Biomarker lipids of the freshwater fern Azolla and its fossil counterpart from the Eocene Arctic Ocean

Eocene sediments recovered from the Lomonosov Ridge in the central Arctic Ocean during Integrated Ocean Drilling Program Expedition 302 contain high amounts of fossil remains of the free floating freshwater fern Azolla. Both extant Azolla and the sediments from the Arctic Azolla interval were found to contain relatively high quantities of compounds identified as 1,ω20 C₃₀–C₃₆ diols. Furthermore, structurally related mid-chain hydroxy fatty acids, long chain n-alkanols and keto-ols were discovered. The different series have a common feature: there is always a hydroxy group at the ω20 position. In addition, structurally related C₂₉ ω20,ω21 diols, C₂₉ 1,20,21 triols, C₂₉ dihydroxy fatty acids as well as a series of wax esters containing these mono- and dihydroxy lipids are reported. Selective extraction of Azolla surface lipids revealed that these compounds are most likely present in the leaf waxes of the fern. The suite of long-chain, mid-chain ω20 hydroxy wax constituents is described for the first time. As they are well preserved in the Eocene sediments, these lipids may serve as palaeo-environmental indicators of the Arctic Azolla interval and as markers for the past occurrence of Azolla in general.     

Mathematical modeling of the aquatic macrophyte inputs of mid-chain n-alkyl lipids to lake sediments: Implications for interpreting compound specific hydrogen isotopic records

We present a systematic study of chain-length distributions and D/H ratios of n-alkyl lipids (both n-alkanes and n-alkanoic acids) in a wide range of terrestrial and aquatic plants around and in Blood Pond, Massachusetts, USA. The primary goal is to establish a model to quantitatively assess the aquatic plant inputs of the mid-chain length n-alkyl lipids to lake sediments and to determine the average hydrogen isotopic ratios of these lipids in different plants. Our results show that middle-chain n-alkyl lipids (C₂₁-C₂₃n-alkanes and C₂₀-C₂₄n-alkanoic acids) are exceptionally abundant in floating and submerged aquatic plants, in contrast to the dominance of long-chain n-alkyl lipids (C₂₇-C₃₁n-alkanes and C₂₆-C₃₂n-alkanoic acids) in other plant types, which are consistent with previously published data from Mountain Kenya and the Tibetan Plateau. Combining available data in different environmental settings allows us to establish statistically robust model distributions of n-alkyl lipids in floating/submerged macrophytes relative to other plant types. Based on the model distributions, we established a multi-source mixing model using a linear algebra approach, in order to quantify the aquatic inputs of mid-chain n-alkyl lipids in lake sediments. The results show that ∼97% of the mid-chain n-alkyl lipids (C₂₃n-alkane and C₂₂n-acid (behenic acid)) in Blood Pond sediments are derived from floating and submerged macrophytes. In addition, D/H ratios of C₂₂n-acid and C₂₃n-alkane in the floating and submerged plants from Blood Pond display relatively narrow ranges of variation (−161 ± 16‰ and −183 ± 18‰, respectively). Our study demonstrates that mid-chain n-alkyl lipids such as C₂₃n-alkane and C₂₂n-acid could be excellent recorders of past lake water isotopic ratios in lakes with abundant floating and submerged macrophyte inputs.     

Carbon isotope composition of long chain leaf wax n-alkanes in lake sediments: A dual indicator of paleoenvironment in the Qinghai-Tibet Plateau

