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.     

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.     

尿素络合法分离-气相色谱/同位素质谱法分析土壤和植物中低含量(ppm级)正构烷烃的碳同位素

尿素络合法和5A分子筛法是常用的分离富集环境样品中正构烷烃的方法,但由于复杂的处理流程对于低含量正构烷烃的回收率普遍较低。本文通过优化尿素络合法分离富集正构烷烃的实验条件,建立了尿素络合法分离-气相色谱/同位素质谱分析土壤和植物中低含量正构烷烃单体碳同位素的方法。即采用正己烷-丙酮溶解样品,在4℃冰箱中与2 m L尿素-甲醇饱和溶液反应48 h;用去离子水溶解尿素络合物,加入正己烷后分离出有机相和水相,分别用正己烷、丙酮-正己烷萃取有机相和水相中的正构烷烃。中长链正构烷烃的回收率达79%~104%,高于5A分子筛法和已有尿素络合法的富集效果;单体碳同位素的分析精度为0.09‰~0.63‰(1σ)。利用改进的方法分析实际样品,大幅降低了未分峰和共流出物的干扰,提高了实际样品中ppm级中长链正构烷烃的回收率。     

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.     

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.     

The variations of stable carbon isotope ratio of land plant-derived n-alkanes in deep-sea sediments from the Bering Sea and the North Pacific Ocean during the last 250,000 years

Two piston cores, one located far from the continents (The North Pacific Ocean: ES core), and another located comparatively closer to the continents (The Bering Sea: BOW-8a core) were investigated to reconstruct environmental changes on source land areas. The results show significant contribution of terrestrial organic matter to sediments in both cores. The δ¹³C values of n-C₂₇, n-C₂₉, and n-C₃₁ alkanes in sediments from the North Pacific ES core show significant glacial to interglacial variation whereas those from the Bering Sea core do not. Variations of δ¹³C values of land plant n-alkanes are related to the environmental or vegetational changes in the source land areas. Environmental changes, especially, aridity, rainfall, and pCO₂ during glacial/interglacial transitional periods can affect vegetation, and therefore C₃ / C₄ plant ratios, resulting in δ¹³C changes in the preserved land plant biomarkers. Maximum values of δ¹³C as well as maximum average chain length values of long chain n-alkanes in the ES core occur mostly at the interglacial to glacial transition zones reflecting a time lag related to incorporation of living organic matter into soil and transportation into ocean basins via wind and/or ability of C₄ plants to adapt for a longer period before being replaced by C₃ plants when subjected to gradual climatic changes. Irregular variations with no clear glacial to interglacial trends in the BOW-8a core may result from complex mixture of aerosols from westerly winds and riverine organic matter from the Bering Sea catchments. In addition, terrestrial organic matter entering the Bering Sea could originate from multiple pathways including eolian, riverine, and ice rafted debris, and possibly be disturbed by turbidity and other local currents which can induce re-suspension and re-sedimentation causing an obliterated time relation in the Bering Sea biomarker records.     

地质样品正构烷烃组分分离纯化的部分问题探究

用实验室自配的标准正构烷烃样品分别经硅胶或氧化铝柱层析后发现,等量溶剂洗脱的情况下硅胶对长链正构烷烃无吸附而氧化铝具有一定吸附性。进一步通过用植物样品测试4种层析柱填充方法,发现不论是只用氧化铝填充还是上部硅胶下部氧化铝和上部氧化铝下部硅胶,都会对长链正构烷烃产生一定的吸附,且这种吸附效果随着碳链的增长而增强。在实验条件下,当碳链加长到C36时,用硅胶加氧化铝填充层析柱的吸附量已达到20%左右,而只用氧化铝填充层析柱的吸附量则高达50%。故建议对研究高碳数正构烷烃的地质样品组分提取时用单一的硅胶柱层析方法。同时,实验显示对于一些杂质多的正构烷烃样品经过尿素络合后比络合前"干净"得多。18个黄土-古土壤和植物样品平均回收率为50%左右,经过尿素络合后的样品正构烷烃各组分相对含量基本不会发生改变,也不会产生明显的同位素分馏效应。因此在进行非正构组分干扰较大的正构烷烃各组分相对含量或同位素分析时,可以选择尿素络合的方法来将其纯化。     

Tropical Atlantic SST history inferred from Ca isotope thermometry over the last 140ka

