The diagenetic behavior of cutin acids in buried conifer needles and sediments from a coastal marine environment

Abstract

Whole green, litter, and sedimentary fir, hemlock, and cedar needles and bulk sediments collected from the Dabob Bay region in Washington state were analyzed for their cutin-derived CuO reaction products. All samples yielded dihydroxyhexadecanoic acid isomers (x,ω-C 16), 16-hydroxyhexa-decanoic acid (ω-C 16), 14-hydroxytetradecanoic acid (ω-C 14), and 18-hydroxyoctadec-9-enoic acid (ω-C 18: 1) as the major cutin acids. Fir/hemlock needle mixtures were characterized by a high abundance of the 9,16-dihydroxyhexadecanoic acid positional isomer, while cedar needles produced primarily the 10,16-dihydroxy counterpart. Cutin acids accounted for ~3% of tissue C in green needles, ~4% in needle litter, 0.5–1.5% in sedimentary needles, and about 0.1% of the organic carbon (OC) in bulk sediments. Approximately 80% of the original cutin acids in fresh green needles were lost from the deepest (~100 years old) sedimentary tissues. Cutin was more reactive than lignin and polysaccharides, but more stable than the cyclitol components of the same needles. Comparative diagenetic losses of the individual cutin acids were not uniform and suggest that additional hydroxy groups and the presence of C double bonds both increase overall reactivity. The relative stability series derived for all the molecular constituents measured is: total vanillyl phenols > total P- hydroxy phenols, ferulic acid, most aldoses, bulk organic matter > mannose, ω-C 14, ω-C 16 ⩾ ω-C 18:1 > glucose, p- coumaric acid, x, ω-C 16 > all cyclitols. Diagenetically induced changes in the various cutin parameters used to characterize nonwoody vascular plant tissues were not large enough to confuse degraded conifer tissues with other cutin sources. Based on these trends, the finely disseminated cutin-bearing tissues in Dabob Bay sediments appear to be comprised approximately of equal amounts of highly degraded fir/hemlock and cedar needle fragments. According to this estimate, nonwoody vascular plant debris accounted for roughly 15% of the total organic matter present in these sediments.