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.     

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.     

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.     

The source and paleoclimatic implication of hydrogen isotopic composition of n-alkanes in sediments from the Yixian Formation,western Liaoning Province,NE China

Hydrogen isotopic composition of n-alkanes was measured in sediments from an excavated profile of the Early Cretaceous Yixian Formation in Liaoning Province, NE China, aiming to assess the significance of the δD value of n-alkanes in ancient lacustrine sediments as the indicator for determining the source inputs of organic matters and paleoclimatic conditions. The δD values of n-alkanes are in the range of − 250‰ to − 85‰ and display an obvious three-stage variation pattern through the profile, which is consistent with the distribution of the dominated n-alkanes and the profile of their δ¹³C values. The δD and δ¹³C values of n-alkanes suggest that short-chain n-alkanes are primarily derived from photosynthetic bacteria and algae; n-C₂₉ and n-C₃₁ are mainly originated from terrestrial higher plants; n-C₂₈ and n-C₃₀ may be derived from the same precursor but via the different biological mechanism of hydrogen isotopic fractionation; while the source inputs of medium-chain n-alkanes are more complicated, with n-C₂₃ being derived from some specific algae or biosynthesized by various aquatic organisms. The paleoclimatic conditions are reconstructed via two approaches. The reconstructed hydrogen isotopic values of lake water and meteoric water (expressed as δD_LW and δD_MW, respectively) were at the intervals of − 51.8‰ to 17.0‰ and − 118.1‰ to − 43.5‰, respectively, indicating a general climate transition from semi-arid to arid. The calculated ΔδD_LW-MW values vary from 37.0‰ to 89.1‰ and display a similar but a significant large-scale variation trend with the ΔδD_{C23 ‐ long} (− 28.8‰ to 85.0‰; long represents long-chain n-alkanes) and ΔδD_mid-long (− 15.4‰ to 43.4‰; mid represents medium-chain n-alkanes) values. The discrepancy may be attributed to the source input overlap for n-alkanes and the uncertainties of ε_water/lipid values. The coupling of ΔδD_{C23 ‐ long}, ΔδD_mid-long and ΔδD_LW-MW values with the paleoclimatic evidence indicates that the δD values of n-alkanes could be more sensitive to the change of paleoclimatic conditions.     

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‰).     

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.     

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.     

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 geochemistry of serpentinites in the Lost City Hydrothermal System (30°N, MAR)

The carbon geochemistry of serpentinized peridotites and gabbroic rocks recovered at the Lost City Hydrothermal Field (LCHF) and drilled at IODP Hole 1309D at the central dome of the Atlantis Massif (Mid-Atlantic Ridge, 30°N) was examined to characterize carbon sources and speciation in oceanic basement rocks affected by long-lived hydrothermal alteration. Our study presents new data on the geochemistry of organic carbon in the oceanic lithosphere and provides constraints on the fate of dissolved organic carbon in seawater during serpentinization. The basement rocks of the Atlantis Massif are characterized by total carbon (TC) contents of 59 ppm to 1.6 wt% and δ¹³C_TC values ranging from −28.7‰ to +2.3‰. In contrast, total organic carbon (TOC) concentrations and isotopic compositions are relatively constant (δ¹³C_TOC: −28.9‰ to −21.5‰) and variations in δ¹³C_TC reflect mixing of organic carbon with carbonates of marine origin. Saturated hydrocarbons extracted from serpentinites beneath the LCHF consist of n-alkanes ranging from C₁₅ to C₃₀. Longer-chain hydrocarbons (up to C₄₀) are observed in olivine-rich samples from the central dome (IODP Hole 1309D). Occurrences of isoprenoids (pristane, phytane and squalane), polycyclic compounds (hopanes and steranes) and higher relative abundances of n-C₁₆ to n-C₂₀ alkanes in the serpentinites of the southern wall suggest a marine organic input. The vent fluids are characterized by high concentrations of methane and hydrogen, with a putative abiotic origin of hydrocarbons; however, evidence for an inorganic source of n-alkanes in the basement rocks remains equivocal. We propose that high seawater fluxes in the southern part of the Atlantis Massif likely favor the transport and incorporation of marine dissolved organic carbon and overprints possible abiotic geochemical signatures. The presence of pristane, phytane and squalane biomarkers in olivine-rich samples associated with local faults at the central dome implies fracture-controlled seawater circulation deep into the gabbroic core of the massif. Thus, our study indicates that hydrocarbons account for an important proportion of the total carbon stored in the Atlantis Massif basement and suggests that serpentinites may represent an important—as yet unidentified—reservoir for dissolved organic carbon (DOC) from seawater.     

