CPI values of terrestrial higher plant-derived long-chain n-alkanes: a potential paleoclimatic proxy

Carbon Preference Index (CPI values) of higher plant-derived long-chain n-alkanes extracted from 62 surface soil samples in eastern China exhibited a specific pattern of variations, namely gradual increase with the increasing latitudes. Such regular variations existed in both forest soil and grassland soil. Our data implied that CPI values of higher plant-derived long-chain n-alkanes had a certain connection with climatic conditions, and such a connection was not influenced by vegetation types. Together with previous data from marine sediments, loess/paleosol sequences, tertiary red clay and modern plants, our observation made us conclude that CPI values of higher plant-derived long-chain n-alkanes may be used as an excellent proxy for paleoclimatic studies.     

Characterisation of n-alkanes and their hydrogen isotopic composition in sediments from Lake Qinghai, China

The distributions of n-alkanes and their hydrogen isotopic composition (δD) in surface and core sediments from the saline Qinghai Lake were measured to assess whether or not biological source information was recorded in the δD values of n-alkanes. The results indicate that the n-alkane distributions between shallow water surface and core sediments were similar, and closer to those of terrestrial herbaceous plants from the Qinghai Lake surrounding areas, rather than the aquatic plants living in the lake. The n-alkanes in the surface and core sediments had similar mean δD values, ranging from −185‰ to −133‰ and −163‰ to −142‰, respectively. The mean δD values of n-alkanes in the sediments showed that the even n-alkanes were heavier in D compared with the odd homologues.     

Distributions of n-alkanes and their hydrogen isotopic composition in plants from Lake Qinghai (China) and the surrounding area

Various aquatic plants from Lake Qinghai, the largest inland saline lake in China, and terrestrial plants from the surrounding area were investigated for the distribution of n-alkanes and their δD values. The n-alkanes in the samples range from C₁₅ to C₃₃ with C preference index (CPI) values of 4.0–29.7. The n-C₂₃ or n-C₂₅ alkane is the dominant compound in the aquatic submerged plants. The aquatic emergent and terrestrial plants have an abundance maximum at n-C₂₇, n-C₂₉ or n-C₃₁. The average chain length (ACL) values, ranging from 26.0 to 29.6, are closely related to the plant species. The n-alkanes from the aquatic plants have mean δD values of −169‰ to −121‰ and those from the terrestrial plants values of −173‰ to −109‰. The H isotopic composition (δD) and fractionation differ significantly among the plants studied. Comparison shows that additional evaporative enrichment of the lake water associated with saline lakes and humidity influence the δD values of the n-alkanes in aquatic and terrestrial plants, respectively. The mean δD values of n-alkanes in the plants decrease with increasing ACL value. The n-alkanes from the different types of plants are more depleted in D relative to environmental water and those from aquatic plants (with a mean value of −143‰) have a greater isotopic fractionation than terrestrial plants (mean value −113‰).     

Leaf wax n-alkane δD values of field-grown barley reflect leaf water δD values at the time of leaf formation

Leaf wax n-alkanes from barley (Hordeum vulgare) from a field in Switzerland exhibited changes in δD values on the order of 20‰ over a growing season, while source water (soil water) and leaf water varied by 40‰. Additionally the seasonal variability in δD values of leaf wax n-alkanes of different barley leaves can only be found across different leaf generations (i.e. leaves that were produced at different times during the growing season) while n-alkane δD values did not vary significantly within a leaf generation. Interestingly, δD values of n-alkanes correlated best with the δD values of leaf water at midday of the sampling day but showed no significant correlation with soil water (e.g. precipitation) δD values. These results provide empirical evidence that leaf wax δD values record leaf water enrichment, and therefore integrate the isotopic effects of precipitation and evapotranspiration. Our results show that leaf wax n-alkane δD values from grasses are ‘locked in’ early during leaf development and hence record the environmental drivers of leaf water enrichment, such as vapor pressure deficit (VPD). Our data have important implications for the interpretation of paleorecords of leaf wax δD. We suggest that leaf wax n-alkane δD values from sedimentary records could be used to estimate changes in the degree of leaf water enrichment and hence VPD.     

