n-alkane carbon isotope ratios in plants and recent lake sediments from Cameroon

Trees and shrubs in tropical Africa use the C3 cycle as a carbon fixation pathway during photosynthesis, while grasses and sedges mostly use the C4 cycle. Leaf-wax lipids from sedimentary archives such as the long-chain n-alkanes (e.g., n-C27 to n-C33) inherit carbon isotope ratios that are representative of the carbon fixation pathway. Therefore, n-alkane d13C values are often used to reconstruct past C3/C4 composition of vegetation, assuming that the relative proportions of C3 and C4 leaf waxes reflect the relative proportions of C3 and C4 plants. We have compared the d13C values of n-alkanes from modern C3 and C4 plants with previously published values from recent lake sediments and provide a framework for estimating the fractional contribution (areal-based) of C3 vegetation cover (fC3) represented by these sedimentary archives. Samples were collected in Cameroon, across a latitudinal transect that accommodates a wide range of climate zones and vegetation types, as reflected in the progressive northward replacement of C3-dominated rain forest by C4-dominated savanna. The C3 plants analysed were characterised by substantially higher abundances of n-C29 alkanes and by substantially lower abundances of n-C33 alkanes than the C4 plants. Furthermore, the sedimentary d13C values of n-C29 and n-C31 alkanes from recent lake sediments in Cameroon (-37.4 per mil to -26.5 per mil) were generally within the range of d13C values for C3 plants, even when from sites where C4 plants dominated the catchment vegetation. In such cases simple linear mixing models fail to accurately reconstruct the relative proportions of C3 and C4 vegetation cover when using the d13C values of sedimentary n-alkanes, overestimating the proportion of C3 vegetation, likely as a consequence of the differences in plant wax production, preservation, transport, and/or deposition between C3 and C4 plants. We therefore tested a set of non-linear binary mixing models using d13C values from both C3 and C4 vegetation as end-members. The non-linear models included a sigmoid function (sine-squared) that describes small variations in the fC3 values as the minimum and maximum d13C values are approached, and a hyperbolic function that takes into account the differences between C3 and C4 plants discussed above. Model fitting and the estimation of uncertainties were completed using the Monte Carlo algorithm and can be improved by future data addition. Models that provided the best fit with the observed d13C values of sedimentary n-alkanes were either hyperbolic functions or a combination of hyperbolic and sine-squared functions. Such non-linear models may be used to convert d13C measurements on sedimentary n-alkanes directly into reconstructions of C3 vegetation cover.

A relationship between aerosol transport and compound-specific d13C land plant biomarker and pollen records

We examined near-surface, late Holocene deep-sea sediments at nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) along the Southwest African continental margin. Contents, distribution patterns and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) are indicators of land plant vegetation of different biosynthetic types, which can be correlated with concentrations and distributions of pollen taxa in the same sediments. Calculated clusters of wind trajectories and satellite Aerosol Index imagery afford information on the source areas for the lipids and pollen on land and their transport pathways to the ocean sites. This multidisciplinary approach on an almost continental scale provides clear evidence of latitudinal differences in lipid and pollen composition paralleling the major phytogeographic zonations on the adjacent continent. Dust and smoke aerosols are mainly derived from the western and central South African hinterland dominated by deserts, semi-deserts and savannah regions rich in C4 and CAM plants. The northern sites (Congo Fan area and northern Angola Basin), which get most of their terrestrial material from the Congo Basin and the Angolan highlands, may also receive some material from the Chad region. Very little aerosol from the African continent is transported to the most southerly sites in the Cape Basin. As can be expected from the present position of the phytogeographic zones, the carbon isotopic signatures of the n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. The results of the study suggest that this combination of pollen data and compound-specific isotope geochemical proxies can be effectively applied in the reconstruction of past continental phytogeographic developments.

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.

