Stable carbon isotope composition (δ13C values) of the halogenated monoterpene MHC-1 as found in fish and seaweed from different marine regions.

Six samples of the red seaweed Plocamium cartilagineum (two both from Helgoland/Germany, Ireland, and the Antarctic) were analyzed by stable isotope analysis. The bulk δ(13)C values (-31 to -38‰) confirmed that this seaweed was exceptionally highly depleted in (13)C. The δ(15)N values were in the reported range for algae, and a moderate correlation between (13)C and (15)N content was observed. These measurements indicated that the season had a higher impact on the δ(13)C values than the location. Compound specific carbon isotope analysis by gas chromatography coupled with isotope ratio mass spectrometry (GC-IRMS) was used to verify an even stronger depletion in (13)C in the halogenated natural product (HNP) MHC-1 isolated from the seaweed samples. The δ(13)C values of MHC-1 in the range -42 to -45‰ are the lightest determined to date for polyhalogenated compounds in the molecular mass range between 250 and 800 Da. MHC-1 was also isolated from two fish samples. The much higher (13)C content in MHC-1 from the fish samples (-35.6 to -39.2‰) indicated carbon isotope enrichment due to partial transformation. In processes such as the reductive debromination, the partial transformation is associated with an increase in the (13)C content in the remaining non-metabolized share of a compound. Stable isotope analysis may thus provide insights into the degree of transformation of HNPs in environmental samples.