Distribution of n-alkanes in lacustrine sediments from subtropical lake in Brazil

The geochemical composition of lake bed sediments of a tropical reservoir in Brazil have been investigated. The C, N, P composition showed almost no variation between the different sampling points. All samples contained inorganic phosphorus (IP) ranging from 52 to 70%. The Redfield ratios show that the lake is without significant anthropogenic inputs. Most of the organic matter is composed by higher plants decomposition revealed in the total organic carbon (TOC):nitrogen (N) ratio ranging from 15.4 to 57.2. Also, TOC:organic phosphorus (OP) ranged from 265.3 to 933.6, suggesting that most of the organic matter has terrestrial origin from wood plants. The ratios suggest that most organic matter is influenced by the terrestrial characteristics of the watershed. Furthermore, the relative abundance of n-alkane homologues in the sediments was investigated. All samples have been analyzed for the n-alkanes C₈ to C₄₀. The sediments were dominated by n-alkanes C₂₅–C₃₈. It is concluded that n-alkane in sediments mainly come from terrestrial plants, however there is a contribution of submerged aquatic plants, especially in those sites in deeper areas of the lake. On the basis of P_aq index the n-alkanes in sediments comes from terrestrial plants, however there is a contribution from emerged/floating plants.The investigated lake seems to be considered as meso to eutrophic. Because of the relatively high primary productivity in the lakes, there is a substantial organic-matter flux to the sediments, which rapidly becomes anoxic. According to the pristine/phytane ratio the sediments represent an anoxic environment with values found between 0.38 and 1.72.     

Spatial heterogeneity in lipid biomarker distributions in the catchment and sediments of a crater lake in central India

The basin-scale spatial variability in lipid biomarker proxies in lacustrine sediments, which are established tools for studying continental environmental change, has rarely been examined. It is often implicitly assumed that a lake sediment core provides an average integral of catchment sources. Here we evaluated the distribution of lipid biomarkers in a modern ecosystem and compared it with the sedimentary record. We analyzed lipid biomarkers in terrestrial and aquatic organisms and in lake surface sediments from 17 locations within the saline–alkaline Lonar crater lake in central India. Terrestrial vegetation and lake surface sediments were characterized by relatively high average chain length (ACL) index values (29.6–32.8) of leaf wax n-alkanes, consistent with suggestions that plants in drier and warmer climates produce longer chain alkyl lipids than plants in cooler and humid areas. A heterogeneous spatial distribution of ACL values in lake surface sediments was found: at locations away from the shore, the values were highest (31 or more), possibly indicating different sources and/or transport of terrestrial biomarkers. In floating, benthic microbial mats and surface sediment, n-heptadecane, carotenoids, diploptene, phytol and tetrahymanol occurred in large amounts. Interestingly, these biomarkers of a unique bacterial community were found in substantially higher concentrations in nearshore sediment samples. We suggest that human influence and subsequent nutrient supply resulted in increased primary productivity, leading to an unusually high concentration of tetrahymanol in the nearshore sediments.In summary, the data showed that substantial heterogeneity existed within the lake, but leaf wax n-alkanes in a core from the center of the lake represented an integral of catchment conditions. However, lake level fluctuation may potentially affect aquatic lipid biomarker distributions in lacustrine sediments, in addition to source changes.     

Effect of climate change on delivery and degradation of lipid biomarkers in a Holocene peat sequence in the Eastern European Russian Arctic

Lipid biomarkers from a peat plateau profile from the Northeast European Russian Arctic were analyzed. The peat originated as a wet fen ca. 9 ka BP and developed into a peat bog after the onset of permafrost ca. 2.5 ka BP. The distributions and abundances of n-alkanols, n-alkanoic acids, n-alkanes, n-alkan-2-ones and sterols were determined to study the effect of degradation on their paleoclimate proxy information. Plant macrofossil analysis was also used in combination with the lipid distributions. The n-alkanol and n-alkanoic acid distributions in the upper part of the sequence generally correspond to compositions expected from plant macrofossil assemblages. Their carbon preference index (CPI) values increase with depth and age, whereas those of the n-alkanes decrease. The different CPI patterns suggest that n-alkanoic acids and n-alkanols deeper in the sequence may be produced during humification through alteration of other lipids. Excursions in the n-alkanoic acid content also suggest an important contribution of invasive roots to the lipid biomarker composition. The CPIs associated with these compounds show that under permafrost conditions organic material from Sphagnum is better preserved than material from vascular plants. Increasing stanol/stenol ratio values and decreasing n-alkane CPI values indicate progressive degradation of organic matter (OM) with depth. The n-alkan-2-one/n-alkane and n-alkan-2-one/n-alkanoic acid ratios were shown to be useful proxies that can reflect the degree of OM preservation and suggest that both microbial oxidation of n-alkanes and decarboxylation of n-alkanoic acids produce n-alkan-2-ones in this peat sequence.     

