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.     

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.     

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.     

Fractionation of hydrogen,oxygen and carbon isotopes in n-alkanes and cellulose of three Sphagnum species

Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C₂₁–C₂₅ n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ¹⁸O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C₂₃ n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ¹³C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C₂₃ n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores.     

Characterization of the hydrogen isotopic composition of individual n-alkanes in terrestrial source rocks

In order to characterize the H isotopic compositions of individual lipid compounds from different terrestrial depositional environments, the δD values of C-bound H in individual n-alkanes from typical terrestrial source rocks of the Liaohe Basin and the Turpan Basin, China, were measured using gas chromatography–thermal conversion–isotope ratio mass spectrometry (GC–TC–IRMS). The analytical results indicate that the δD values of individual n-alkanes in the extracts of terrestrial source rocks have a large variation, ranging from −140‰ to −250‰, and are obviously lighter than the δD of marine-sourced n-alkanes. Moreover, a trend of depletion in ²H(D) was observed for individual n-alkanes from different terrestrial depositional environments, from saline lacustrine to freshwater paralic lacustrine, and to swamp. For example, the δD values of n-alkanes from a stratified saline lacustrine environment vary from −140‰ to −200‰, δD for n-alkanes from swamp facies range from −200‰ to −250‰, while those from freshwater paralic lacustrine–lacustrine environments fall between the δD values of the end members. The shift toward lighter δD from saltwater to freshwater environments indicates that the source water δD is the major controlling factor for the H isotopic composition of individual compounds. In addition, H exchange between formation water and sedimentary organic matter may possibly be important in regard to the δD of individual n-alkanes. Therefore, other lines of geochemical evidence must be considered when depositional paleoenvironments of source rocks are reconstructed based on the H isotopic composition of individual n-alkanes.     

Influence of physiology and climate on δD of leaf wax n-alkanes from C3 and C4 grasses

We measured hydrogen isotope compositions (δD) of high-molecular-weight n-alkanes (C₂₇-C₃₃) from grasses grown in greenhouses and collected from the US Great Plains. In both cases, n-alkanes from C₄ grasses are enriched in D by more than 20‰ relative to those from C₃ grasses. The apparent enrichment factor (ε_C29-GW) between C₂₉n-alkane and greenhouse water is −165 ± 12‰ for C₃ grasses and −140 ± 15‰ for C₄ grasses. For samples from the Great Plains, δD values of C₂₉n-alkanes range from −280 to −136‰, with values for C₄ grasses ca. 21‰ more positive than those for C₃ grasses from the same site. Differences in C₃ and C₄ grass n-alkane δD values are consistent with the shorter interveinal distance in C₄ grass leaves, and greater back-diffusion of enriched water from stomata to veins, than in C₃ grass leaves. Great Plains’ grass n-alkane isotopic ratios largely reflect precipitation δD values. However, the offset or apparent fractionation between n-alkanes and precipitation is not uniform and varies with annual precipitation and relative humidity, suggesting climatic controls on lipid δD values. The dryer sites exhibit smaller absolute apparent fractionation indicative of D-enrichment of source waters through transpiration and/or soil evaporation. To explore the relationship between climate and n-alkane δD values, we develop three models. (1) The ‘direct analog’ model estimates δD_C29 values simply by applying the apparent enrichment factors, ε_C29-GW, observed in greenhouse grasses to precipitation δD values from the Great Plains. (2) The ‘leaf-water’ model uses a Craig-Gordon model to estimate transpirational D-enrichment for both greenhouse and field sites. The transpiration-corrected enrichment factors between C₂₉ and bulk leaf-water, ε_C29-GW, calculated from the greenhouse samples (−181‰ for C₃ and −157‰ for C₄) are applied to estimate δD_C29 values relative to modeled bulk leaf-water δD values. (3) The ‘soil- and leaf-water’ model estimates the combined effects of soil evaporation, modeled by analogy with a flow-through lake, and transpiration on δD_C29 values. Predictions improve with the addition of the explicit consideration of transpiration and soil evaporation, indicating that they are both important processes in determining plant lipid δD values. D-enrichment caused by these evaporative processes is controlled by relative humidity, suggesting that important climatic information is recorded in leaf wax n-alkane δD values. Calibration studies such as this one provide a baseline for future studies of plant-water-deuterium systematics and form the foundation for interpretation of plant wax hydrogen isotope ratios as a paleo-aridity proxy.     

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.     

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.     

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.     

