Spatial gradients in plant leaf wax D/H across a coastal salt marsh in southern California

Coastal salt marsh ecosystems contain strong environmental gradients that are anticipated to influence the D/H ratios recorded in the leaf waxes of salt-tolerant plants. We characterized the molecular and hydrogen isotopic composition of alkanes in plant and sediment samples as well as the D/H ratios of environmental and plant waters across an elevation and inundation gradient in a southern Californian, coastal salt marsh. We sampled the dominant salt marsh plant species: Salicornia virginica, Arthrocnemum subterminale and Jamuea carnosa (all succulents), as well as Monanthochloe littoralis and Limonium californicum (nonsucculents). Plant xylem water hydrogen isotopic compositions indicate a shift in source waters from meteoric influences at upland sites (δD value −20‰) to seawater dominated values (0‰) at lowland areas. We found leaf water D enrichment relative to xylem water ranging from mean δD values of +54‰ (upland) to +28‰ (lowland), interpreted as a reduction of transpiration with increasing inundation time. This has the effect of increasing the net fractionation between source water and leaf wax product across the environmental gradient from mean values of −101‰ (upland) to −134‰ (lowland), with an attenuated signal recorded in the δD values of plant leaf wax n-alkanes (−122‰ to −136‰). These results constrain the hydrogen isotopic composition of salt marsh organic matter that may contribute to marine carbon budgets of the Santa Barbara Basin, and further indicate the potential for plant leaf waxes to resolve paleoenvironmental change, including sea level change, in sediment cores from salt marsh ecosystems.     

The measurement of D/H ratio in alkenones and their isotopic heterogeneity

Previous paleoenvironmental studies reported the δD values of a mixture of coeluting alkenones. Here, we present a semi-preparative normal-phase high-performance liquid chromatography–mass spectrometry (NP-HPLC–MS) method for purifying long chain (C₃₇ and C₃₈) unsaturated methyl and ethyl ketones (alkenones) on the basis of chain length and degree of unsaturation.The method was applied to purify alkenones in suspended particles and surface sediments from a site in Chesapeake Bay, eastern USA. The hydrogen isotopic composition of di- and triunsaturated C₃₇ and C₃₈ alkenones differed significantly on the basis of chain length and the degree of unsaturation, demonstrating the importance of gas chromatography–isotope ratio-mass spectrometry (GC–irMS) analysis of individual alkenones for accurate paleoenvironmental reconstruction. Constant fractionation factors between alkenones with different chain length but the same degree of unsaturation (${\alpha }_{{\text{C}}_{37:2}''–''{\text{C}}_{38:2}}\text{and}{\alpha }_{{\text{C}}_{37:3}''–''{\text{C}}_{38:3}}=1.01$) and those with the same chain length but different degree of unsaturation (${\alpha }_{{\text{C}}_{37:2}''–''{\text{C}}_{37:3}}\text{and}{\alpha }_{{\text{C}}_{38:2}''–''{\text{C}}_{38:3}}=0.97$) in all samples suggest that the values may represent hydrogen isotope fractionation associated with elongation and desaturation during alkenone biosynthesis.     

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.     

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 tubular-coring device for use in biogeochemical sampling of succulent and pulpy plants

A hand-operated, tubular-coring device developed for use in biogeochemical sampling of succulent and pulpy plants is described. The sampler weighs about 500 g (1.1 lb); and if 25 × 175 mm (1 × 7 in) screw-top test tubes are used as sample containers, the complete sampling equipment kit is easily portable, having both moderate bulk and weight.     

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.     