Exploring the potentials of new methods in palaeothermometry is essential to improve our understanding of past climate change. Here, we present a refinement of the published δ^44/40Ca-temperature calibration investigating modern specimens of planktonic foraminifera Globigerinoides sacculifer and apply this to sea surface temperature (SST) reconstructions over the last two glacial-interglacial cycles. Reproduced measurements of modern G. sacculifer collected from surface waters describe a linear relationship for the investigated temperature range (19.0-28.5 °C): δ^44/40Ca [‰] = 0.22 (±0.05)∗SST [°C] −4.88. Thus a change of δ^44/40Ca[‰] of 0.22 (±0.05) corresponds to a relative change of 1 °C. The refined δ^44/40Ca_modern-calibration allows the determination of both relative temperature changes and absolute temperatures in the past. This δ^44/40Ca_modern-calibration for G. sacculifer has been applied to the tropical East Atlantic sediment core GeoB1112 for which other SST proxy data are available. Comparison of the different data sets gives no indication for significant secondary overprinting of the δ^44/40Ca signal. Long-term trends in reconstructed SST correlate strongly with temperature records derived from oxygen isotopes and Mg/Ca ratios supporting the methods validity. The observed change of SST of approximately 3 °C at the Holocene-last glacial maximum transition reveals additional evidence for the important role of the tropical Atlantic in triggering global climate change, based on a new independent palaeothermometer.     

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‰).     

Comparative evolution of the Senegal and eastern central Atlantic Basins, from mineralogical and geochemical investigations

ABSTRACT
Cretaceous to Palaeogene sedimentary series in two long, continously recovered boreholes from the Senegal coastal basin and adjacent Cape Verde deep-sea basin have been compared by mineralogical, geochemical, electron-microscope and microprobe investigations. The transition between the diagenetic influences related to the depth of burial and the palaeoenvironmental influences, identified in the thick coastal-basin successions, is complicated by the tectonic instability of the margin during periods of high subsidence rates and crustal thinning. As the deep-sea basin sediments are only slightly affected by diagenetic changes, the comparison between the deep sea and coastal series allows the relative effects of lithostatic pressure, tectonics and other palaeoenvironmental factors to be evaluated. The disappearance of synsedimentary signatures (tectonics, climate, depositional conditions, etc.) expressed by clay mineralogy occurs below 4.5 km; there are no significant diagenetic changes in sediments at less than 2 km depth. By comparing identical time slices in coastal and deep-sea basins, it is possible to recognize from the clay stratigraphic record the main African detrital sources, the hot and often semi-arid character of the continental climate during the Cretaceous, the existence of minor but extensive stages of tectonic activity (Barremian-late Aptian, late Albian-early Cenomanian), the temporary existence of semi-closed basins on the shelf (Late Cretaceous, early Palaeogene) and the complexity of transport and sedimentation relationships between proximal and distal environments.     

Predominance of even carbon-numbered n-alkanes from lacustrine sediments in Linxia Basin,NE Tibetan Plateau: Implications for climate change

This study reports the first observation of predominant even C-numbered n-alkanes from sediments in the continuous lacustrine-sedimentary section (Maogou) from the Late Miocene to the Early Pliocene (13–4.4 Ma) in the Linxia Basin, NE Tibetan Plateau. The n-alkanes showed a bimodal distribution that is characterised by a centre at n-C₁₆–n-C₂₀ with maximum values at n-C₁₈ and n-C₂₇–n-C₃₁ as well as at n-C₂₉. The first mode shows a strong even C-number predominance (OEP_16–20 0.34–0.66). In contrast, the second mode has a strong odd C-number predominance (OEP_27–31 1.20–2.45). Certain types of special autochthonous bacteria are a possible source for this distribution of even C-numbered n-alkanes in lacustrine sediments. These bacteria may have a high production rate in weak oxic–anoxic and arid depositional environments, in which a variety of geochemical parameters have recorded palaeoclimate change.     

Carbon isotope evidence implying high O2/CO2 ratios in the Permo-Carboniferous atmosphere

Theoretical models predict a marked increase in atmospheric O₂ to ∼35% during the Permo-Carboniferous (∼300 Ma) occurring against a low (∼0.03%) CO₂ level. An upper O₂ value of 35%, however, remains disputed because ignition data indicate that excessive global forest fires would have ensued. This uncertainty limits interpretation of the role played by atmospheric oxygen in Late Paleozoic biotic evolution. Here, we describe new results from laboratory experiments with vascular land plants that establish that a rise in O₂ to 35% increases isotopic fractionation (Δ¹³C) during growth relative to control plants grown at 21% O₂. Despite some effect of the background atmospheric CO₂ level on the magnitude of the increase, we hypothesize that a substantial Permo-Carboniferous rise in O₂ could have imprinted a detectable geochemical signature in the plant fossil record. Over 50 carbon isotope measurements on intact carbon from four fossil plant clades with differing physiological ecologies and ranging in age from Devonian to Cretaceous reveal a substantial Δ¹³C anomaly (5‰) occurring between 300 and 250 Ma. The timing and direction of the Δ¹³C excursion is consistent with the effects of a high O₂ atmosphere on plants, as predicted from photosynthetic theory and observed in our experiments. Preliminary calibration of the fossil Δ¹³C record against experimental data yields a predicted O₂/CO₂ mixing ratio of the ancient atmosphere consistent with that calculated from long-term models of the global carbon and oxygen cycles. We conclude that further work on the effects of O₂ in the combustion of plant materials and the spread of wildfire is necessary before existing data can be used to reliably set the upper limit for paleo-O₂ levels.     