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.     

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.     

Assessment of petroleum biodegradation using stable hydrogen isotopes of individual saturated hydrocarbon and polycyclic aromatic hydrocarbon distributions in oils from the Upper Indus Basin,Pakistan

The stable hydrogen isotopic compositions (δD) of selected aliphatic hydrocarbons (n-alkanes and isoprenoids) in eight crude oils of similar source and thermal maturity from the Upper Indus Basin (Pakistan) were measured. The oils are derived from a source rock deposited in a shallow marine environment. The low level of biodegradation under natural reservoir conditions was established on the basis of biomarker and aromatic hydrocarbon distributions. A plot of pristane/n-C₁₇ alkane (Pr/n-C₁₇) and/or phytane/n-C₁₈ alkane (Ph/n-C₁₈) ratios against American Petroleum Institute (API) gravity shows an inverse correlation. High Pr/n-C₁₇ and Ph/n-C₁₈ values and low API gravity values in some of the oils are consistent with relatively low levels of biodegradation. For the same oils, δD values for the n-alkanes relative to the isoprenoids are enriched in deuterium (D). The data are consistent with the removal of D-depleted low molecular weight (LMW) n-alkanes (C₁₄–C₂₂) from the oils. The δD values of isoprenoids do not change with progressive biodegradation and are similar for all the samples. The average D enrichment for n-alkanes with respect to the isoprenoids is found to be as much as 35‰ for the most biodegraded sample. For example, the moderately biodegraded oils show an unresolved complex mixture (UCM), loss of LMW n-alkanes (<C₁₅) and moderate changes in the alkyl naphthalene distributions. The relative susceptibility of alkyl naphthalenes at low levels of biodegradation is discussed. The alkyl naphthalene biodegradation ratios were determined to assess the effect of biodegradation. The dimethyl, trimethyl and tetramethyl naphthalene biodegradation ratios show significant differences with increasing extent of biodegradation.     

A kinetic model for thermally induced hydrogen and carbon isotope fractionation of individual n-alkanes in crude oil

A quantitative kinetic model has been proposed to simulate the large D and ¹³C isotope enrichments observed in individual n-alkanes (C₁₃-C₂₁) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ¹³C values increase by ∼4‰ and δD values increase by ∼50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed ¹³C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH^‡) and entropy (ΔΔS^‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C₂₀ (n-icosane), the changes in enthalpy are calculated to be ∼1340 J mol^-1 (320 cal mol^-1) and 230 J mol^-1 (55 cal mol^-1) for D-H and ¹³C-¹²C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in ¹³C and D for n-icosane at equivalent vitrinite reflectance values corresponding to the onset of thermal cracking of normal alkanes. The experimental and theoretical results of this study have significant implications for the use of compound-specific hydrogen isotope data in petroleum geochemical and paleoclimatological studies. However, there are many other geochemical processes that will significantly affect observed hydrogen isotopic compositions (e.g., biodegradation, water washing, isotopic exchange with water and minerals) that must also be taken into consideration.     

