Angela H. Squier

Sedimentary pigments as markers for environmental change in an Antarctic lake

Abstract Fossil pigments were identified in a sediment core from Kirisjes Pond, a small lake in the Larsemann Hills, east Antarctica, using reversed-phase HPLC and LC–MS/MS. Chlorophyll a- and b -derived components indicate the presence of oxygenic primary producers; steryl chlorin esters provide evidence of grazing, while shifts in their esterifying sterol composition record changes in the primary producer community. Bacteriochlorophyll c- and d -derived components, indicative of photic zone anoxia, were identified with structural variations including extensive alkylation in the macrocycle up to C 6 . The pigment distribution reveals a change from oxygenated freshwater to a stratified water body with development of photic zone anoxia. This coincides with a marine incursion identified from diatom records and is followed by re-isolation and reversion to oxygenated freshwater conditions.

Evidence of late Quaternary environmental change in a continental east Antarctic lake from lacustrine sedimentary pigment distributions

A sediment core from Progress Lake, one of the oldest lacustrine sequences in East Antarctica, contains distinct zones dating from a previous interglacial (most likely Marine Isotope Stage 5e, c. 125–115 kyr BP) and the present interglacial (Marine Isotope Stage 1), separated by a transition zone representing when the lake became sub-glacial. Profiles of fossil pigments, determined using high performance liquid chromatography and liquid chromatography-tandem mass spectrometry, show distinct differences in the photoautotrophic community during these two interglacial periods. The first was dominated by algae and purple phototrophic bacteria, with periods of photic zone euxinia indicated by pigments from anoxygenic phototrophic bacteria. Specific chlorophyll a derivatives reveal periods when grazing pressure impacted significantly on the phytoplankton community. The virtual absence of pigments in the transition zone reflects severe restriction of photoautotrophic activity, consistent with the lake having become sub-glacial. Retreat of snow and ice in the late Holocene (3345 14C yr BP) allowed establishment of a less diverse primary producer community, restricted to algae and cyanobacteria. Grazers were severely restricted and oxidative transformation was more important than during the previous interglacial. The pigment data provide a unique and detailed insight in to the evolution of the lake ecology over an interglacial-glacial-interglacial transition and strong evidence that the Marine Isotope Stage 5e interglacial in this region of coastal East Antarctica was several degrees warmer than at present.

Origin and significance of 132-hydroxychlorophyll derivatives in sediments

Abstract The authenticity of hydroxychlorophyll derivatives in sediments has been verified by subjecting pure chlorophyll preparations to the extraction method used for sediments. Model studies of chlorophyll autoxidation reveal hydroxychlorophyll as the major product formed in the presence of hydrogen peroxide. Its stability to further oxidation implies that hydroxychlorophyll derivatives are not precursors of aetioporphyrins and are more likely to produce cycloalkanoporphyrins via the processes of diagenesis. The occurrence of 13 2 -hydroxyphaeophytin a throughout a sediment core from Loch Ness confirms it to be a widespread chlorophyll oxidation product formed during early diagenesis. Profiles of hydroxychlorophyll derivatives in a sediment core from an Antarctic lake demonstrate their potential for use as markers of oxidation processes in palaeoenvironmental assessment.

Identification of novel sulfur-containing derivatives of chlorophyll a in a Recent sedimentElectronic supplementary information (ESI) available: 1H NMR data. See http://www.rsc.org/suppdata/cc/b2/b212243j/

Novel transformation products of chlorophyll a incorporating a methyl sulfide group in the substituent at the C-3 position have been identified in Recent sediments from an Antarctic lake.