Abundances and d13C values of n-alkanes extracted from sediment samples of ODP Hole 116-717C

Siwalik paleosol and Bengal Fan sediment samples were analyzed for the abundance and isotopic composition of n-alkanes in order to test for molecular evidence of the expansion of C4 grasslands on the Indian subcontinent. The carbon isotopic compositions of high-molecular-weight alkanes in both the ancient soils and sediments record a shift from low d13C values (ca. -30 per mil) to higher values (ca. -22 per mil) prior to 6 Ma. This shift is similar in magnitude to that recorded by paleosol carbonate and fossil teeth, and is consistent with a relatively rapid transition from dominantly C3 vegetation to an ecosystem dominated by C4 plants typical of semi-arid grasslands. The n-alkane values from our paleosol samples indicate that the isotopic change began as early as 9 Ma, reflecting either a growing contribution of C4 plants to a dominantly C3 biomass or a decrease in water availability to C3 plants. Molecular and isotopic analyses of other compounds, including n-alcohols and low-molecular weight n-alkanes indicate paleosol organic matter contains contributions from a mixture of sources, including vascular plants, algae and/or cyanobacteria and microorganisms. A range of inputs is likewise reflected in the isotopic composition of the total organic carbon from these samples. In addition, the n-alkanes from two samples show little evidence for pedegenic inputs and we suggest the compounds were derived instead from the paleosol's parent materials. We suggest the record of vegetation in ancient terrestrial ecosystems is better reconstructed using isotopic signatures of molecular markers, rather than bulk organic carbon. This approach provides a means of expanding the spatial and temporal records of C4 plant biomass which will help to resolve possible tectonic, climatic or biological controls on the rise of this important component of the terrestrial biosphere.

Contents and isotopic composition of black carbon from ODP Sites 184-1147 and 184-1148

A 30 m.y. stable isotopic record of marine-deposited black carbon from regional terrestrial biomass burning from the northern South China Sea reveals photosynthetic pathway evolution for terrestrial ecosystems in the late Cenozoic. This record indicates that C3 plants negatively adjusted their isotopic discrimination and C4 plants appeared gradually as a component of land vegetation in East Asia since the early Miocene, a long time before sudden C4 expansion occurred during the late Miocene to the Pliocene. The changes in terrestrial ecosystems with time can be reasonably related to the evolution of East Asian monsoons, which are thought to have been induced by several intricate mechanisms during the late Cenozoic and could contribute significantly to the post-Miocene marine carbonate isotope decline.

Pollen profile and age determination for sediment core M72/5_619-1 (22-GC3)

Sediments from the Black Sea, a region historically dominated by forests and steppe landscapes, are a valuable source of detailed information on the changes in regional terrestrial and aquatic environments at decadal to millennial scales. Here we present multi-proxy environmental records (pollen, dinoflagellate cysts, Ca, Ti and oxygen isotope data) from the uppermost 305 cm of the core 22-GC3 (42°13.53' N, 36°29.55' E) collected from a water depth of 838 m in the southern part of the Black Sea in 2007. The records span the last ~ 18 kyr (all ages are given in cal kyr BP). The pollen data reveal the dominance of the Artemisia-steppe in the region, suggesting rather dry/cold environments ~ 18-14.5 kyr BP. Warming/humidity increase during melt-water pulses (~ 16.1-14.5 kyr BP), indicated by d18O records from the 22-GC3 core sediment and from the Sofular Cave stalagmite, is expressed in more negative d13C values from the Sofular Cave, usually interpreted as the spreading of C3 plants. The records representing the interstadial complex (~ 14.5-12.9 kyr BP) show an increase in temperature and moisture, indicated by forest development, increased primary productivity and reduced surface run-off, whereas the switch from primary terrigenous to primary authigenic Ca origin occurs ~ 500 yr later. The Younger Dryas cooling is clearly demonstrated by more negative d13C values from the Sofular Cave and a reduction of pines. The early Holocene (11.7-8.5 kyr BP) interval reveals relatively dry conditions compared to the mostly moist and warm middle Holocene (8.5-5 kyr BP), which is characterized by the establishment of the species-rich warm mixed and temperate deciduous forests in the low elevation belt, temperate deciduous beech-hornbeam forests in the middle and cool conifer forest in upper mountain belt. The border between the early and middle Holocene in the vegetation records coincides with the opening of the Mediterranean corridor at ~ 8.3 kyr BP, as indicated by a marked change in the dinocyst assemblages and in the sediment lithology. Changes in the pollen assemblages indicate a reduction in forest cover after ~ 5 kyr BP, which was likely caused by increased anthropogenic pressure on the regional vegetation.

