Widespread distribution and molecular diversity of diatom frustule bound aliphatic long chain polyamines (LCPAs) in marine sediments

Abstract

The siliceous skeletal remains of diatoms are a primary component of sediments, covering vast areas of the sea floor. We used high performance liquid chromatography–electrospray ionization–tandem mass spectrometry (HPLC–ESI–MSn) under high resolution time-of-flight MS (TOF-MS) conditions, as well as nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FTIR), to investigate the distribution and molecular diversity of long chain polyamines (LCPAs) entrapped in sedimentary diatom biosilica in sediments from the Indian sector of the Southern Ocean, the Bering Sea and the Northeast Pacific. This revealed the existence of complex polyamine populations with both known and unknown structural features, including the presence of ketone and carboxylic acid groups in the LCPA backbone, functional groups that likely modulate the silica precipitating properties of LCPAs in the environment and which may constitute points of initial silica deposition (Wallace, A.F., De Yoreso, J.J., Dove, P.M., 2009. Kinetics of silica nucleation on carboxy- and amine-terminated surfaces: insights for biomineralization. Journal of the American Chemical Society 131, 5244–5250). Although various LCPA species overlapped between samples (putrescine-based LCPAs with various degrees of methylation and N-methyl propylamine repeat units were ubiquitous in all samples), clear regional differences were shown in composition and structural characteristics, likely reflecting the various diatom species contributing to the total LCPA pool for each sedimentary environment. We further show, using scanning electron microscopy and energy dispersive X-ray analysis (SEM–EDX) that LCPAs purified from diatom skeletal remains rapidly re-direct the formation of silica nanospheres in vitro, and become embedded in the precipitated silicified matrix, forming an LCPA–silica composite material. The results show that aliphatic polyamines produced by diatoms for morphogenesis of their cell walls are widespread in sediments where the fossil frustules are preserved. These newly assigned components constitute useful biological markers of diatom input to sediments.