Evaluation of long chain 1,14-alkyl diols in marine sediments as indicators for upwelling and temperature

Long chain alkyl diols form a group of lipids occurring widely in marine environments. Recent studies have suggested several palaeoclimatological applications for proxies based on their distributions, but also revealed uncertainties about their applicability. Here we evaluate the use of long chain 1,14-alkyl diol indices for reconstruction of temperature and upwelling conditions by comparing index values, obtained from a comprehensive set of marine surface sediments, with environmental factors like sea surface temperature (SST), salinity and nutrient concentrations. Previous cultivation efforts indicated a strong effect of temperature on the degree of saturation and the chain length distribution of long chain 1,14-alkyl diols in Proboscia spp., quantified in the diol saturation index (DSI) and diol chain length index (DCI), respectively. However, values of these indices in surface sediments show no relationship with annual mean SST of the overlying water. It remains unknown what determines the DSI, although our data suggests that it may be affected by diagenesis, while the relationship between temperature and DCI may be different for different Proboscia species. In addition, contributions of algae other than Proboscia diatoms may affect both indices, although our data provide no direct evidence for additional long chain 1,14-alkyl diol sources. Two other indices using the abundance of 1,14-diols vs. 1,13-diols and C30 1,15-diols have previously been applied as indicators for upwelling intensity at different locations. The geographical distribution of their values supports the use of 1,14 diols vs. 1,13 diols [C28 + C30 1,14-diols]/[(C28 + C30 1,13-diols) + (C28 + C30 1,14-diols)] as a general indicator for high nutrient or upwelling conditions.

Freshwater mesocosm experiment 2012 in Vancouver, Canada on effects of increased temperature and food chain length on oxygen fluxes and plankton community structure

Over broad thermal gradients, the effect of temperature on aerobic respiration and photosynthesis rates explains variation in community structure and function. Yet for local communities, temperature dependent trophic interactions may dominate effects of warming. We tested the hypothesis that food chain length modifies the temperature-dependence of ecosystem fluxes and community structure. In a multi-generation aquatic food web experiment, increasing temperature strengthened a trophic cascade, altering the effect of temperature on estimated mass-corrected ecosystem fluxes. Compared to consumer-free and 3-level food chains, grazer-algae (2-level) food chains responded most strongly to the temperature gradient. Temperature altered community structure, shifting species composition and reducing zooplankton density and body size. Still, food chain length did not alter the temperature dependence of net ecosystem fluxes. We conclude that locally, food chain length interacts with temperature to modify community structure, but only temperature, not food chain length influenced net ecosystem fluxes.

n-Alkane analyses from an transect of marine surface sediments off southwest Africa

An isobathic transect of marine surface sediments from 1°N to 28°S off southwest Africa was used to further evaluate the potential of the chain length distribution and carbon stable isotope composition of higher plant n-alkanes as proxies for continental vegetation and climate conditions. We found a strong increase in the n-C29-33 weighted mean average d13C values from -33 per mil near the equator to around -26 per mil further south. Additionally, C25-35n-alkanes reveal a southward trend of increasing average chain length from 30.0 to 30.5. The data reflect the changing contribution of plants employing different photosynthetic pathways (C3 and C4) and/or being differently influenced by the environmental conditions of their habitat. The C4 plant proportions calculated from the data (ca. 20% for rivers draining the rainforest, to ca. 70% at higher latitude) correspond to the C4 plant abundance in continental catchment areas postulated by considering prevailing wind systems and river outflows. Furthermore, the C4 plant contribution to the sediments correlates with the mean annual precipitation and aridity at selected continental locations in the postulated catchment areas, suggesting that the C4 plant fraction in marine sediments can be used to assess these environmental parameters.

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.

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.

Accumulation rates of plant-wax-derived long-chain C25 to C35 odd-numbered n-alkanes and d13C values of the n-C31 alkane of ODP Hole 175-1077B

The dominant forcing factors for past large-scale changes in vegetation are widely debated. Changes in the distribution of C4 plants-adapted to warm, dry conditions and low atmospheric CO2 concentrations (Collatz et al., 1998, doi:10.1007/s004420050468) -have been attributed to marked changes in environmental conditions, but the relative impacts of changes in aridity, temperature (Pagani et al., 1999, doi:10.1126/science.285.5429.876; Huang et al., 2001, doi:10.1126/science.1060143) and CO2 concentration (Cerling et al., 1993, doi:10.1038/361344a0; Kuypers et al., 1999, doi:10.1038/20659) are not well understood. Here, we present a record of African C4 plant abundance between 1.2 and 0.45 million years ago, derived from compound-specific carbon isotope analyses of wind-transported terrigenous plant waxes. We find that large-scale changes in African vegetation are linked closely to sea surface temperatures in the tropical Atlantic Ocean. We conclude that, in the mid-Pleistocene, changes in atmospheric moisture content - driven by tropical sea surface temperature changes and the strength of the African monsoon - controlled aridity on the African continent, and hence large-scale vegetation changes.

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.