Stable oxygen and carbon isotopes ratios of sediment core GeoB9528-3

The carbon isotopic composition of individual plant leaf waxes (a proxy for C3 vs. C4 vegetation) in a marine sediment core collected from beneath the plume of Sahara-derived dust in northwest Africa reveals three periods during the past 192,000 years when the central Sahara/Sahel contained C3 plants (likely trees), indicating substantially wetter conditions than at present. Our data suggest that variability in the strength of Atlantic meridional overturning circulation (AMOC) is a main control on vegetation distribution in central North Africa, and we note expansions of C3 vegetation during the African Humid Period (early Holocene) and within Marine Isotope Stage (MIS) 3 (approx. 50-45 ka) and MIS 5 (approx. 120-110 ka). The wet periods within MIS 3 and 5 coincide with major human migration events out of sub-Saharan Africa. Our results thus suggest that changes in AMOC influenced North African climate and, at times, contributed to amenable conditions in the central Sahara/Sahel, allowing humans to cross this otherwise inhospitable region.

Organic carbon isotope ratios of sea surface sediments and sea-ice from the Amerasian Continental shelf

Organic matter origins are inferred from carbon isotope ratios (delta13C) in recent continental shelf sediments and major rivers from 465 locations from the north Bering-Chukchi-East Siberian-Beaufort Sea, Arctic Amerasia. Generally, there is a cross-shelf increase in delta13C, which is due to progressive increased contribution seaward of marine-derived organic carbon to surface sediments. This conclusion is supported by the correlations between sediment delta13C, OC/N, and delta15N. The sources of total organic carbon (TOC) to the Amerasian margin sediments are primarily from marine water-column phytoplankton and terrigenous C3 plants constituted of tundra taiga and angiosperms. In contrast to more temperate regions, the source of TOC from terrigenous C4 and CAM plants to the study area is probably insignificant because these plants do not exist in the northern high latitudes. The input of carbon to the northern Alaskan shelf sediments from nearshore kelp community (Laminaria solidungula) is generally insignificant as indicated by the absence of high sediment delta13C values (-16.5 to -13.6 per mil) which are typical of the macrophytes. Our study suggests that the isotopic composition of sediment TOC has potential application in reconstructing temporal changes in delivery and accumulation of organic matter resulting from glacial-interglacial changes in sea level and environments. Furthermore, recycling and advection of the extensive deposits of terrestrially derived organic matter from land, or the wide Amerasian margin, could be a mechanism for elevating total CO2 and pCO2 in the Arctic Basin halocline.

delta13Corg of Paleozoic land plants

Based on the evaluation of 1323 carbon isotope values for Silurian to Permian terrestrial organic carbon, measured on plant fossils, cuticules, humic coals and bulk terrestrial organic matter (TOM), we conclude that the temporal trend in d13CTOM records variations in the global carbon cycle, notably an increase in the fractional burial of light (terrestrial) organic matter in Late Palaeozoic sediments. d13CTOM values suggest that the Late Palaeozoic pO2 peak could have been restricted to a time frame of ca. 40 Ma. Carbon isotope data from four taxonomic groups reveal small differences that could be a consequence of habitat conditions. No significant differences in organic carbon isotopic composition in relation to variable climatic conditions are discernible. The carbon isotopic composition solely reflects C3 plant metabolism.