Nitrogen isotopes in chlorophyll and the origin of Eastern Mediterranean sapropels

Abstract

The goals of this thesis were: (1) to establish methods for the determination of nitrogen and carbon isotope ratios in marine particulate and sedimentary chlorophyll derivatives; (2) to establish chlorophyll δ15N and δl3C as proxies for the nitrogen and carbon isotopic composition of marine phytoplankton; and (3) to use chlorophyll nitrogen isotopic ratios to understand the origin of Late Quaternary Eastern Mediterranean sapropels. Techniques are presented for the determination of chlorin nitrogen and carbon isotopic ratios in marine particles and sediments with a precision greater than 0.15 per mil for both isotopes. The procedure can be performed in about 4 hours for particulate and 8 hours for sediment samples, and relies on multiple chromatographic purifications. About 20 g of a moderately organic-rich sediment are required. A technique is also presented for the determination of chlorin nitrogen and carbon isotopic ratios by isotope-ratio monitoring gas chromatography-mass spectrometry (irmGC-MS) by synthesizing bis-(tert.-butyldimethylsiloxy)Si(IV) chlorin derivatives. However, yields for the 4-step synthesis were only about 5-6% and there was a net isotopic depletion of 1.2 (± 0.3) per mil in the derivative, relative to the starting material. These techniques are then used to show that the nitrogen isotopic difference between chlorophyll and whole cells in six species of marine phytoplankton is 5.16 ± 2.40 per mil. For carbon, the isotopic difference between chlorophyll and whole cells in five species of marine phytoplankton is -0.02 ± 2.12 per mil. A model of the distribution of 15N in phytoplankton is constructed and it is demonstrated that the interspecies variability observed for the nitrogen isotopic difference between chlorophyll and whole cells can be attributed to differences in the partitioning of cellular nitrogen between non-protein biochemicals. In the field, where mixed assemblages of phytoplankton prevail, the isotopic difference beween chlorophyll and whole cells is expected to tend toward the average value of 5.16 per mil. Finally, the average nitrogen isotopic composition of chlorins from six Late Quaternary Eastern Mediterranean sapropels (-5.01 + 0.38 per mil) was found to be very similar to the δ15N of chlorophyll from the modem deep chlorophyll maximum (-6.38 ± 1.80 per mil) in the Eastern Mediterranean. In addition, sapropel photoautotrophic material, calculated from the chlorin δ15N, had the same isotopic composition (0.15 per mil) as both bulk sapropel sediments (-0.08 ± 0.53 per mil) and deep water nitrate (-0.05 per mil). These data suggest (a) that bottom waters were anoxic, (b) that organic matter burial efficiency was enhanced, and (c) that oligotrophic conditions similar to today persisted, in the Eastern Mediterranean during sapropel deposition. These results contradict earlier interpretations of Late Quaternary bulk sedimentary δ15N in the Eastern Mediterranean. The latter concluded that the pattern of high δ15N values in intercalated marl oozes and low values in sapropels was the result of decreased nutrient utilization, and hence, increased primary production, during sapropel events. The low δ15N of deep water nitrate in the Eastern Mediterranean suggests a significant source of new nitrogen from biological N2-fixation. It is suggested that attempts to reconstruct the nitrogen isotopic composition of marine organic matter in the past by measuring the δ15N of whole sediments may be subject to misinterpretation due to the alteration of isotopic ratios during diagenesis. The partial oxidation of marine organic matter can result in significant isotopic enrichment of the preserved residual. The magnitude of this enrichment appears to be large when bottom waters are well-oxygenated, and small when bottom waters are anoxic. Environments where large temporal reqox changes have occurred are expected to be the most problematic for the interpretation of bulk sedimentary δ15N. In these environments, the diagenetic signal can be at least as large as the primary isotopic signal being sought. The Eastern Mediterranean Sea during the Late Quaternary appears to be one such environment.