The carbon isotope composition (δ¹³C values) of long chain n-alkanes in lake sediments has been considered a reliable means of tracking changes in the terrigenous contribution of plants with C₃ and C₄ photosynthetic pathways. A key premise is that long chain leaf wax components used for isotope analysis are derived primarily from terrigenous higher plants. The role of aquatic plants in affecting δ¹³C values of long chain n-alkanes in lacustrine sediments may, however, have long been underestimated. In this study, we found that a large portion of long chain n-alkanes (C₂₇ and C₂₉) in nearshore sediments of the Lake Qinghai catchment was contributed by submerged aquatic plants, which displayed a relatively positive carbon isotope composition (e.g. −26.7‰ to −15.7‰ for C₂₉) similar to that of terrestrial C₄ plants. Thus, the use of δ¹³C values of sedimentary C₂₇ and C₂₉ n-alkanes for tracing terrigenous vegetation composition may create a bias toward significant overestimation/underestimation of the proportion of terrestrial C₄ plants. For sedimentary C₃₁, however, the contribution from submerged plants was minor, so that the δ¹³C values for C₃₁ n-alkane in surface sediments were in accord with those of the modern terrestrial vegetation in the Lake Qinghai region. Moreover, we found that changes in the δ¹³C values of sedimentary C₂₇ and C₂₉ n-alkanes were closely related to water depth variation. Downcore analysis further demonstrated the significant influence of endogenous lipids in lake sediments for the interpretation of terrestrial C₄ vegetation and associated environment/climate reconstruction. In conclusion, our results suggest that the δ¹³C values of sedimentary long chain n-alkanes (C₂₇, C₂₉ and C₃₁) may carry different environmental signals. While the δ¹³C values of C₃₁ were a reliable proxy for C₄/C₃ terrestrial vegetation composition, the δ¹³C values of C₂₇ and C₂₉ n-alkanes may have recorded lake ecological conditions and sources of organic carbon, which might be affected by lake water depth.     

n-Alkane distribution and carbon stable isotope composition in leaf waxes of C3 and C4 plants from Angola

Palaeoenvironmental assessment of past C₃ and C₄ vegetation distributions relies on end member data from plant analyses. In southwestern Africa, end member data of the carbon number distribution of n-alkanes from leaf waxes and their carbon isotopic composition were available for the rainforest and the savannah. To complement this, we analysed the n-alkane parameters of 41 C₃ plants and 11 C₄ plants from the transition region, i.e., the wood- and shrubland of Angola. The combined results for the rainforest, the wood- and shrubland and the savannah show an increase in the average chain length (ACL) of C₃ and C₄ plants and an increasingly enriched carbon stable isotope composition for the C₃ plants from the equator towards southern Africa. The enlarged database was applied to the data of a north–south transect of deep-sea surface sediments already used in a previous study, which resulted in the proxies showing a good reflection of the vegetation on the adjacent southwest African continent in terms of %C₄ plant cover. Applying end member values for ACL and δ¹³C obtained from the enlarged database by two different averaging methods (arithmetic average and median) to the n-alkane data from the sediment transect yielded similar vegetation reconstructions. In addition, a correlation between ACL and growth height of the plants is discussed, indicating that the ACL may be useful as a tree abundance parameter. Thus, the enlarged end member database strengthens the n-alkane parameters as tools for palaeoenvironmental studies.     

Biomarkers in surface sediments from the Cross River and estuary system,SE Nigeria: Assessment of organic matter sources of natural and anthropogenic origins

Herein, lipid biomarker analysis is applied to surface sediments from the southeastern Niger Delta region for the quantitative determination of aliphatic lipids, steroids and triterpenoids in order to differentiate between natural (autochthonous vs. allochthonous) and anthropogenic organic matter (OM) inputs to this deltaic environment. This ecosystem, composed of the Cross, Great Kwa and Calabar Rivers, is receiving new attention due to increased human and industrial development activities and the potential effects of these activities impacting its environmental health. While the presence of low molecular weight n-alkanes (<C₂₂) and the fossil biomarkers pristane and phytane in all samples, are indicative of a minor petroleum related input, the total extractable organic component of the surface sediments of these rivers remains predominantly of a natural origin as characterized by the variety and predominance of lipid classes that are mainly derived from the epicuticular waxes of vascular plants and include n-alkanes, n-alkanols, n-alkan-2-ones, n-alkanoic acids, steroids and triterpenoids. In addition, recent OM inputs from microorganisms are indicated by the presence of lower molecular weight n-alkanoic acids (C_max = 16), while the major triterpenoids of the sediments, taraxerol and friedelin, and the major sterol, sitosterol, indicate recent OM inputs from vascular plants. Plankton-derived sterols, such as fucosterol and dinosterol, are also found in sediments from the Cross and Great Kwa Rivers and likely originate from autochthonous primary productivity. Furthermore, the coprosterols coprostanol and 24-ethylcoprostanol are present in most samples and indicate measurable anthropogenic contributions from domestic untreated sewage inputs and agricultural run-off, respectively. Of the three rivers studied, the Cross River system was excessively influenced by human and industrial development activities, including drivers such as urbanization and population center growth, land-use change to support agricultural production and animal husbandry, and petroleum exploration and production. These influences were found to be regionally specific as controlled by point sources of pollution based on the relative distributions measured and on the fact that the molecular characteristics of sedimentary OM were not distributed smoothly along a gradient.     