Effect of precipitation regime on δD values of soil n-alkanes from elevation gradients - Implications for the study of paleo-elevation

We measured δD values of long chain n-alkanes isolated from 30 surface soil samples along two elevation transects on the Tibetan Plateau differing in precipitation regime and water source. The East Asian Monsoon precipitation dominates the wetter regime on the eastern slope (from 1230 to 4300 m) of Gongga Shan on the eastern Tibetan Plateau. Precipitation from the Polar Westerlies dominates the drier region on the slope from 1900 to 5000 m in the West Kunlun Shan on the northwestern Tibetan Plateau. The decrease in δD value with elevation in the wetter region greatly exceeded that in drier region by, −1.9 ± 0.1‰/100 m and −1.4 ± 1.0‰/100 m respectively. The apparent fractionation between leaf wax and precipitation ε_wax-p values in the wetter region (ca. −164‰) were more negative than those in drier region (ca. −125‰ above 3200 m).We also measured δD values in leaves of six common living trees (values from −287‰ to −193‰) from Gongga Shan, ranging from about 2900-4200 m. The abundance-weighted average values of the n-alkanes (δD_wax) show a strong reverse correlation with sample source elevation (R² 0.78 for soils from Gongga Shan; R² 0.85 for soils from West Kunlun Shan above 3200 m), suggesting that n-alkane δD_wax faithfully records the precipitation δD and that the isotopic altitude effect of precipitation controls δD_wax altitudinal gradients in the mountains. The data show a fairly strong monotonic dependency of n-alkane δD values on elevation for the eastern Plateau, but a complex relationship between n-alkane δD values and elevation for the northwestern Plateau. The δD_wax values at sites below 3200 m from the Kunlun Shan area exhibit an unexpected positive correlation with elevation. The study confirms the potential for using sediment δD_wax values to reconstruct paleo-elevation in wetter regions, but suggests caution in applying the approach to dry regions. Our results also show it is essential to consider the intricacy of the pattern of atmospheric circulation and water sources and their influence on the lapse rate of δD values with elevation.     

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.     

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.     

Hydrogen-isotopic variability in lipids from Santa Barbara Basin sediments

We conducted an extensive survey of hydrogen-isotopic compositions (D/H ratios) of diverse sedimentary lipids from the Santa Barbara Basin (SBB), offshore southern California. The main goal of this survey was to assess the diversity of D/H ratios in lipids from marine sediments, in order to provide a more detailed understanding of relevant biological and geochemical factors impacting lipid isotopic variability. A total of 1182 individual δD values are reported from two stations in SBB, one located in the suboxic basin depocenter and the other on the fully oxic flank of the basin. Sediments collected from the basin depocenter span a depth of ∼2.5 m and reach the methanogenic zone. Lipids that were analyzed include n-alkanes, n-alkanols and alkenols, short- and long-chain fatty acids, linear isoprenoids, steroids, and hopanoids, and exhibit several systematic patterns. First, there are no significant differences in δD values between the two sampling locations, nor with increasing depth for most lipids, indicating that degradation does not influence sedimentary lipid δD values. Second, relatively large differences in δD values among differing molecular structures are observed in all samples. n-Alkyl lipids of probable marine origin have typical δD values between −150 and −200‰, those from terrestrial leaf waxes and aquatic plants range from −80 to −170‰, while petroleum n-alkanes are typically −90 to −150‰. Third, lipids inferred to derive from bacteria (branched fatty acids and hopanols) living at the sediment surface or in the water column tend to be D-enriched relative to similar algal products by 30‰ or more. At the same time, several other lipids have δD values that decrease strongly with depth, presumably as a result of in situ production by anaerobic bacteria. This dichotomy in isotopic compositions of bacterial lipids is inconsistent with a nearly constant D/H fractionation during lipid biosynthesis, and likely reflects significant variations associated with metabolism.     

Different response of δD values of n-alkanes, isoprenoids, and kerogen during thermal maturation

This study investigates the extent of post-depositional alteration of δD values of n-alkyl lipids, isoprenoids, and kerogen isolated from a continuous 450 m core that covers the transition from thermally immature to early mature sediments in the lacustrine Kissenda Formation, Lower Cretaceous, Gabon Basin. Large variations in δD values (up to 40‰ for nC₁₇ and up to 30‰ for nC₂₉ alkanes as well as up to 10‰ for kerogen) in closely spaced samples are evident throughout the core and remain preserved even at the bottom of the section. δD values of individual n-alkanes show a slight overall D-enrichment with depth, and a general trend of increasing δD values with increasing n-alkane chain length characterizes all samples, particularly in those below 600 m depth. Hydrogen isotopic compositions of kerogen samples overlap with those of n-alkanes throughout the section. δD values of pristane and phytane are more negative than those of nC₁₇ alkane by as much as 120‰ at shallow depths but increase dramatically and approach δD values of nC₁₇ alkane in the samples closest to the oil window. Integration of analytical and computational results indicates that: (1) n-alkanes and isoprenoids have the potential to preserve the original biological signal before the onset of oil generation; (2) isomeric and structural rearrangements taking place at the beginning stages of oil generation do not influence significantly the δD values of n-alkanes and kerogen. However, these processes have a major effect on the isotopic composition of isoprenoids, causing isotopic D-enrichment up to 90‰.     

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.     