D/H variation in terrestrial lipids from Santa Barbara Basin over the past 1400 years: A preliminary assessment of paleoclimatic relevance

We analyzed D/H ratios of common terrestrial leaf wax lipids in a 1400 year sediment core from the Santa Barbara Basin (SBB) to test whether they accurately record terrestrial climate in Southern California. The D/H ratios of long chain n-alkanes vary substantially with depth, but are poorly correlated with other terrestrial climate proxies. Interference from fossil hydrocarbons may be at least partly responsible. Long chain n-alkanoic acids exhibit nearly constant downcore D/H ratio values. This constancy in the face of known climatic shifts presumably reflects a substantial residence time for leaf wax compounds in terrestrial soil and/or on the basin flanks. Alternatively, the isotopic composition of meteoric waters in Southern California may not covary with climate, particularly aridity. However, the δD values of n-C₂₂ and n-C₂₄ fatty acids, commonly attributed to terrestrial aquatic sources, are partially correlated with Southern California winter Palmer Drought Severity Index, a tree ring-based climatic proxy (R² 0.25; p < 0.01) on multi-centennial scales with an inferred ca. 215 year time lag. The improved correlation of these biomarkers can be explained by the fact that they are not stored in terrestrial soil nor are subject to interference from fossil hydrocarbons. Our study indicates that the SBB is unlikely to preserve high resolution leaf wax D/H records that can serve as quantitative paleoclimate proxies, though some qualitative information may be retained. More generally, the sources of lipids in marginal marine basins need to be carefully evaluated prior to attempting paleoclimate reconstruction based on the leaf wax D/H proxy.     

Latitudinal distribution of terrestrial lipid biomarkers and n-alkane compound-specific stable carbon isotope ratios in the atmosphere over the western Pacific and Southern Ocean

We investigated the latitudinal changes in atmospheric transport of organic matter to the western Pacific and Southern Ocean (27.58°N-64.70°S). Molecular distributions of lipid compound classes (homologous series of C₁₅ to C₃₅n-alkanes, C₈ to C₃₄n-alkanoic acids, C₁₂ to C₃₀n-alkanols) and compound-specific stable isotopes (δ¹³C of C₂₉ and C₃₁n-alkanes) were measured in marine aerosol filter samples collected during a cruise by the R/V Hakuho Maru. The geographical source areas for each sample were estimated from air-mass back-trajectory computations. Concentrations of TC and lipid compound classes were several orders of magnitude lower than observations from urban sites in Asia. A stronger signature of terrestrial higher plant inputs was apparent in three samples collected under conditions of strong terrestrial winds. Unresolved complex mixtures (UCM) showed increasing values in the North Pacific, highlighting the influence of the plume of polluted air exported from East Asia. n-Alkane average chain length (ACL) distribution had two clusters, with samples showing a relation to latitude between 28°N and 47°S (highest ACL values in the tropics), whilst a subset of southern samples had anomalously high ACL values. Compound-specific carbon isotopic analysis of the C₂₉ (−25.6‰ to −34.5‰) and C₃₁n-alkanes (−28.3‰ to −37‰) revealed heavier δ¹³C values in the northern latitudes with a transition to lighter values in the Southern Ocean. By comparing the isotopic measurements with back-trajectory analysis it was generally possible to discriminate between different source areas. The terrestrial vegetation source for a subset of the southernmost Southern Ocean is enigmatic; the back-trajectories indicate eastern Antarctica as the only intercepted terrestrial source area. These samples may represent a southern hemisphere background of well mixed and very long range transported higher plant organic material.     

Crassulacean acid metabolism influences D/H ratio of leaf wax in succulent plants