Distribution patterns and stable carbon isotopic composition of alkanes and alkan-1-ols from plant waxes of African rain forest and savanna C3 species

Leaf wax components of terrestrial plants are an important source of biomass in the geological records of soils, lakes and marine sediments. Relevant to the emerging use of plant wax derived biomarkers as proxies for past vegetation composition this study provides key data for C₃ plants of tropical and subtropical Africa. We present analytical results for 45 savanna species and 24 rain forest plants sampled in their natural habitats. Contents and distribution patterns of long chain n-alkanes (n-C₂₅ to n-C₃₅) and n-alkan-1-ols (n-C₂₄ to n-C₃₄) as well as bulk and molecular carbon isotopic data are presented. The variations of the analysed parameters among different growth forms (herb, shrub, liana and tree) are small within the vegetation zones, whereas characteristic differences occur between the signatures of rain forest and savanna plants. Therefore, we provide averaged histogram representations for rain forest and savanna C₃ plants.The findings were compared to previously published data of typical C₄ grass waxes of tropical and subtropical Africa. Generally, trends to longer n-alkane chains and less negative carbon isotopic values are evident from rain forest over C₃ savanna to C₄ vegetation. For n-alkanols of rain forest plants the maximum of the averaged distribution pattern is between those of C₃ savanna plants and C₄ grasses. The averaged presentations for tropical and subtropical vegetation and their characteristics may constitute useful biomarker proxies for studies analysing the expansion and contraction of African vegetation zones.     

n-Alkan-2-ones in peat-forming plants from the Roñanzas ombrotrophic bog (Asturias, northern Spain)

We determined the distribution of lipids (n-alkanes and n-alkan-2-ones) in present-day peat-forming plants in the Roñanzas Bog in northern Spain. Consistent with the observation of others, most Sphagnum (moss) species alkanes maximized at C₂₃, whereas the other plants maximized at higher molecular weight (C₂₇ to C₃₁). We show for the first time that plants other than seagrass and Sphagnum moss contain n-alkan-2-ones. Almost all the species analysed showed an n-alkan-2-one distribution between C₂₁ and C₃₁ with an odd/even predominance, maximizing at C₂₇ or C₂₉, except ferns, which maximized at lower molecular weight (C₂₁-C₂₃). We also observed that microbial degradation can be a major contributor to the n-alkan-2-one distribution in sediments as opposed to a direct input of ketones from plants.     

Hydrocarbons in 60 northeast Gulf of Mexico shelf sediments: a preliminary survey