Controls on the D/H ratios of plant leaf waxes in an arid ecosystem

The extent to which leaf water D-enrichment (transpiration) and soil water D-enrichment (evaporation) affect the D/H ratio of plant leaf waxes remains a contentious issue, with important implications for paleohydrologic reconstructions. In this study we measure δD values of precipitation (δD_p), groundwater (δD_gw), plant xylem water (δD_xw) and leaf water (δD_lw) to understand their impact on the δD values of plant leaf wax n-alkanes (δD_wax) in an arid ecosystem. Our survey includes multiple species at four sites across an aridity gradient (80-30% relative humidity) in southern California.We find that many species take up groundwater or precipitation without significant fractionation. D-enriched soil water is a minor source even in species known to perform and utilize waters from hydraulic lift, such as Larrea tridentata (+10‰). Measurements of leaf water isotopic composition demonstrate that transpiration is an important mechanism for D-enrichment of leaf waters (+74 ± 20‰, 1σ), resulting in the smallest net fractionation yet reported between source water and leaf waxes (L. tridentata −41‰; multi-species mean value is −94 ± 21‰, 1σ). We find little change in leaf water D-enrichment or net fractionation across the climatic gradient sampled by our study, suggesting that a net fractionation of ca. −90‰ may be appropriate for paleohydrologic reconstructions in semi-arid to arid environments. Large interspecies offsets in net fractionations (1σ = 21‰) are potentially troublesome, given the observed floristic diversity and the likelihood of species assemblage changes with climate shifts.     

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.     

Variation in n-alkane δD values from terrestrial plants at high latitude: Implications for paleoclimate reconstruction

The molecular hydrogen isotope composition (δD) of leaf waxes from terrestrial plants is increasingly used to infer hydrological characteristics of ancient high latitude climates. Analysis of the hydrogen isotope composition of n-alkanes (δD_n-alkane) from a global dataset of individual plants growing at low and middle latitudes indicates that plant ecological life form is an important factor in determining the hydrogen isotope fractionation. However, environmental and biological controls of high latitudinal leaf wax δD values are poorly understood because of a lack of δD records from modern flora in these regions. We previously noticed smaller apparent hydrogen isotope fractionations between n-alkanes and environmental water (ε_alk-water) in deciduous trees growing at high latitudes (>59°N; Liu, W.-G., Yang, H., 2008. Multiple controls for the variability of hydrogen isotopic compositions in higher plant n-alkanes from modern ecosystems. Global Change Biology 14, 2166-2177.) To further examine these issues, we measured δD_n-alkane from a variety of plants that inhabit high latitude environments and added critically needed leaf wax δD data from grass and herbs to the existing global δD_n-alkane database. Inclusion of these new data with the existing global dataset (n = 408) confirms plant ecological life form as an important control for leaf wax δD variation for terrestrial plants living at high latitudes. Our results suggest that, while precipitation δD is captured in these high latitude plants, physiological characters such as leaf area, venation pattern and hydraulic system, that enhance transpiration rate during summer growth, may impart δD_n-alkane differences among plants with different ecological life forms.     

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‰).     

Hydrogen isotope ratios of leaf wax n-alkanes in grasses are insensitive to transpiration

We analyzed hydrogen isotope ratios of high-molecular weight n-alkanes (δD_l) and oxygen isotope ratios of α-cellulose (δ¹⁸O_C) for C₃ and C₄ grasses grown in the field and in controlled-environment growth chambers. The relatively firm understanding of ¹⁸O-enrichment in leaf water and α-cellulose was used to elucidate fractionation patterns of δD_l signatures. In the different relative humidity environments of the growth chambers, we observed clear and predictable effects of leaf-water enrichment on δ¹⁸O_C values. Using a Craig-Gordon model, we demonstrate that leaf water in the growth chamber grasses should have experienced significant D-enriched due to transpiration. Nonetheless, we found no effect of transpirational D-enrichment on the δD_l values. In field samples, we saw clear evidence of enrichment (correlating with relative humidity of the field sites) in both δ¹⁸O_C and δD_l. These seemingly contrasting results could be explained if leaf waxes are synthesized in an environment that is isotopically similar to water entering plant roots due to either temporal or spatial isolation from evaporatively enriched leaf waters. For grasses in the controlled environment, there was no enrichment of source water, whereas enrichment of grass source water via evaporation from soils and/or stems was likely for grass samples grown in the field.Based on these results, evaporation from soils and/or stems appears to affect δD_l, but transpiration from leaves does not. Further evidence for this conclusion is found in modeling expected net evapotranspirational enrichment. A Craig-Gordon model applied to each of the field sites yields leaf water oxygen isotope ratios that can be used to accurately predict the observed δ¹⁸O_C values. In contrast, the calculated leaf water hydrogen isotope ratios are more enriched than what is required to predict observed δD_l values. These calculations lend support to the conclusion that while δ¹⁸O_C reflects both soil evaporation and transpiration, δD_l appears to only record evaporation from soils and/or stems. Therefore, the δD of n-alkanes can likely be used to reconstruct the δD of water entering a leaf, supporting the soil-enrichment model of Smith and Freeman (2006). In both the field and controlled studies, we found significant photosynthetic pathway effects on n-alkane δD suggesting that biochemical pathways or plant phylogeny have a greater effect on leaf wax δD than leaf-water enrichment in grasses.