植物亲缘关系影响植物叶蜡正构烷烃的含量和分布特征

沉积物中的长链正构烷烃主要来自陆生高等植物叶蜡,在古环境重建中有着广泛应用。植物叶蜡正构烷烃的含量和分布特征受植物遗传因素控制。尽管前人对遗传因素的影响有报道,但还没有学者从植物系统进化发育学的角度来揭示植物的亲缘关系对植物叶蜡正构烷烃含量和分布特征的影响。为此,本研究选择了气候差异显著的北京东灵山（温带半湿润气候）和宁夏沙坡头（温带干旱气候）作为植物样品采集地点,于2004~2019年每年9月中旬进行样品采集,通过超声提取法分离植物叶片的叶蜡正构烷烃并进行测定。结果显示,两个地区相同科的植物主峰碳（C_max）分布相似,叶蜡正构烷烃总量（Σalk）和碳优势指数（CPI）存在显著性差异（p < 0.05）,东灵山Σalk和CPI的平均值分别是393μg/g和12,沙坡头是952μg/g和15。两个地区的平均碳链长度（ACL）没有显著性差异（p>0.05）,东灵山的ACL是29.4,沙坡头是29.6。本研究还发现东灵山和沙坡头地区都存在着不同科植物之间的叶蜡正构烷烃含量和分布特征具有显著差异,同一科不同属植物间差异相对较小,同一属不同种植物之间基本一致的规律,表明植物正构烷烃在植物间的分布基本上符合生态位保守理论,即亲缘关系越近的植物其叶蜡正构烷烃分布特征越相似,呈现出较强的系统发育保守性。由于两个地区都存在这样的规律,说明该规律不会受到局地气候环境的影响,具有普适性的意义。这在古环境重建中的意义是,当利用沉积物正构烷烃信号重建古环境时,除了考虑气候变化对植物叶蜡正构烷烃的直接影响,也应考虑气候变化会导致植物种类发生变化,从而改变正构烷烃含量和分布特征,最终影响沉积物中的正构烷烃信号。另外,沉积物正构烷烃信号与其他指标,如孢粉相结合,有可能提供植物群落结构变化的准确信息。

     

Geochemical influences on H40/1 bacteriophage inactivation in glaciofluvial sands

Geochemical heterogeneities may cause spatial variations in virus inactivation rates resulting from interactions with minerals leading to differences in natural disinfection capacity within an aquifer. Column studies investigating the interaction of the bacteriophage H40/1 with natural sands sampled from the Kappelen test site (Kappelen), Bern, Switzerland indicated that inactivation rates are higher for adsorbed bacteriophages than for those suspended in groundwater. Moreover, breakthrough curves obtained from field-based tracer tests at Kappelen indicated that the adsorbed H40/1 is inactivated in-situ at comparable rates. Statistical analyses of mineralogical data failed to demonstrate significant spatial variations in aquifer composition either across the site or with depth. In contrast hydrochemical analyses of groundwater samples collected at Kappelen demonstrated that iron-reducing groundwater occurs below aerobic waters. Tracer breakthrough curves indicate that H40/1 survival is not affected by variable redox conditions. Investigation results suggest that spatial geochemical variability does not significantly affect H40/1s inactivation rate at Kappelen.     

Variable190Os/184Os ratio in acid residues of iron meteorites

In residual materials obtained on dissolution of iron meteorites in 2M H₂SO₄, the ratio of¹⁹⁰Os/¹⁸⁴Os has been measured by radiochemical neutron activation analysis. Most residues have a normal isotopic ratio (to within ±2%). However, in some residues both positive and negative deviations in the isotopic ratio are seen. The most spectacular deviations are in the insoluble fragments (nuggets) from Sikhote Alin iron meteorite where the¹⁹⁰Os/¹⁸⁴Os ratio is about 50% of the normal value. The new results confirm our earlier observations that iron meteorites contain pre-solar grains.     