Hydrocarbon results from gas chromatography of 60 recent sediment and 10 benthic algae samples delineate two distinct shelf environments in the northeastern Gulf of Mexico.Sediments off Florida (shell hashes and sands) have moderate amounts of lipids/total sediment (average 113ppm ± 80%) but low hydrocarbon levels (average 3.06 ppm ± 41%). Aliphatic hydrocarbons are dominated by a series of branched or cyclic, unsaturated C₂₅ isomers. The major n-alkane is n-C₁₇. The n-alkane and isoprenoid patterns are consistent with a marine hydrocarbon source.Sediments closer to the Mississippi River (silts and clays) contain large amounts of lipids (average 232 ppm ± 53%) and hydrocarbons (average 11.7 ppm ± 55%) to total sediment. Aliphatic hydrocarbons are mainly odd carbon number high molecular weight n-alkanes, indicating a terrigenous hydrocarbon source. Isoprenoids are present in greater abundance than in sediments off Florida (n-C₁₇/ pristane and n-C₁₈/phytane ratios ~2to 3). Relatively large amounts of n-C₁₆, together with an even distribution of n-alkanes in the range C₁₄–C₂₀ and a substantial unresolved envelope all point to a fossil fuel input to the Mississippi samples.Samples off the Alabama coast show intermediate characteristics.     

Biogeochemical controls on reaction of sedimentary organic matter and aqueous sulfides in holocene sediments of Mud Lake, Florida

The distribution and quantity of organic sulfur and iron sulfur species were determined in the Holocene sediments from Mud Lake, Florida. The sediments of this shallow, sinkhole lake are characterized by high sulfur and organic carbon contents as well as active sulfate reduction. They record a shift from a basal peat (below 2 m) comprised of water lily-dominated organic matter to the present cyanobacterial/algal-dominated lake deposit (upper 1 m). This shift in depositional environment and subsequent organic matter source was accompanied by variation in the amount of reactive iron delivered to the sediments, which in turn influenced the type and extent of organic matter sulfurization. Extractable intramolecular organic sulfur is principally found as C₂₅ highly branched isoprenoid (HBI) thiolanes. Extractable polysulfide-linked lipids, determined by selective chemical cleavage with MeLi/MeI and analyzed as methylthioethers (MTE), are dominated by n-alkanes with sulfur attachments at position 1 and 2, as well as lower amounts of C₂₅ HBI-MTE. The δ¹³C values and carbon-chain length distribution of both series of n-alkylMTE indicate that they are derived from distinct biological precursors. Among the n-alkylMTE with sulfur attachment at position 1 there are three homologous series: one saturated and two with both cis and trans enethiol isomers. The identification of the enethiol in the sulfur-linked macromolecules indicates that n-alkylaldehydes are precursors lipids. The intervals of high concentration of bulk organic sulfur and sulfurized lipids coincide with the intervals of high mineral sulfur content (acid volatile sulfide and chromium reducible sulfur). We suggest that the main control on the enhanced addition of sulfur to the organic matter in Mud Lake was the increased formation of polysulfides during the reduction of iron hydroxides and the subsequent reaction of those polysulfides with mildly oxidized sedimentary organic matter.     

Carbon isotope analyses of n-alkanes in dust from the lower atmosphere over the central eastern Atlantic

Atmospheric dust samples collected along a transect off the West African coast have been investigated for their lipid content and compound-specific stable carbon isotope compositions. The saturated hydrocarbon fractions of the organic solvent extracts consist mainly of long-chain n-alkanes derived from epicuticular wax coatings of terrestrial plants. Backward trajectories for each sampling day and location were calculated using a global atmospheric circulation model. The main atmospheric transport took place in the low-level trade-wind layer, except in the southern region, where long-range transport in the mid-troposphere occurred. Changes in the chain length distributions of the n-alkane homologous series are probably related to aridity, rather than temperature or vegetation type. The carbon preference of the leaf-wax n-alkanes shows significant variation, attributed to a variable contribution of fossil fuel- or marine-derived lipids. The effect of this nonwax contribution on the δ¹³C values of the two dominant n-alkanes in the aerosols, n-C₂₉ and n-C₃₁ alkane, is, however, insignificant. Their δ¹³C values were translated into a percentage of C₄ vs. C₃ plant type contribution, using a two-component mixing equation with isotopic end-member values from the literature. The data indicate that only regions with a predominant C₄ type vegetation, i.e. the Sahara, the Sahel, and Gabon, supply C₄ plant-derived lipids to dust organic matter. The stable carbon isotopic compositions of leaf-wax lipids in aerosols mainly reflect the modern vegetation type along their transport pathway. Wind abrasion of wax particles from leaf surfaces, enhanced by a sandblasting effect, is most probably the dominant process of terrigenous lipid contribution to aerosols.     