This study sought to characterize hydrogen isotopic fractionation during biosynthesis of leaf wax n-alkanes in succulent plants capable of crassulacean acid metabolism (CAM). The metabolic and physiological features of CAM represent crucial strategies for survival in hot and dry climates and have been hypothesized to impact hydrogen isotope fractionation. We measured the stable carbon and hydrogen isotopic compositions (δ¹³C and δD, respectively) of individual n-alkanes in 20 species of succulent plants from a global collection of the Huntington Botanical Gardens, San Marino, California. Greenhouse conditions and irrigation with water of constant δD value enabled determination of interspecies differences in net D/H fractionation between source water and leaf wax products. Carbon isotope ratios provide constraints on the extent of CAM vs. C₃ photosynthesis and indicate a wide range of CAM use, with δ¹³C values ranging from −33.01‰ to −18.54‰ (C₂₇–C₃₃ n-alkanes) and −26.66‰ to −17.64‰ (bulk tissue). Despite the controlled growth environment, we observed ca. 90‰ interspecies range in δD values from −193‰ to −107‰. A positive correlation between δ¹³C_bulk and δD_C31 values with R² = 0.60 (δ¹³C_C31 and δD_C31 values with R² = 0.41) implicates a metabolic isotope effect as the dominant cause of interspecies variation in the hydrogen isotopic composition of leaf wax n-alkanes in CAM-intermediate plants.     

Altitudinal shift in stable hydrogen isotopes and microbial tetraether distribution in soils from the Southern Alps,NZ: Implications for paleoclimatology and paleoaltimetry

The Southern Alps are an ideal locality for studying patterns of isotopic fractionation associated with orographic precipitation. We have evaluated whether altitudinal change is reflected in the stable hydrogen isotopic composition (δ²H) of stream water, plant stem water and leaf wax lipids (n-alkanes) from living plants and soils, as well as in soil temperature. Samples were collected along an altitudinal transect from the windward side of the Southern Alps to Lake Hawea in the rain shadow. The results indicate that δ²H values of stem water overlap with stream water, demonstrating a gradual decrease with elevation that complied with modeled Rayleigh distillation, reflecting an isotopic lapse rate of −18.0 (± 1.1, 1σ)‰/km. Leaf and soil n-alkanes shared similar δ²H values and were ²H depleted relative to stem/stream waters. The values for soil n-alkanes indicated an isotopic lapse rate of −21.8 (± 2.0, 1σ)‰/km, consistent with precipitation data and long term observations. MBT/CBT derived soil temperature values based on the relative distribution of microbial tetraether lipids were similar to midsummer temperature observations, displaying an elevational decrease rate of −5.6 (± 1.5, 1σ) °C/km, consistent with regional and global observations.The results indicate that sedimentary lipid δ²H and microbial tetraether temperature estimates captured altitudinal trends in the isotopic composition of precipitation and mean temperature and further support their application in the reconstruction of past climate and surface uplift histories. However, notable differences in isotopic composition and temperature estimates between in situ soils and those with downslope transport of material emphasize the importance of facies analysis when interpreting past systems.     

Soil n-alkane δD vs. altitude gradients along Mount Gongga, China

The altitude effect on the isotopic composition of precipitation and its application to paleoelevation reconstruction using authigenic or pedogenic minerals have been intensively studied. However, there are still no studies on variations in biomarker δD along altitude transects to investigate its potential as a paleoelevation indicator, although it has been observed that δD of higher plant lipid may record changes in precipitation δD (δD_p). Here, we present δD values of higher plant-derived C₂₇, C₂₉, and C₃₁n-alkanes from surface soil along the eastern slope of Mount Gongga, China with great changes in physical variables and vegetation over a range from 1000 to 4000 m above sea level. The weighted-mean δD values of these n-alkanes (δD_wax) show significant linear correlations with predicted δD_p values (R² = 0.76) with an apparent isotopic enrichment (ε_wax-p) of −137 ± 9‰, indicating that soil δD_wax values track overall δD_p variation along the entire altitudinal transect. Leaf δD_wax is also highly correlated with mountain altitude by a significant quadratic relationship (R² = 0.80). Evapotranspiration is found declining with altitude, potentially lowering δD_wax values at higher elevations. However, this evapotranspiration effect is believed to be largely compensated by the opposing effect of vegetation changes, resulting in less varied ε_wax-p values over the slope transect. This study therefore confirms the potential of using leaf δD_wax to infer paleoelevations, and more generally, to infer the δD of precipitation.     

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.