Biomarkers, stable carbon isotope record and pollen distribution of the soutwest African continental margin

This is part 2 of a study examining southwest African continental margin sediments from nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) representing two glacial (MIS 2 and 6a) and two interglacial stages (MIS 1 and 5e). Contents, distribution patterns, and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) as indicators of land plant vegetation of different biosynthetic types were correlated with concentrations and distributions of pollen taxa in sediments of the same time horizons. Selected single pollen type data reveal details of vegetation changes, but the overall picture is best illustrated by summing pollen known to predominantly derive from C4 plants or C4 plus CAM plants. The C4 plant signals in the biomarkers are recorded in the delta13C data and in the abundances of C31 and C33 n-alkanes, and the C32 n-alkanol. Calculated clusters of wind trajectories for austral summer and winter situations for the Holocene and the Last Glacial Maximum afford information on the source areas for the lipids and pollen and their transport pathways to the ocean. This multidisciplinary approach provides clear evidence of latitudinal differences in leaf wax lipid and pollen composition, with the Holocene sedimentary data paralleling the current major phytogeographic zonations. The northern sites (Congo Fan area and northern Angola Basin) get most of their terrestrial material from the Congo Basin and the Angolan highlands dominated by C3 plants. Airborne particulates derived from the western and central South African hinterland dominated by deserts, semideserts, and savannah regions are rich in organic matter from C4 plants. As can be expected from the present and glacial positions of the phytogeographic zones, the carbon isotopic signatures of n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. In the northern part of the transect the relative importance of C4 plant indicators is higher during the glacials than in the interglacials, indicating a northward extension of arid zones favoring grass vegetation. In the south, where grass-rich vegetation merges into semidesert and desert, the difference in C4 plant indicators is small.

(Table 1) n-alkane distribution, and stable carbon and deuterium isotope ratios of DSDP Hole 10-94

Hydrology, source region, and timing of precipitation are important controls on the climate of the Great Plains of North America and the composition of terrestrial ecosystems. Moisture delivered to the Great Plains varies seasonally and predominately derives from the Gulf of Mexico/Atlantic Ocean with minor contributions from the Pacific Ocean and Arctic region. For this work, we evaluate long-term relationships for the past ~ 35 million years between North American hydrology, climate, and floral change, using isotopic records and average carbon chain lengths of higher plant n-alkanes from Gulf of Mexico sediments (DSDP Site 94). We find that carbon isotope values (d13C) of n-alkanes, corrected for variations in the d13C value of atmospheric CO2, provide minor evidence for contributions of C4 plants prior to the Middle Miocene. A sharp spike in C4 input is identified during the Middle Miocene Climatic Optimum, and the influence of C4 plants steadily increased during the Late Miocene into the Pleistocene - consistent with other North American records. Chain-length distributions of n-alkanes, indicative of the composition of higher plant communities, remained remarkably constant from 33 to 4 Ma. However, a trend toward longer chain lengths occurred during the past 4 million years, concurrent with an increase in d13C values, indicating increased C4 plant influence and potentially aridity. The hydrogen isotope values (dD) of n-alkanes are relatively invariant between 33 and 9 Ma, and then become substantially more negative (75 per mil) from 9 to 2 Ma. Changes in the plant community and temperature of precipitation can solely account for the observed variations in dD from 33 to 5 Ma, but cannot account for Plio-Pleistocene dD variations and imply substantial changes in the source region of precipitation and seasonality of moisture delivery. We posit that hydrological changes were linked to tectonic and oceanographic processes including the shoaling and closure of the Panamanian Seaway, amplification of North Atlantic Deep Water Production and an associated increase of meridional winds. The southerly movement of the Intertropical Convergence Zone near 4 Ma allowed for the development of a near-modern pressure/storm track system, driving increased aridity and changes in seasonality within the North American interior.

