Geochemical tools and paleoclimate clues : multi-molecular and isotropic investigations of tropical marine sediments and alpine ice

Abstract

South American climate has undergone dramatic changes since the last glacial period, as evidenced from Cariaco Basin (Venezuelan coast) and Peru Margin marine sediment biomarker records. Compounds derived from vascular plant leaf waxes and delivered to the marine sedimentary environment, including long-chain (C24-C32) n-alkanoic acids, were used as proxies for terrestrial vegetation type, aridity, and atmospheric circulation. Marine biomarkers, such as sterols and phytol, were used to reconstruct productivity in the Peru Margin upwelling zone, where sedimentary conditions are not conducive to the preservation of foraminifera. Through the use of organic molecular isotopic techniques and multi-molecular stratigraphy, a great deal can be learned about communities of marine organisms and terrestrial plants that existed in the past and the environments in which they lived. Vascular plant leaf wax carbon and hydrogen isotopic records were generated from n-alkanoic acids preserved in Cariaco Basin marine sediments. These records were compared to previously established pollen and climate records and were found to parallel local millennial-scale climate changes between the late Glacial and Preboreal periods, which were characterized by migrations of the inter-tropical convergence zone.

(cont.) Differences in 6D between C,6-C18 and C24-C30 n-alkanoic acids suggest a marine source for the shorter chain lengths and a terrestrial source for the longer chains. Stacked 6D and 613C records both exhibited isotopic enrichment during the late Glacial and Younger Dryas periods and depletion during the B011ing-Aller0d and Preboreal periods. If interpreted as an aridity proxy, the 6D record is in agreement with Cariaco Basin sediment grey scale records, suggesting that the late Glacial and Younger Dryas were more arid than the B011ing-Aller0d and Preboreal periods. n-Alkanoic acid 613C, which is a proxy for C3 versus C4 plant type, indicates that C3 plants predominated in this area of the tropics during warm and wet periods, such as the Bolling-Aller0d and the Holocene, and C4 plants proliferated during cooler and more arid periods, such as the Glacial and Younger Dryas. The biomarker 613C record agrees with pollen data previously developed from Cariaco Basin sediments, confirming that leaf wax compounds preserved in marine sediments can accurately record terrestrial vegetation changes. Analytical methods utilizing stir bar sorptive extraction (SBSE) and thermal desorption were developed and applied to investigate lipid organic matter in a suite of alpine ice cores.

(cont.) These methods permit use of small volume (10-30 ml) samples, as would be required for high-resolution down-core analyses. SBSE involves using a polymer coated stir bar to extract organic matter from aqueous samples, after which it is loaded directly into a thermal desorption unit and the organic matter transferred in its entirety to a gas chromatograph inlet. To test these methods and the organic content of tropical ice, post-industrial samples from two South American, two Asian, and one African ice core were analyzed. Compounds identified in the modem ice core samples included natural and anthropogenic biomarkers such as n-alkanes, n-alkanoic acids, n-alkyl amides and nitriles, polycyclic aromatic hydrocarbons (PAHs), and diterpenoids. Variability in the distributions of these compounds between different cores demonstrated that the lipid organic fraction in each core was representative of mostly local inputs. To further investigate natural inputs, several pre-industrial samples were analyzed from the Sajama ice core in the Andes and The Puruogangri core on the Tibetan Plateau. Inputs of terrestrial vegetation combustion biomarkers such as PAHs, diterpenoids, and alkyl amides were consistent with periods of enhanced aridity in each core.

(cont.) The results of this investigation demonstrate the utility of the methodology, which could now be applied to generate very high-resolution biomarker records from tropical ice cores. Gas chromatography/time-of-flight mass spectrometry (GC/TOF-MS) was used to generate a high-resolution, multi-molecular organic biomarker record from Peru Margin sediments (-110S, 252 m water depth) for the last 15 ka. Because of their position beneath the oxygen minimum zone of a productive upwelling region, these sediments contain a wealth of compounds that can be exploited as paleoclimate indicators. TOF-MS and fast GC techniques allowed me to generate this record in a short amount of time and without employing the traditional suite of purification techniques. Before about 9 ka, organic carbon and biomarker concentration records exhibited similar variability, implying a forcing mechanism that affected input and/or preservation of both marine and terrestrial organic matter, such as large-scale climate change. ...