Variations in the content and distribution of n-alkanes in a series of carboniferous vitrinites and sporinites of bituminous rank

n-Alkanes in the soluble organic matter extracted from a series of vitrinite and sporinite concentrates have been analysed by gas chromatography. The macerals were isolated from coals ranging in rank from 77.1% to 86.6% carbon (vitrinite: dry, ash-free), and yields of n-alkanes ranged from 10 to 580 ppm for vitrinites and from 20 to 970 ppm for sporinites. The maximum yields were found at a rank of 85.4% C from vitrinites and 86.6% C from sporinites.Distribution maxima of the n-alkanes, as shown by gas chromatography, range from C₂₇ and C₂₉ at lower ranks to as low as C₁₆ at higher ranks. The distributions also show a progressive decrease in the preference of odd-carbon-number homologues with increasing rank. Virtually smooth distributions were attained in high-volatile bituminous A coals. Quantitative data show that the loss of the odd-carbon-number preference occurred, for the most part, while individual long-chain homologues increased in concentration.There is a progressive increase in the amounts of shorter-chain n-alkanes with increasing rank. It is suggested that sequential processes may have occurred whereby the rate of formation of long-chain n-alkanes in high-volatile bituminous A rank macerals becomes slower than their rate of subsequent fragmentation to shorter chain lengths. Consequently, assuming derivation from the insoluble maceral matrices, the chain-length distributions of parent n-alkyl structures within the insoluble material may retain characteristics pertaining more to the nature of the source organic matter at the time of deposition than do the extractable n-alkane patterns, especially at higher ranks.     

Paleoclimatic significance of quartz/illite variations in cores from the eastern equatorial north Atlantic

Detailed X-ray diffraction analysis of cores taken in the eastern equatorial Atlantic suggest that during approximately the last 600,000 yr a relatively constant background of clay mineral deposition has existed on which are superimposed large oscillations in quartz input (relative to illite). The quartz is transported from the Sahara Desert by the northeast trade winds and the quartz/illite oscillations appear to reflect past changes in the transporting effectiveness (intensity) of the trade winds. Comparison of the quartz/illite variations with paleotemperature variations for the northeast Atlantic suggests that major inputs of quartz correlate with cold periods and that warm periods correlate with low quartz input. The parallelism between the curves indicates a fundamental link between trade wind intensity and past climatic fluctuations, and further suggests that the changes of intensity are closely atuned to temperature fluctuations in the northern latitudes. The relationship between the quartz/illite variations and wind intensity is complicated by the fact that other climatically controlled factors may also affect quartz deposition in the equatorial Atlantic.     

Seasonal changes in stable carbon isotopic composition of n-alkanes in the marine aerosols from the western North Pacific: Implications for the source and atmospheric transport

To constrain seasonal changes in the long-range atmospheric transport of land-derived lipid biomarker compounds, we investigated the compound-specific stable isotopic composition of marine aerosol n-alkanes collected from 1990 to 1993 at a remote island, Chichi-Jima (27°04′N, 142°13′E), in the western North Pacific. Compound-specific isotope analysis revealed, in particular, strong seasonal changes in the δ¹³C values of the C₂₉ and C₃₁n-alkanes (biomarkers for higher plants). Lighter δ¹³C values were observed in winter (typically −32 to −34‰), with a transition to heavier values in summer (typically −28 to −31‰). Using a mixing equation and typical end members for C₃ and C₄ plants, we found that this is due to relative increases in the contributions from C₄ plants in the summer season. Using backward air-mass trajectory analyses, it was shown that the Asian continent was the major source region for C₃ plant material during winter/spring, whereas Indonesia/Australia and possibly the Americas were the major source regions for C₄ material during the summer/autumn. Also observed was an enhanced atmospheric transport of n-alkanes from C₄ plants in 1991 summer/autumn during a strong El Nino event, which was associated with forest and bushfires in Indonesia and Australia. In addition to providing information on contemporary processes, this study also provides a base for future paleoclimatological work in ocean sediments.     

