 3067 had mass fractions an order of magnitude greater than the air particulate SRMs, which ranged from 0.568 +/- 0.018 ng g(-1) dry mass (B9-2006 in SRM 1648a) to 12.9 +/- 0.20 ng g(-1) dry mass (B9-715 (P 58) in SRM 1649a). The three air particulate SRMs all had different mass fractions and proportions of congeners relative to the sum of the toxaphene congeners. SRM 3067 may be useful as a technical mixture toxaphene congener calibrant. SRMs 1648a and 1649b will serve as reference materials for the analysis of 21 (three congeners were not included due to values below the detection limit or a potential polychlorinated biphenyl co-elution) toxaphene congeners in atmospheric particulate samples.

Using quantitative structural property relationships, chemical fate models, and the chemical partitioning space to investigate the potential for long range transport and bioaccumulation of complex halogenated chemical mixtures

“…Other studies targeted individual components of a mixture, selected typically because they could be isolated analytically from other components and/or because their physical-chemical property data had been established. 16,18,32,53,54,62,63,91,[94][95][96] In this approach it is rarely established whether these components indeed are representative of the entire mixture. For example, Health Canada's most recent risk assessment on LCCPs relied on three congeners with in more detail as its intake estimates were approximately one order of magnitude higher than for the other three components.…”

“…36,46,52,53 Most measurements quantify "total environmental toxaphene" (TET) comprising potentially over 120 000 components (Table 1), 8,26,29 although analytical methods now also allow for the targeting of individual toxaphene constituents. 8,14,16,18,32,54,55 When toxaphene is assessed as a chemical of concern, the TET approach is commonly used. 1 Halogenated dioxins and furans are unintentional sideproducts of combustion processes, and the PCDD/Fs are listed under Annex C of the Stockholm Convention, which means that Parties to the Convention are required to make efforts to reduce releases of such compounds.…”

“…Either the focus is on the mixture as a whole and differences in the behavior of individual constituents are ignored [3][4][5][6][7][8][9][10][11][12][13] or a few components within the mixture are selected to represent the entire set. [14][15][16][17][18][19][20] Modeling studies of such compounds are faced with the challenge to select chemical properties that appropriately represent the entire mixture. When properties are available for individual constituents, average or median values can be selected; otherwise the most reliable experimental values for the entire mixture can be used.…”

Optimisation of pressurised liquid extraction for the ultra-trace quantification of 20 priority substances from the European Water Framework Directive in atmospheric particles by GC–MS and LC–FLD–MS/MS

“…Very often, only 0003-2670/$ -see front matter © 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.aca.2011.03.008 samples of less than one hundred milligrams are available [26] [38] while published methods on other environmental solid matrices (such as soil, sediment) require a few grams [36,37,39].…”