Chemical analysis with regard to global and local climatic forcing measured on sediment core GeoB3711-1, GeoB3711-3 and GeoB4917-8

Global and local climatic forcing, e.g. concentration of atmospheric CO2 or insolation, influence the distribution of C3 and C4 plants in southwest Africa. C4 plants dominate in more arid and warmer areas and are favoured by lower pCO2 levels. Several studies have assessed past and present continental vegetation by the analysis of terrestrial n-alkanes in near-coastal deep sea sediments using single samples or a small number of samples from a given climatic stage. The objectives of this study were to evaluate vegetation changes in southwest Africa with regard to climatic changes during the Late Pleistocene and the Holocene and to elucidate the potential of single sample simplifications. We analysed two sediment cores at high resolution, altogether ca. 240 samples, from the Southeast Atlantic Ocean (20°S and 12°S) covering the time spans of 18 to 1 ka and 56 to 2 ka, respectively. Our results for 20°S showed marginally decreasing C4 plant domination (of ca. 5%) during deglaciation based on average chain length (ACL27-33 values) and carbon isotopic composition of the C31 and C33 n-alkanes. Values for single samples from 18 ka and the Holocene overlap and, thus, are not significantly representative of the climatic stages they derive from. In contrast, at 12°S the n-alkane parameters show a clear difference of plant type for the Late Pleistocene (C4 plant domination, 66% C4 on average) and the Holocene (C3 plant domination, 40% C4 on average). During deglaciation vegetation change highly correlates with the increase in pCO2 (r² = 0.91). Short-term climatic events such as Heinrich Stadials or Antarctic warming periods are not reflected by vegetation changes in the catchment area. Instead, smaller vegetation fluctuations during the Late Pleistocene occur in accordance with local variations of insolation.

(Table 1) Age, fork length, tissue d15N and d13C and mercury content of arctic char (Salvelinus alpinus) across the Canadian Arctic

Among-lake variation in mercury (Hg) concentrations in landlocked Arctic char was examined in 27 char populations from remote lakes across the Canadian Arctic. A total of 520 landlocked Arctic char were collected from 27 lakes, as well as sediments and surface water from a subset of lakes in 1999, 2002, and 2005 to 2007. Size, length, age, and trophic position (d15N) of individual char were determined and relationships with total Hg (THg) concentrations investigated, to identify a common covariate for adjustment using analysis of covariance (ANCOVA). A subset of 216 char from 24 populations was used for spatial comparison, after length-adjustment. The influence of trophic position and food web length and abiotic characteristics such as location, geomorphology, lake area, catchment area, catchment-to-lake area ratio of the lakes on adjusted THg concentrations in char muscle tissue were then evaluated. Arctic char from Amituk Lake (Cornwallis Island) had the highest Hg concentrations (1.31 µg/g wet wt), while Tessisoak Lake (Labrador, 0.07 µg/g wet wt) had the lowest. Concentrations of THg were positively correlated with size, d15N, and age, respectively, in 88,71, and 58% of 24 char populations. Length and d15N were correlated in 67% of 24 char populations. Food chain length did not explain the differences in length-adjusted THg concentrations in char. No relationships between adjusted THg concentrations in char and latitude or longitude were found, however, THg concentrations in char showed a positive correlation with catchment-to-lake area ratio. Furthermore, we conclude that inputs from the surrounding environment may influence THg concentrations, and will ultimately affect THg concentrations in char as a result of predicted climate-driven changes that may occur in Arctic lake watersheds.

Effects of increasing seawater carbon dioxide concentrations on chain formation of the diatom Asterionellopsis glacialis

Diatoms can occur as single cells or as chain-forming aggregates. These two strategies affect buoyancy, predator evasion, light absorption and nutrient uptake. Adjacent cells in chains establish connections through various processes that determine strength and flexibility of the bonds, and at distinct cellular locations defining colony structure. Chain length has been found to vary with temperature and nutrient availability as well as being positively correlated with growth rate. However, the potential effect of enhanced carbon dioxide (CO2) concentrations and consequent changes in seawater carbonate chemistry on chain formation is virtually unknown. Here we report on experiments with semi-continuous cultures of the freshly isolated diatom Asterionellopsis glacialis grown under increasing CO2 levels ranging from 320 to 3400 µatm. We show that the number of cells comprising a chain, and therefore chain length, increases with rising CO2 concentrations. We also demonstrate that while cell division rate changes with CO2 concentrations, carbon, nitrogen and phosphorus cellular quotas vary proportionally, evident by unchanged organic matter ratios. Finally, beyond the optimum CO2 concentration for growth, carbon allocation changes from cellular storage to increased exudation of dissolved organic carbon. The observed structural adjustment in colony size could enable growth at high CO2 levels, since longer, spiral-shaped chains are likely to create microclimates with higher pH during the light period. Moreover increased chain length of Asterionellopsis glacialis may influence buoyancy and, consequently, affect competitive fitness as well as sinking rates. This would potentially impact the delicate balance between the microbial loop and export of organic matter, with consequences for atmospheric carbon dioxide.