银川盆地35ka以来古植被演化的类脂分子记录

为了更好地了解干旱-半干旱区的植被类型及其演化规律,利用气相色谱仪对银川盆地冰沟剖面河湖相沉积物中的正构烷烃进行了检测,结果显示其正构烷烃碳数分布范围为C15~C34,奇碳优势明显,以C29或C31为主峰的单峰型为主,但少量样品也出现双峰型分布模式。通过对冰沟剖面正构烷烃分布特征、碳优势指数CPI和L/H（ΣC21-/ΣC22+）指标的详细分析得知其有机质来源以陆生高等植物占主导优势。结合年代数据、有机碳同位素、长链正构烷烃平均链长ACL和C33/(C33+C27)值重建出35.0ka以来银川盆地植被类型以 C3植物为主,并且C3和C4植物的相对比例变化主导受温度制约,而木本和草本植被的演化主要受控于水分条件。     

A compound-specific n-alkane δC and δD approach for assessing source and delivery processes of terrestrial organic matter within a forested watershed in northern Japan

We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ¹³C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ¹³C values of odd carbon numbered C₂₃-C₃₃n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ¹³C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C₂₅-C₃₁n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.     

Abundance and distribution of leaf wax n-alkanes in leaves of Acacia and Eucalyptus trees along a strong humidity gradient in northern Australia

Environmental parameters such as rainfall, temperature and relative humidity can affect the composition of higher plant leaf wax. The abundance and distribution of leaf wax biomarkers, such as long chain n-alkanes, in sedimentary archives have therefore been proposed as proxies reflecting climate change. However, a robust palaeoclimatic interpretation requires a thorough understanding of how environmental changes affect leaf wax n-alkane distributions in living plants. We have analysed the concentration and chain length distribution of leaf wax n-alkanes in Acacia and Eucalyptus species along a 1500 km climatic gradient in northern Australia that ranges from subtropical to arid. We show that aridity affected the concentration and distribution of n-alkanes for plants in both genera. For both Acacia and Eucalyptus n-alkane concentration increased by a factor of ten to the dry centre of Australia, reflecting the purpose of the wax in preventing water loss from the leaf. Furthermore, Acacian-alkanes decreased in average chain length (ACL) towards the arid centre of Australia, whereas Eucalyptus ACL increased under arid conditions. Our observations demonstrate that n-alkane concentration and distribution in leaf wax are sensitive to hydroclimatic conditions. These parameters could therefore potentially be employed in palaeorecords to estimate past environmental change. However, our finding of a distinct response of n-alkane ACL values to hydrological changes in different taxa also implies that the often assumed increase in ACL under drier conditions is not a robust feature for all plant species and genera and as such additional information about the prevalent vegetation are required when ACL values are used as a palaeoclimate proxy.     

Molecular and isotopic stratigraphy in an ombrotrophic mire for paleoclimate reconstruction

A 40 cm deep Sphagnum-dominated peat monolith from Bolton Fell Moss in Northern England was systematically investigated by lipid molecular stratigraphy and compound-specific δ¹³C and δD analysis using gas chromatography (GC), GC-mass spectrometry (GC-MS), GC-combustion-isotope ratio-MS (GC-C-IRMS) and GC-thermal conversion-IRMS (GC-TC-IRMS) techniques. ²¹⁰Pb dating showed the monolith accumulated during the last ca. 220 yr, a period encompassing the second part of Little Ice Age. While the distributions of lipids, including n-alkan-1-ols, n-alkan-2-ones, wax esters, sterols, n-alkanoic acids, α,ω-alkandioic acids and ω-hydroxy acids, display relatively minor changes with depth, the cooler climate event was recorded in the concentrations of n-alkanes and organic carbon, CPI values of n-alkanes and n-alkanoic acids, and the ratio of 5-n-alkylresorcinols/sterols. Superimposed on the fossil fuel effect, the relatively cooler climate event was also recorded by δ¹³C values of individual hydrocarbons, especially the C₂₃n-alkane, a major compound in certain Sphagnum spp. The δD values of the C₂₉ and C₃₃n-alkanes correlated mainly with plant composition and were relatively insensitive to climatic change. In contrast the C₂₃n-alkane displayed variation that correlated strongly with recorded temperature for the period represented by the monolith, agreeing with previously reported deuterium records in tree ring cellulose spanning the same period in Scotland, Germany and the USA, with more negative values occurring during the second part of Little Ice Age. These biomarker characteristics, including the compound-specific δ¹³C and δD records, provide a new set of proxies of climatic change, potentially independent of preserved macrofossils which will be of value in deeper sections of the bog where the documentary records of climate are unavailable and humification is well advanced.     