Lipid geochemistry in a sediment core from Ruoergai Marsh deposit (Eastern Qinghai-Tibet plateau, China)

Peats in a sediment core from Ruoergai bog, which has a cold and moist plateau climate with major source input from herbaceous plants, have been studied by GC–MS in order to understand the composition and diagenetic processes of lipids in this depositional environment. Long chain components (C₂₁–C₃₅) predominate in the n-alkanes, n-alk-1-enes, n-fatty acids, n-alkan-2-ones and n-alkanols with a maximum of C₃₁, C_27, C₂₂ or C_24, C₂₃ or C₂₅ and C₂₂, respectively. A herbaceous origin for these long chain compounds is suggested, and this is supported by their stable carbon isotopic compositions. Diterpenoid hydrocarbons with abietane, pimarane and kaurane skeletons, some of which have not been reported often in modern sediments, are prominent and are derived from higher plants. Several triterpenoid ketones and alcohols with oleanane or lupane skeletons, and a series of des-A-triterpenoid hydrocarbons which have not been reported often in modern sediments are also present, and are assigned to a higher plant source. Hopanoids, including their alkanes, alkenes, ketones, alcohols and esters, are abundant and of bacterial origin. Steroid ketones and alkanols are dominated by C₂₉ homologues. C₂₈ and C₂₉ steroids are derived mainly from higher plants, whereas the C₂₇ component is assigned to a microbial source. The presence of short-chain n-alkanes with no odd-even carbon predominance, bacterially derived fatty acids (C₁₄, C₁₅, iso- and unsaturated acids), n-alkan-2-ones, des-A-triterpenoid hydrocarbons, hopanoids and some steroid ketones indicate that intense microbial reworking of the organic matter has taken place in this depositional environment. The chemical and biochemical conversions of some cyclic alkenes to alkanes, such as tricyclic diterpenoids, tetracyclic terpenoids and steroid ketones, are also evident with depth. The dominance of C₂₀ components in the diterpenoid hydrocarbons may reflect an oxidizing or reducing depositional condition.     

Occurrence and distribution of long-chain acyclic ketones in immature coals

Seven coal and carbonaceous mudstone samples were collected from outcropping Jurassic coal beds, on the margin of the Dingxi Basin, Northwestern China. The n-alkane distributions in all of the samples are characterised by high concentrations of the C₁₉–C₂₉ homologues, and very much lower amounts outside of this range. C₂₃ or C₂₄ are usually the most abundant n-alkanes. Straight chain n-alkanes from C₂₃ to C₂₉ show moderate odd-to-even C number predominances (CPI range: 1.26–2.70). Long-chain acyclic n-alkan-2-ones, n-alkan-3-ones and n-alkan-4-ones ranging from C₁₅ to C₃₃ with moderate odd-to-even C number predominances, were detected together with one isoprenoid methyl ketone (6,10,14-trimethylpentadecan-2-one) in all of the samples. The C number distributions of the three series of alkanones show a similar distribution to that of the n-alkanes, but the correspondence is not sufficient to substantiate a product–precursor relationship. It can be concluded that the n-alkan-2-ones are a mixture of the products of microbially-mediated β-oxidation of corresponding n-alkanes in the sediments and from the microbial oxidation of higher plant-derived n-alkanes prior to incorporation in the sediments. The n-alkan-3-ones and n-alkan-4-ones were formed from microbially mediated oxidation of the corresponding n-alkanes in the γ and δ positions, respectively. Generation of the ketones from higher plant n-fatty alcohols and n-alkanoic acids could be a possible way to form some of the ketones observed, but it can only play a minor role in the samples analysed.     

n-Alkane parameters from a deep sea sediment transect off southwest Africa reflect continental vegetation and climate conditions

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-C_29–33 weighted mean average δ¹³C values from −33‰ near the equator to around −26‰ further south. Additionally, C_25–35 n-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.     