亚热带落叶乔木叶蜡正构烷烃单体碳同位素季节变化特征及影响因素

叶蜡正构烷烃单体碳同位素组成已经成为陆相沉积古生态重建的重要研究方法。现代过程研究是提升叶蜡正构烷烃指标解译的重要环节,而目前关于落叶乔木叶蜡烷烃单体碳同位素组成(δ¹³C_alk)的季节性变化研究还比较有限。本文对两种典型亚热带落叶乔木（小叶栎、枫香）开展了为期2年的叶蜡烷烃δ¹³C_alk研究。两个树种叶蜡烷烃的δ¹³C_alk值在春季偏正,随后迅速偏负,秋季变幅较小,趋于稳定。这种季节性变化特征和初期利用储存的老碳而后期利用新合成的糖类有关。在生长季末期,两种落叶乔木叶蜡烷烃相对于叶片的碳同位素分馏系数处于-6‰～-8‰,相对于文献报道的平均值偏负,这可能是因为生长季后期仍有少量的长链正构烷烃合成。研究结果揭示,基于落叶乔木叶蜡烷烃单体碳同位素进行古环境重建时需要考虑环境信号的季节性。     

A preliminary study of D/H ratios of chlorites

Chemistry dependence of D of chlorites is inferred from data for natural chlorites. D of water equilibrated with those chlorites is estimated to be –2–8.     

Site amplification investigation in Dhaka, Bangladesh, using H/V ratio of microtremor

The degree of damage during earthquakes strongly depends on dynamic characteristics of buildings as well as amplification of seismic waves in soils. Among the other approaches, microtremor is, perhaps, the easiest and cheapest way to understand the dynamic characteristics of soil. Non-reference microtremor measurements have been carried out in 45 locations in and around the capital Dhaka city of Bangladesh. Subsoil investigations (Standard Penetration Test and Shear Wave Velocity) have also been executed in those locations. Soil model has been developed for those locations for site response analysis by means of the program SHAKE. Among those 45 locations, predominant frequency of microtremor observation varies from 0.48 to 3.65 Hz. Out of those 45, for 35 locations Transfer function obtained from the program SHAKE have higher frequency compared to microtremor H/V ratio and for one location it has lower predominant frequency. For six locations, frequencies obtained from two methods are identical. For three other locations, there are no similarities between predominant frequency obtained from microtremor and transfer function. The seismic Vulnerability Index (Kg) for 45 sites varies between 0.45 and 31.85. Ten sites have been identified as having moderate vulnerability of soil layers to deform.     

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.     

Seasonal changes in D/H fractionation accompanying lipid biosynthesis in Spartina alterniflora

To investigate potential variability in the biosynthetic fractionation of hydrogen isotopes between environmental water and plant lipids, the cord grass Spartina alterniflora was sampled from a single location in a coastal marsh over a period of 16 months. Values of δD for a variety of lipids were measured by gas chromatography/pyrolysis/isotope ratio mass spectrometry. S. alterniflora grows partially submerged in seawater, so it has a virtually unlimited supply of water with nearly unvarying isotopic composition. Temporal changes in the δD values of lipids can thus be interpreted as representing mainly variations in biosynthetic fractionation. Fatty acids, n-alkanes, and phytol extracted from S. alterniflora have nearly constant δD values from ∼October through May, but exhibit marked decreases of up to 40‰ during summer months. These shifts in lipid δD values are interpreted as representing a change in the source of organic substrates, principally acetate, used for their biosynthesis. Lower summertime δD values for lipids are consistent with an increasing reliance on current photosynthate as feedstock for biosynthesis, whereas stored carbohydrate reserves are utilized more extensively during other times of the year. Regardless of the specific mechanism, the data emphasize that overall fractionations between water and plant lipids depend on biological as well as environmental variables, and that the biosynthetic fractionation is not necessarily constant even for a single plant. Because lipids such as fatty acids are present in all cells and turn over on timescales of weeks to months, measurements of δD values in fatty acids may also provide useful constraints for distinguishing biologic versus environmental controls on cellulose δD values in trees.     