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.     

Effect of leaf litter degradation and seasonality on D/H isotope ratios of n-alkane biomarkers

During the last decade, compound-specific hydrogen isotope analysis of plant leaf-wax and sedimentary n-alkyl lipids has become a promising tool for paleohydrological reconstructions. However, with the exception of several previous studies, there is a lack of knowledge regarding possible effects of early diagenesis on the δD values of n-alkanes. We therefore investigated the n-alkane patterns and δD values of long-chain n-alkanes from three different C3 higher plant species (Acer pseudoplatanus L., Fagus sylvatica L. and Sorbus aucuparia L.) that have been degraded in a field leaf litterbag experiment for 27 months.We found that after an initial increase of long-chain n-alkane masses (up to ∼50%), decomposition took place with mean turnover times of 11.7 months. Intermittently, the masses of mid-chain n-alkanes increased significantly during periods of highest total mass losses. Furthermore, initially high odd-over-even predominances (OEP) declined and long-chain n-alkane ratios like n-C₃₁/C₂₇ and n-C₃₁/C₂₉ started to converge to the value of 1. While bulk leaf litter became systematically D-enriched especially during summer seasons (by ∼8‰ on average over 27 months), the δD values of long-chain n-alkanes reveal no systematic overall shifts, but seasonal variations of up to 25‰ (Fagus, n-C₂₇, average ∼13‰).Although a partly contribution by leaf-wax n-alkanes by throughfall cannot be excluded, these findings suggest that a microbial n-alkane pool sensitive to seasonal variations of soil water δD rapidly builds up. We propose a conceptual model based on an isotope mass balance calculation that accounts for the decomposition of plant-derived n-alkanes and the build-up of microbial n-alkanes. Model results are in good agreement with measured n-alkane δD results. Since microbial ‘contamination’ is not necessarily discernible from n-alkane concentration patterns alone, care may have to be taken not to over-interpret δD values of sedimentary n-alkanes. Furthermore, since leaf-water is generally D-enriched compared to soil and lake waters, soil and water microbial n-alkane pools may help explain why soil and sediment n-alkanes are D-depleted compared to leaves.     

Significant seasonal variation in the hydrogen isotopic composition of leaf-wax lipids for two deciduous tree ecosystems (Fagus sylvativa and Acerpseudoplatanus)

Compound specific hydrogen isotope ratios (δD) of long chain sedimentary n-alkanes, which mostly originate from the leaf waxes of higher terrestrial plants, are increasingly employed as paleoclimate proxies. While soil water is the ultimate hydrogen source for these lipids and the isotopic fractionation during biosynthesis of lipids is thought to remain constant, environmental parameters and plant physiological processes can alter the apparent hydrogen isotopic fractionation between leaf-wax lipids and a plant’s source water. However, the magnitude and timing of these effects and their influence on the isotopic composition of lipids from higher terrestrial plants are still not well understood. Therefore we investigated the seasonal variability of leaf-wax n-alkane δD values for two different temperate deciduous forest ecosystems that are dominated by two different tree species, Beech (Fagus sylvatica) and Maple (Acerpseudoplatanus).We found significant seasonal variations for both tree species in n-alkane δD values of up to 40‰ on timescales as short as one week. Also, the isotopic difference between different n-alkanes from the same plant species did vary significantly and reached up to 50‰ at the same time when overall n-alkane concentrations were lowest.Since δD values of soil water at 5 and 10 cm depth, which we assume represent the δD value of the major water source for the investigated beech trees, were enriched in autumn compared to the spring by 30‰, whereas n-alkane δD values increased only by 10‰, we observed variations in the apparent fractionation between beech leaf derived n-alkanes and soil water of up to 20‰ on a seasonal scale. This observed change in the apparent fractionation was likely caused by differences in leaf water isotopic enrichment. Based on mechanistic leaf water models we conclude that changes in the isotopic difference between water vapor and soil water were the most likely reason for the observed changes in the apparent fractionation between n-alkanes and soil water.The large variability of n-alkane concentrations and δD values over time implies a continuous de novo synthesis of these compounds over the growing season with turnover times possibly as short as weeks. The signal to reach the soil therefore represents an integrated record of the last weeks before leaf senescence. This holds true also for the sedimentary record of small catchment lakes in humid, temperate climates, where wind transport of leaf-wax lipids is negligible compared to transfer through soil and the massive input of leaves directly into the lake in autumn.     