Characterization and sources of extractable organic matter from sediment cores of an urban lake (Tasik Perdana), Kuala Lumpur,Malaysia

The extractable organic matter of sediment samples from six sampling sites in Lake Perdana, Kuala Lumpur, was analyzed to characterize the source inputs. The analysis of aliphatic homologous series indicated that terrestrial higher plant waxes can be assigned as the major sources of the identified aliphatic components in the lake sediments. The presence of an unresolved complex mixture of branched and cyclic compounds and a series of hopanes ranging from C₂₇ to C₃₅ reflected the contamination by petroleum residues from urban vehicular emissions brought in by runoff and fallout. The steroids present included stenols and stanols and showed an input of organic matter from higher plants. The detected pentacyclic triterpenoids comprised oleanane, ursane, lupane and friedelane skeletons including unsaturated oxygenated, mono-, di- and triaromatic counterparts. They are recognized as biomarkers for angiosperms. The presence of des-A-triterpenoids and their aromatized derivatives as the major diagenetic products of triterpenoids reflected the degradation of natural organic matter in the sediments occurring under mainly anoxic conditions. In addition, the presence of tetrahymanol and ββ-bishomohopan-32-ol indicated a minor algal/plankton and bacterial input to the sediments.     

东海泥质区单体正构烷烃的碳同位素组成及物源分析 *

利用气相色谱(GC)和气相色谱/同位素比值质谱(GC/IRMS)对东海近岸泥质区、济州岛西南泥质区和冲绳海槽北部表层沉积物中正构烷烃的单体碳同位素组成及分布进行了分析。结果显示东海不同泥质区典型海洋藻类源正构烷烃C₁₉同位素组成基本相似,在-27.4 ‰ ~-28.0 ‰ 之间,平均为-27.7 ‰ 。典型海洋水生植物源C₂₃同位素组成在-28.5 ‰ ~-31.6 ‰ 之间,平均为-30.5 ‰ ,碳同位素组成从近岸泥质区到冲绳海槽北部逐渐变重,表明海槽区与陆架区海洋水生植物种类有所不同。陆架区长链正构烷烃(C₂₅~C₃₁)部分随着碳数的增加,其同位素组成逐渐变轻,但海槽区这一变化不大,显示陆架区的陆源高等植物蜡具有相似的物源,而冲绳海槽北部由于黑潮主干区和黑潮分支(对马暖流)对陆架沉积物进入深海的控制性阻隔作用,其物源与陆架区区别较大。现代输入东海的陆源植物以C₃植物为显著优势,C₃植物对近岸泥质区北部、近岸泥质区南部、远端济州岛西南泥质区和冲绳海槽北部陆源植物的贡献分别为83 % ,95 ％,75 % 和70 % 。     

Late Quaternary environmental change of Yellow River Basin: An organic geochemical record in Bohai Sea (North China)

Bulk geochemical characterization (total organic carbon, grain size distribution, carbon isotope composition) and molecular biomarkers (lignin phenols, straight chain aliphatic hydrocarbons, glycerol dialkyl glycerol tetraethers) were analyzed for a 21 m core from the Bohai Sea (North China), spanning ca 21 ka BP. These paleo-proxies presented remarkable differences between the late glacial period and the Holocene, reflecting continental and coastal environments, respectively. Two peat layers were deposited during the period of ca 9000-8460 yr BP. Thereafter the core site has been consistently covered by seawater until recent reclamation of land from the sea. The occurrence of a total organic carbon maximum from ca 6000-3800 yr BP was attributed to delivery of organic carbon enriched sediments via the Yellow River, consistent with increased vegetation density and higher development of soil under warm and humid mid-Holocene climate conditions. The distributions of lignin phenol compositions and C₃₁/C₂₉n-alkane ratio suggested the largest expansion of woody plants between ca 5300 and 4000 yr BP, corresponding to the extremely favorable climatic conditions. Since ca 3800 yr BP, an abrupt increase in the C₃₁/C₂₉n-alkane ratio suggested higher abundance of grasses, consistent with a drying climate trend after the mid-Holocene. Since our coastal sediments close to the Yellow River outflow contain catchment-integrated environmental signals of the river basin, molecular proxies demonstrate that the variability of vegetation distributions in the Holocene is a widespread phenomenon in those areas adjacent to Yellow River Basin.     