Marine and terrigenous lipids in ODP Leg 175 holes

Lipid compositions of sediments recovered during Ocean Drilling Program Leg 175 in the eastern South Atlantic reflect a variety of oceanographic and climatological environments. Most of the identified lipids can be ascribed to marine sources, notably haptophytes, eustigmatophytes, dinoflagellates, archaea, and diatoms. Elevated concentrations of cholesterol suggest zooplankton herbivory, characteristic for sites influenced by upwelling. At these sites, sulfurized highly branched isoprenoids from diatoms are also present in high amounts. Sterols, sterol ethers, hopanoids, and midchain hydroxy fatty acids could also be detected. Terrigenous lipids are n-alkanes, fatty acids, n-alcohols, and triterpenoid compounds like taraxerol and -amyrine. n-Alkanes, fatty acids, and n-alcohols are derived from leaf waxes of higher land plants and transported to the sea by airborne dust or fresh water. Triterpenoid compounds are most probably derived from mangroves and transported solely by rivers. Lipid compositions below the Congo low-salinity plume are strongly influenced by terrigenous material from the Congo River. Elevated organic carbon contents and predominantly marine lipid distributions at the Angola margin may indicate a highly productive plankton population, probably sustained by the Angola Dome. Sedimentary lipids in the Walvis Basin contain an upwelling signal, likely transported by the Benguela Current. Sedimentary lipids off Lüderitz Bay and in the southern Cape Basin are dominated by plankton lipids in high to intermediate amounts, reflecting persistent and seasonal upwelling, respectively.

Plant-wax, alkenone and major element analyses of ODP Site 659 for the Last Glacial cycle and associated coretop data

We present a hydrologic reconstruction of the Sahara-Sahel transition, covering the complete last glacial cycle (130 ka), based on a combination of plant-wax-specific hydrogen (dD) and carbon isotopes (d13C). The dD and d13C signatures of long-chain n-alkanes from ODP Site 659 off NW Africa reveal a significant anti-correlation. Complementary to published pollen data, we infer that this plant-wax signal reflects sensitive responses of the vegetation cover to precipitation changes in the Sahel region, as well as varying contributions from biomes north of the Sahara (C3 domain) by North-East Trade Winds (NETW). During arid phases, especially the northern parts of the Sahel likely experienced crucial water stress, which resulted in a pronounced contraction of the vegetation cover, thus reducing the amount of C4 plant waxes from the region. The increase in NETW strength during dry periods further promoted a more pronounced C3-plant-wax signal derived from the North African C3 plant domain. During humid periods, the C4-dominated Sahelian environments spread northward into the Saharan realm, in association with lower NETW inputs of C3 plant waxes. Arid-humid cycles deduced from plant-wax dD are in accordance with concomitant changes in weathering intensity reflected in varying major element distributions. Environmental shifts are generally linked to periods with large fluctuations in Northern Hemisphere summer insolation. During Marine Isotope Stages 2 and 3, when insolation variability was low, coupling of the hydrologic regime to alkenone-based estimates of NE Atlantic sea-surface temperatures becomes apparent.

Distribution and stable isotopic compositions of hydrogen and carbon of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments

Reconstructing terrestrial water budgets is of prime importance for understanding past climate and environment. To shed more light on how plant-wax derived n-alkanes may be used for this purpose we investigated the distribution and stable isotopic compositions of hydrogen (dD) and carbon (d13C) of plant-wax derived n-C29 and -C31 alkanes in terrestrial, coastal and offshore surface sediments in relation to hydrology along a NW-SE transect east of the Italian Apennines from the Po River to the Eastern Gulf of Taranto. The plant wax average chain length increases southward and may relate to increasing temperature and/or aridity. The plant wax dD of the terrestrial and coastal samples also increases southward and mainly reflects changes in the dD of precipitation. The d13C of plant waxes is primarily interpreted in terms of C3 vegetation changes rather than varying contributions by C4 plants. The plant wax d13C-dD composition of the Po River and Apennine rivers differs considerably from that in southern Italy, and suggests a mainly southern source for plant waxes in marine sediments of the Gulf of Taranto. This calibration provides a basis for the reconstruction of past changes in the Italian water balance and n-alkane source areas.

