Novel decomposition products of chlorophyll- a in continental shelf (Louisiana shelf) sediments: formation and transformation of carotenol chlorin esters

Abstract

In April 2000, we collected box cores from five stations along a cross-shelf transect on the Louisiana (LA) continental shelf. Novel esters of carotenols and chlorins (carotenoid chlorin esters, CCEs), which are highly specific grazing markers, were identified in surface and deep sediments (>10 cm) from the LA shelf. Chlorophyll- a inventory indicated that CCEs are one of the major decay products of chlorophyll- a in shelf sediments. Abundances of total CCEs (9–18%) in surface sediments along the cross-shelf transect were comparable to the abundance of pheophytin- a, pyropheophytin- a, and total steryl chlorin esters (SCEs). Prior work has identified four CCEs which have dehydrated fucoxanthin/fucoxanthinol as a substitute alcohol of phytol. We report on four newly identified CCEs associated with nondehydrated fuxocanthin/fucoxanthinol esterified to (pyro)pheophorbide- a. These nondehydrated CCEs were generally present in lower concentrations than their dehydrated counterparts, but were detectable by atmospheric pressure chemical ionization (APCI) mass spectrometry coupled with high-performance liquid chromatography (HPLC). We attributed differences between this study and previous work to the time allowed for predepositional decay and grazing processes to occur. The rapid sedimentation of CCEs in the shallow water column (ca. 10 m) on the LA shelf allowed for effective burial of all CCEs compared to the deeper water column regions sampled by previous work. This speculation is supported by the fact that the concentrations of CCEs with nondehydrated fucoxanthin/fucoxanthinol were extremely low in sediments from the site on the outer LA shelf with a deeper (253 m) water column. We also tentatively identified an additional CCE and its isomer as fucoxanthinol didehydrate pyropheophorbide- a ester. We suggest that the formation and transformation of CCEs are primarily controlled by the following three biologically mediated reactions: demethoxycarbonylation, dehydration, and deacetylation. Our laboratory copepod grazing experiment also confirmed that CCEs can be excellent class-specific biomarkers of zooplankton grazing on phytoplankton.