A 35 kyr record of organic matter composition and δ13C of n-alkanes in bog sediments close to Lake Baikal: Implications for paleoenvironmental studies

We characterized the compositions of organic compounds in a Cheremushka bog sediment core (deposited over the last 35 kyr), located at the eastern coast of Lake Baikal, to obtain basic information about the terrestrial organic matter (OM) which contributed to Lake Baikal sediments. The bog sediment was analyzed for the molecular composition of n-alkanes, lignin phenols and n-C₂₄ to C₃₀ alkanoic acids, as well as the carbon isotopic composition of plant wax derived n-C₂₇ to C₃₃ alkanes.Concentrations of lignin phenols [vanillyl (V) plus syringyl (S) phenols] normalized to total organic carbon (TOC) in the Holocene are twice those for the last glacial maximum (LGM), while concentrations of TOC-normalized n-C₂₄ to C₃₀ alkanoic acids do not change markedly in this period. Thus, the ratio of lignin phenols to n-C₂₄ to C₃₀ alkanoic acids increases from the LGM to the Holocene. This result is essentially consistent with pollen analysis indicating an expansion of woody plants in the Holocene and a prevailing herb-abundant environment for the LGM. The δ¹³C values of n-C₂₇ to C₃₃ alkanes (e.g. ?29‰ to ?33‰ for C₃₁) indicate the presence of C₃-dominant plants throughout the core.The contribution of terrestrial OM to Lake Baikal sediments was estimated using the biomarkers, on the assumption that the OM in the bog sediments is a representative of the terrestrial OM around the lake. Hence, the estimation using lignin phenol or n-C₂₄ to C₃₀ alkanoic acid parameters indicates that 11–24% of the TOC in the Academician Ridge sediments is land-derived for both the Holocene and the LGM, which is similar to the estimates from C/N values of bulk OM. However, the estimates for terrestrial OM using the n-C₂₇ to C₃₃ alkane parameter are generally higher than those using lignin phenol or n-C₂₄ to C₃₀ alkanoic acid parameters. The difference is thought to be associated with the difference in source and behavior of these biomarkers.     

Isotopic compositions of tropical East African flora and their potential as source indicators of organic matter in coastal marine sediments