Isotopic signatures and mercury content of arctic char and their prey, and water chemistry of 18 arctic Canadian lakes

Concentrations of mercury (Hg) have increased slowly in landlocked Arctic char over a 10- to 15-year period in the Arctic. Fluxes of Hg to sediments also show increases in most Arctic lakes. Correlation of Hg with trophic level (TL) was used to investigate and compare biomagnification of Hg in food webs from lakes in the Canadian Arctic sampled from 2002 to 2007. Concentrations of Hg (total Hg and methylmercury [MeHg]) in food webs were compared across longitudinal and latitudinal gradients in relation to d13C and d15N in periphyton, zooplankton, benthic invertebrates, and Arctic char of varying size-classes. Trophic magnification factors (TMFs) were calculated for the food web in each lake and related to available physical and chemical characteristics of the lakes. The relative content of MeHg increased with trophic level from 4.3 to 12.2% in periphyton, 41 to 79% in zooplankton, 59 to 72% in insects, and 74 to 100% in juvenile and adult char. The d13C signatures of adult char indicated coupling with benthic invertebrates. Cannibalism among char lengthened the food chain. Biomagnification was confirmed in all 18 lakes, with TMFs ranging from 3.5 ± 1.1 to 64.3 ± 0.8. Results indicate that TMFs and food chain length (FCL) are key factors in explaining interlake variability in biomagnification of [Hg] among different lakes.

Biomarker records of DSDP Hole 24-231 and terrestrial sediments

ntegrated terrestrial and marine records of northeast African vegetation are needed to provide long high resolution records of environmental variability with established links to specific terrestrial environments. In this study, we compare records of terrestrial vegetation preserved in marine sediments in the Gulf of Aden [Deep Sea Drilling Project (DSDP) Site 231] and an outcrop of lacustrine sediments in the Turkana Basin, Kenya, part of the East African Rift System. We analyzed higher plant biomarkers in sediments from both deposits of known equivalent age, corresponding to a ca. 50-100 ka humid interval prior to the b-Tulu Bor eruption ca. 3.40 Ma, when the Lokochot Lake occupied part of the Turkana Basin. Molecular abundance distributions indicate that long chain n-alkanoic acids in marine sediments are the most reliable proxy for terrestrial vegetation (Carbon Preference Index, CPI = 4.5), with more cautious interpretation needed for n-alkanes and lacustrine archives. Marine sediments record carbon isotopic variability in terrestrial biomarkers of 2-3 per mil, roughly equivalent to 20% variability in the C3/C4 vegetation contribution. The proportion of C4 vegetation apparently increased at times of low terrigenous dust input. Terrestrial sediments reveal much larger (2-10 per mil) shifts in n-alkanoic acid delta13C values. However, molecular abundance and isotopic composition suggest that microbial sources may also contribute fatty acids, contaminating the lacustrine sedimentary record of terrestrial vegetation.

Radiocarbon ages and major n-alkane homologues of peat cores LVPS4 and LVPS5B, Russian Arctic

Coupled analyses of n-alkane biomarkers and plant macrofossils from a peat plateau deposit in the northeast European Russian Arctic were carried out to assess the effects of past hydrology on the molecular contributions of plants to the peat. The n-alkane biomarkers accumulated over 9.6 kyr of local paleohydrological changes in this complex peat profile in which a succession of vegetation changes occurred during a transition from a wet fen to a relatively dry peat plateau bog. This study shows that the contribution of the n-C31 alkane from rootlets to peat layers rich in fine and dark roots is important. The results further indicate that the n-alkane Paq and n-C23/n-C29 biomarker proxies that have been useful to reconstruct past water table levels in many peat deposits can be misleading when the contributions of Betula and Sphagnum fuscum to the peat are large. Under these conditions, the C23/(C27 + C31) n-alkane ratio seems to correct for the presence of Betula and S. fuscum and provides a better description for the relative amounts of moisture. The average chain length (ACL) n-alkane proxy also appears to be a good paleohydrology proxy in having larger values during dry and cold conditions in this Arctic bog setting.

General descriptions, organic contents and ratios of geolipid components at DSDP Leg 74 Holes

Two samples of Miocene sediments from Site 525 and four samples of sediments ranging in age from Pleistocene to Miocene from Site 528 have been analyzed for concentrations of organic and carbonate carbon, carbon/nitrogen ratios of organic matter, and extractable hydrocarbons and fatty acids. Organic carbon concentrations average 0.32% and show a diagenetic decrease with greater sediment age. Distributions of n-alkanes and n-alkanoic acids give evidence of considerable microbial reworking and of eolian contributions of terrigenous components. Organic contents of these sediments reflect a history of low marine productivity and poor preservation of organic matter in the eastern South Atlantic since middle Miocene times.