Carbon isotope stratigraphy of Lochkovian to Eifelian limestones from the Devonian of central and southern Europe

Lower to Middle Devonian carbonates of the Prague Syncline, the Carnic Alps, the Montagne Noire, and the Cantabrian Mountains were investigated for δ¹³C_carb and δ¹³C_org. These values were measured on bulk rocks, selected components and cements. Many carbonates exhibit primary marine values, but some are altered by diagenesis. A δ¹³C curve can be presented for the latest Pridolian to Emsian time interval. Several sharp or broad positive excursions are obvious in the woschmidti-postwoschmidti, sulcatus, kitabicus, Late serotinus, and kockelianus conodont zones. The excursion at the Silurian–Devonian boundary is known worldwide and therefore considered global in nature. Some of the others are described for the first time from central and southern Europe, and their global nature has to be verified by further investigations in other regions. Most excursions relate to and/or started during major regressions whereas sea-level highstands correspond to minimal δ¹³C values. Similar relationships between sea-level changes and δ¹³C have been observed from other early Palaeozoic intervals. The transgressive Chote? (?) and Ka?ák events are marked by positive isotope excursions, this type of combination is usually observed in late Palaeozoic to Cenozoic black shale events.     

Gas flux to the atmosphere from mud volcanoes in eastern Romania

Gas flux measurements have for the first time been taken from vents and soil of eastern Romania mud volcanoes, the largest geological structures in Europe releasing methane into the atmosphere. In the quiescent phase, the methane emission from single vents is up to 28 t yr^?1. Diffuse soil microseepage is of the order of 10²?10⁵ mg m^?2 day^?1. A total output of at least 1200 tonnes of CH₄ per year can be conservatively estimated over the area investigated alone (～ 2.3 km²). Helium fluxes are up to five orders of magnitude higher than the average flux in a stable continental area, pointing to a close link between mud volcanoes and crustal degassing through faults crossing the deep hydrocarbon reservoirs. These data represent a key contribution towards refining global CH₄‐emission estimates, which indicate mud volcanoes as a significant and unavoidable source of greenhouse gases for the atmosphere.     

Ionization effects from cosmic sources of x-rays in the lower atmosphere

Detectable ionization effects in the ionosphericD-region from individual, strong and steady x-ray sources such as Sco X-1 and transient x-ray sources such as Cet X-2 have been reported by us and many others previously based on the field strength and phase variations of the VLF data. As a follow up to these investigations, we have examined the integrated effects of many of the known x-ray sources discovered by UHURU, ANS, Ariel V and SAS-3 satellites, in order to understand the totality of their effects. These effects are examined in the present paper for 0° and +38° geographic latitudes corresponding to midnight conditions and for different times of the year. Such effects are compared, in turn, with those of the known steady sources responsible forD-region ionization such as Lyman-alpha and galactic cosmic radiations. The results are presented as profiles of electron production rates as a function of height. Our study leads to the conclusion that there should be detectable annual variations of the electron density which are pronounced around May-August. Further, the results of the computations on electron production rates corresponding to the spectacular x-ray nova A0620-00 are also included in the present paper.     

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.     

Early Pleistocene climate changes in the central Mediterranean region as inferred from integrated pollen and planktonic foraminiferal stable isotope analyses

Vegetation inherited from a Pliocene subtropical climate evolved through obliquity oscillations and global cooling leading to modern conditions. An integrated, highly time-resolved record of pollen and stable isotopes (δ¹⁸O and δ¹³C of Globigerina bulloides) was obtained to understand vegetation responses to Early Pleistocene climate changes. Continental and marine responses are compared in the Central Mediterranean region with a particular consideration of environmental changes during anoxic events.Pollen data illustrate vegetation dynamics as follows: [1] development of mesothermic elements (warm and humid conditions); [2] expansion of mid- and high-altitude elements (cooler but still humid conditions); and [3] strengthening of steppe and herb elements (cooler and dry conditions). These successions correlate with precession. δ¹⁸O variations recorded by Globigerina bulloides define two cycles (MIS 43-40) related to obliquity. At northern low- to mid-latitudes, the pollen signal records temperature and wetness changes related to precession even during global climate changes induced by obliquity. This may result in unexpected increasing wetness during glacial periods, which has to be considered specific to the Central and Eastern Mediterranean region. Lastly, an analysis of anoxic events reveals that enhanced runoff is indicated by increasing frequency of the riparian trees Liquidambar and Zelkova.