The C and N stable isotope compositions of some flora of East Africa from coastal Tanzania and Amboseli National Park (Kenya) are used to assess if they can be used as a terrestrial end member during the estimation of terrestrial fraction in coastal marine sediments. The results of C isotope composition of various tree leaves, which average −29.3 ± 1.4%, indicate that these tropical higher land plant species follow a Calvin-Benson or non-Kranz (C₃) type of metabolism. The results for grass species, which average −13.2 ± 2.4%, indicate that most of them follow a Hatch-Slack or Kranz (C₄) type of metabolism. However, some of the succulent plants from the Amboseli National Park have δ¹³C values that average −14.7%, an indication that they follow a CAM (Crassulacean Acid Metabolism) type of metabolism. The N isotope values are relatively higher than expected for the terrestrial organic material. The average δ¹⁵N values for both tree and grass samples are higher than 5% and fall within the range normally considered to be marine. The high enrichment in ¹⁵N may be related to the environmental conditions in which plants thrive. Plants growing in sandy, dry and overgrazed environments are expected to be enriched in ¹⁵N owing to full utilisation of all available N species, regardless of their isotopic compositions. Other processes which may cause an enrichment in ¹⁵N include adsorption by various types of clay minerals, supply of ¹⁵N-enriched nitrate through sea-spray, and local denitrification, especially in swampy and lake margins where the input of organic matter may be higher than the rate of decomposition.The stable isotopic composition of organic C and N for surficial organic matter for the coastal marine sediments averages −17.0 ± 0.9% and 5.4 ± 1.1%, respectively. These values indicate a substantial contribution of C₄ plants and sea grasses. However, contribution of C₄ relative to that of sea grasses can not be evaluated owing to the fact that there is no significant difference in the isotopic compositions between the two groups.In the savannah environment, where a contribution from the C₄ types of plants might be substantial, the δ¹³C value for a terrestrial end member needs to be established prior to evaluation of the terrestrially derived organic matter in the marine environment. Owing to a significant contribution of sea grasses to the total organic matter preserved in coastal marine sediments, the stable isotopes of organic C seem to have a limited applicability as source indicators in the East African coastal waters. Furthermore, the results indicate that N stable isotopes seem to have a limited applicability as source indicators in coastal waters of East Africa. However, more work needs to be conducted to determine the terrestrial and sea grass end member values for the coastal areas.     

Marine and terrigenous lipids in coastal sediments from the Peru upwelling region at 15°S: Sterols and triterpene alcohols

The distributions of free 4-desmethyl sterols in sediments from the Peru coastal zone at 15°S have been determined. Major free sterols in the surface sediments include cholesterol, which is mainly derived from zooplankton, and two C₂₈ sterols: 24-methylcholesta-5,24(28)-dien-3β-ol and 24-methylcholesta-5,22E-dien-3β-ol both of which are derived fro diatoms. Their concentrations decrease by almost an order of magnitude in the top 20 cm of sediment depth, indicating that free sterols are rapidly degraded in this sedimentary environment. Lipids from higher plants were also detected: long chain fatty acids and alcohols and various triterpenoid alcohols, including taraxerol, lupeol and α- and β-amyrin. The concentrations of most terrigenous lipids varied by less than a factor of 3 over the same depth, and these changes were not correlated with changes in the concentrations of total organic carbon. Below 3 cm, lipids from higher plants predominated in the extractable lipid distributions due to the more rapid degradation of marine lipids. We postulate that there are significant marine sources of the higher plant sterols 24-ethylcholesterol, 24-ethylcholesta-5,22E-dien-3β-ol and 24-methylcholesterol in these sediments. A high proportion of many of the terrigenous lipids in these sediments are probably transported into the coastal zone by rivers, rather than from the atmosphere, and then redistributed by bottom currents.     

Latitudinal and downcore (0–750 ka) changes in n-alkane chain lengths in the eastern equatorial Pacific

The n-alkane C₃₁/(C₂₉ + C₃₁) ratios from surface sediments in the eastern equatorial Pacific (EEP) exhibit higher values to the north and lower values to the south across the southern edge (2–4°N) of the Intertropical Convergence Zone (ITCZ). Since plants tend to synthesize longer chain length n-alkanes in response to elevated temperature and/or aridity, the higher C₃₁/(C₂₉ + C₃₁) ratios at northern sites suggest a higher contribution of vegetation under hot and/or dry conditions. This is consistent with the observation that northern sites receive higher levels of plant waxes transported by northeasterly trade winds from northern South America, where hot and dry conditions prevail. Furthermore, from a sediment core covering the past 750 ka (core HY04; 4°N, 95°W) we found that C₃₁/(C₂₉ + C₃₁) ratios exhibit a long-term decrease from MIS (marine oxygen isotope stage) 17 to 13. During this period, the zonal SST (sea-surface temperature) gradient in the equatorial Pacific increased, suggesting an increase in Walker circulation. Such intensified Walker circulation may have enhanced moisture advection from the equatorial Atlantic warm pool to the adjacent northern South America, causing arid regions in northern South America to contract, which may explain long-term decrease in n-alkane chain lengths.