MASS-SPECTROMETRY AND REVERSE-PHASE HPLC TECHNIQUES FOR THE IDENTIFICATION OF DEGRADED FOSSIL PIGMENTS IN LAKE-SEDIMENTS AND THEIR APPLICATION IN PALEOLIMNOLOGY
Da. Hodgson et al., MASS-SPECTROMETRY AND REVERSE-PHASE HPLC TECHNIQUES FOR THE IDENTIFICATION OF DEGRADED FOSSIL PIGMENTS IN LAKE-SEDIMENTS AND THEIR APPLICATION IN PALEOLIMNOLOGY, Journal of paleolimnology, 18(4), 1997, pp. 335-350
Accurate identification of fossil pigments is essential if they are to
be used as biomarker compounds in palaeolimnological studies. In rece
nt years High Performance Liquid Chromatography (HPLC) has greatly enh
anced the efficiency with which fossil pigments can be characterised a
nd quantified. Using HPLC,undegraded pigments are typically identified
through retention times, absorbance spectra and co-chromatography wit
h authentic reference standards. However, lake sediments may also cont
ain degraded pigments for which there are often no standards, and whic
h may be difficult to identify using HPLC alone. In this study, we sub
mitted HPLC fractions of fossil pigments and pigment derivatives colle
cted from a meromictic lake in south west Tasmania, to a combination o
f Mass Spectrometry (MS) techniques including Electron Impact (EI) and
static Liquid Secondary Ion MS (LSIMS) to identify their molecular io
n characteristics and organic chemical composition. Mass Spectrometry
permitted the detection of specific mass ions which were used to verif
y the identity of pigments and their derivatives. These included five
carotenoids, chlorophyll a and derivatives, three previously described
bacteriochlorophyll c derivatives with molecular weights of 770, 784,
and 802, and two undescribed derivatives of bacteriochlorophyll c wit
h molecular weights of 766 and 788. With these improved identification
s we speculate on the pathways and modes of pigment degradation in the
lake and asses the value of the degraded pigments as biomarkers. The
use of MS permitted the identification of a greater number of signatur
e pigments of algal and bacterial communities thus increasing the pala
eolimnological value of the sediments. These methods are best applied
in fossil pigment studies where there are a large number of unknown pi
gments and pigment degradation products, and where there are no authen
tic standards for co-chromatography Practical suggestions for pigment
MS are included in the discussion.