四川珙县石碑恐龙化石埋藏地红层分子化石特征及其古环境意义

利用气相色谱-质谱仪(GC/MS)从四川珙县石碑恐龙化石埋藏地早侏罗世红层中检出了包括正构烷烃、类异戊二烯烃、长链三环萜、藿烷和甾烷等系列分子化石,这些分子化石来源于低等菌藻类生物和水生、陆生高等植物。利用这些分子化石的特征讨论了恐龙生活时代的古环境特征。姥鲛烷与植烷的比值(Pr/Ph)表明该恐龙化石埋藏地的沉积环境应为淡水、弱氧化的湖泊环境。所研究样品高碳数的正构烷烃均以与水生大型植物有关的C25为主峰,并具有来自陆生高等植物的C27～C31正构烷烃,反映出研究区湖盆水体中发育水生高等植物,周围陆地上发育木本和草本植物的古植物特征,体现了分子化石在恢复古环境研究方面的潜力。     

Possible algal origin of long chain odd n-alkanes in immature sediments as revealed by distributions and carbon isotope ratios

A Pliocene oil shale (Pula, Hungary), a C₃ plant Triticum aestivum and a C₄ plant Zea mays were compared using isotopic composition of bulk organic matter, along with distributions and individual carbon isotope ratios of n-alkanes from organic extracts. The microalga Botryococcus braunii (A race) was thus shown to be the main source of the predominant 27, 29 and 31 n-alkanes of Pula sediment Therefore, the dominance of odd carbon-numbered n-alkanes in the range C₂₅–₃₅ in extracts from immature sediments shall not be systematically assigned to higher plant contribution but algal input is also possible. In fact, the long chain n-alkanes with an odd predominance previously observed in extracts of various immature sediments are likely to be derived at least partially, from algae.     

n-alkane distribution coupled with organic carbon isotope composition in the shell bar section, Qarhan paleolake, Qaidam basin, NE Tibetan Plateau

Lipids extracted from lacustrine deposits in the paleolake Qarhan of the Qaidam basin in the northeastern Tibetan Plateau were determined by conventional gas chromatography-mass spectrometry. Several series of biomarkers were identified, mainly including n-alkanes, n-alkan-2-ones, n-alkanoic acids, branched alkanes, triterpenoids and steroids, indicative of various biogenic contributions. On the basis of cluster analysis, the n-C₁₅, n-C₁₇, n-C₁₉ alkanes were proposed to be derived from algae and/or photosynthetic bacteria, the n-C₂₁, n-C₂₃, n-C₂₅ homologues from aquatic plants, and the n-C₂₉, n-C₃₁ homologues from vascular plants. In contrast, the n-C₂₇ alkane is not categorized in the n-C₂₉ and n-C₃₁ group of alkanes, probably due to more complex origins including both aquatic and vascular plants, and/or differential biodegradation. Stratigraphically, layers-2, 4 and 5 were found to show a close relationship in n-alkane distribution, associated with a positive shift in carbon isotope composition of bulk organic matter (δ¹³C_org), inferring a cold/dry period. Layers-1 and 6 were clustered together in association with a negative δ¹³C_org, excursion, probably indicating a relatively warm/humid climate. The potential coupling between the n-alkane distributions and δ¹³C_org, suggests a consequence of vegetation change in response to climate change, with the late MIS3 being shown to be unstable, thought to be the climatic optimum in the Tibetan Plateau. Our results suggest that the cluster analysis used in this study probably provides an effective and authentic method to investigate the n-alkane distribution in paleolake sediments.     

