Halogenated natural products in five species of Antarctic sponges: compounds with POP-like properties?

Purified extracts of five species of Antarctic sponges (Demospongiae: Kirkpatrickia variolosa, Artemisina apollinis, Phorbas glaberrima, and Halichondria sp. and Calcarea: Leucetta antarctica) from King George Island were analyzed by GC/MS for the presence of persistent and lipophilic halogenated compounds to identify bioaccumulative halogenated natural products. Sample extracts were prepared using methods identical for the determination of POPs, namely, microwave-assisted extraction with organic solvents, gel permeation chromatography, and column chromatography on deactivated silica. In addition, samples were treated with sulfuric acid to remove acid-destructible compounds. PCBs were not detectable and only traces of lindane, p,p'-DDE, and alpha-HCH were detected in these samples in decreasing order of abundance, underscoring their uncontaminated state. In contrast, 146 brominated compounds were identified by correct isotopic ratios m/z 79 and 81, 50% of which eluted prior to lindane including the most abundant peaks. Each sponge sample contained > or = 35 brominated compounds of natural origin, 14 of which were detected in all species. Estimated concentrations ranged from the high ng/kg to mg/kg (air-dried weights) and relative distributions of the same compounds in different sponges were highly variable. The high abundance of these compounds relative to known anthropogenic pollutants strongly suggests a natural origin. Multiple mode (EI-, ECNI-, and PCI-) GC/MS enabled identification of an aliphatic ketone tentatively identified as 1,1,2-tribromo-oct-1-en-3-one, present in all species but highest in Phorbas glaberrima. Several halogenated phenols including 2,4,6-tribromophenol were also abundant in Phorbas glaberrima as were halogenated anisoles in lower relative abundances. The halogenated phenols were analyzed without derivatization. The sample of Halichondria sp. contained the dibromotrichloro monoterpene MHC-1, a recently described environmental contaminant in fish and seals. Retrospective analysis of other marine samples confirmed that 2,4,6-tribromophenol was present in seal blubber from both the Arctic and the Antarctic. The presence of naturally occurring organohalogens such as 2,4,6-tribromophenol and MHC-1 in Antarctic marine invertebrates thus provides a link to their occurrence in marine mammals.