Production of n-alkyl lipids in living plants and implications for the geologic past

Leaf waxes (i.e., n-alkyl lipids or n-alkanes) are land-plant biomarkers widely used to reconstruct changes in climate and the carbon isotopic composition of the atmosphere. There is little information available, however, on how the production of leaf waxes by different kinds of plants might influence the abundance and isotopic composition of n-alkanes in sedimentary archives. This lack of information increases uncertainty in interpreting n-alkyl lipid abundance and δ¹³C signals in ancient settings. We provide here n-alkyl abundance distributions and carbon isotope fractionation data for deciduous and evergreen angiosperm and gymnosperm leaves from 46 tree species, representing 24 families. n-Alkane abundances are significantly higher in angiosperms than gymnosperms; many of the gymnosperm species investigated did not produce any n-alkanes. On average, deciduous angiosperms produce 200 times more n-alkanes than deciduous gymnosperms. Although differences between angiosperms and gymnosperms dominate the variance in n-alkane abundance, leaf life-span is also important, with higher n-alkane abundances in longer-lived leaves. n-Alkanol abundances covary with n-alkanes, but n-alkanoic acids have similar abundances across all plant groups. Isotopic fractionation between leaf tissue and individual alkanes (ε_lipid) varies by as much as 10‰ among different chain lengths. Overall, ε_lipid values are slightly lower (−4.5‰) for angiosperm than for gymnosperm (−2.5‰) n-alkanes. Angiosperms commonly express slightly higher Δ_leaf (photosynthetic discrimination) relative to gymnosperms under similar growth conditions. As a result, angiosperm n-alkanes are expected to be generally 3-5‰ more depleted in ¹³C relative to gymnosperm alkanes for the same locality. Differences in n-alkane production indicate the biomarker record will largely (but not exclusively) reflect angiosperms if both groups were present, and also that evergreen plants will likely be overrepresented compared with deciduous ones. We apply our modern lipid abundance patterns and ε_lipid results to constrain the magnitude of the carbon isotope excursion (CIE) at the onset of the Paleocene-Eocene Thermal Maximum (55.8 Ma). When Bighorn Basin (WY) sediment n-alkanes are interpreted in context of floral changes and modern n-alkane production estimates for angiosperms and gymnosperms, the CIE is greater in magnitude (−5.6‰) by ∼1‰ compared to previous estimates that do not take into account n-alkane production.     

Distributions and hydrogen isotopic compositions of plant leaf wax from Orinus kokonorica along a general aridity gradient around Lake Qinghai,China

To quantitatively analyze the response of distributions and hydrogen isotopic compositions （SD） of plant leaf wax to moisture, and to better understand their implications for paleoclimatic reconstruction, we measured av- erage chain length （ACL） and 8D values of n-alkanes and n-fatty acids （n-FAs） from Orinus kokonorica, a typical and representative plant in Lake Qinghai area, along a distance transect extending from lakeshore to wetland to dry- land in the arid ecosystem. The results showed that the ACL values of n-alkanes and n-FAs were negatively corre- lated with soil water content （SWC） with R2~0.593 and R2=0.924, respectively. This is as a result of plant＇s response to water loss with more abundance in long-chain n-alkyl lipids under increasing aridity by analyzing relationships between the molecular ratios of long-chain n-alkyl lipids （n-alkanes and n-FAs） from O. kokonorica and SWC. The 8D values of C29 n-alkane and C28 n-FA were also negatively correlated with SWC with R2-0.778 and R2-0.760, respectively, which may due to enhanced D-enrichment in leaf water by evapotranspiration （soil water evaporation and leaf water transpiration） with increasing aridity. Our results demonstrated that moisture exerts a significant con- trol on the ACL and 8D values from O. kokonorica in an arid ecosystem. This preliminary study on a modern single plant （O. kokonorica） sets a foundation for comprehending these values as quantitative proxies for paleo-humidity reconstruction.     

Detection of petroleum contamination in river sediments from Quebec City region using GC–IRMS

Isotopic analysis by compound specific gas chromatography–isotope ratio mass spectrometry (GC–IRMS) is used to detect and characterize petroleum pollution in surficial sediments along the St Lawrence River, near Quebec City. Unusually mature n-alkane distributions have been found in some recent intertidal sediments in the region. GC–IRMS results suggest that the n-alkanes are not derived from indigenous organic sources because they carry δ¹³C values between −30.0 and −27.0‰, as well as very small isotopic differences between odd and even numbered n-alkanes, which are both typically associated with petroleum products. Comparison of these sediments with bunker fuel, an oil used in the shipping industry, has shown a close isotopic correlation in some sites, which is further supported by biomarkers. Overall, the contamination has been dispersed along the river but is generally localized around the industrial region where hydrocarbon transfer from shore storage to ships takes place. This study illustrates how GC–IRMS can be used effectively in the detection and characterization of petroleum pollutants in sediments.