植物叶蜡单体氢同位素重建非洲和东亚大陆古降水:亮点与难点

植物利用周围环境中的水分进行光合作用合成有机质, 其叶蜡氢同位素记录了源水中的氢同位素组成, 被认为是重建古水循环的替代性指标。然而从源水(降水)到合成叶蜡脂类化合物, 降水中的氢同位素会发生多步分馏作用。本文综述了对氢同位素分馏造成影响的因素及其校正方法, 通过有效的数据处理, 叶蜡氢同位素可以比较直接地反映降水的氢同位素组成。由于在热带地区降水氢同位素受"雨量效应"影响较大, 所以可以较好地反映降水量变化, 在非洲大陆常被用于重建水循环和气候变化; 在东亚大陆,"雨量效应"不再那么显著, 水汽的来源可能在影响降水氢同位素组成的过程中也起到了重要作用。     

Climatic significance of D/H and13C/12C ratios in Irish oak cellulose

δD and δ¹³C analyses of cellulose nitrate from two modern Irish oak trees that form part of the 7400 year long chronology were carried out, covering a period of 123 years (1861–1983 A.D.) with a 5 year resolution so as to assess the potential of this long chronology for retrieval of palaeoenvironmental data. One of the trees (Q5293) showed significant correlations of δD, δ¹³ C and ring width with mean annual temperatures as recorded at the Armagh weather station nearby and the mean fall temperatures of Central England. The other tree (Q5296) did not exhibit any significant climatic correlations either because it grew utilizing a nearby permanent source of ground water or because the intra-ring isotopic variations in Irish oak are significant enough to mask the climatic signal. Whilst our results have given a positive indication of the usefulness of these trees for palaeoenvironmental information, more trees need to be analysed to confirm our findings. Even though one of the trees did not exhibit climatic correlations, both trees show a significant positive correlation of δ¹³C and a negative correlation of δD with ring width variations. Furthermore, two tree samples that grew during the 1620s B.C., when a volcano is thought to have erupted on the Aegean island of Santorini, show increased δD and decreased δ¹³C for one to two decades following the eruption, though the magnitudes of change seem to vary with site and trees. We have proposed a possible mechanism based on tree phenology to explain both the above effects.     

2H/1H ratio of hopanes,tricyclic and tetracyclic terpanes in oils and source rocks from the Potiguar Basin,Brazil

We report the hydrogen isotope ratio ²H/¹H (expressed as δ²H values) of 8 selected hopanes, tricyclic and tetracyclic terpanes from oils and source rocks in the Potiguar Basin, and of associated formation water. Hopanes ranged in δ²H value from −79‰ to −142‰, whereas tri- and tetracyclic terpanes (TTTs) ranged from −137‰ to −225‰. Formation water δ²H values ranged from −23‰ to −32‰. The most significant pattern in the data is the systematic ²H enrichment of hopanes relative to TTTs, by an average of 45‰ in oils and 78‰ in source rock extracts. The hopanes appear close to hydrogen isotopic equilibrium with coeval formation water, whereas TTTs are significantly more ²H depleted. Given the similarities in structure between the two compound classes, it is unlikely that hopanes would be exchanged completely while the others would not. More likely, both classes have undergone a limited extent of exchange, but with the hopanes being biosynthesized with δ²H values closer to equilibrium. Our data suggest that at least some primary environmental and/or biotic information can be retained in the δ²H values of biomarkers in oils and extracts, and is not completely obscured by hydrogen exchange.     

D/H exchange in pure and Cr-doped enstatite: implications for hydrogen diffusivity

The kinetics of hydrogen diffusion in enstatite was studied by hydrogen–deuterium exchange experiments in the range of 1–5,000 bar and 700–850°C using synthetic single crystals of pure and Cr-doped enstatites. The OH- and OD-content in the samples was quantified after each thermal treatment with Fourier transformed infrared spectroscopy. H–D-exchange rates were measured parallel to the three crystallographic axes. In addition, in order to visualize diffusion profiles, OH and OD were mapped for some samples, utilizing synchrotron IR micro-spectroscopy. Hydrogen self-diffusivities derived from D/H exchange experiments at one atmosphere are very similar to the chemical diffusivity of hydrogen in natural Fe-bearing orthopyroxene, which was reported previously (Stalder and Skogby 2003) to exhibit a small, but significant anisotropy (D[001] > D[100] > D[010]). Activation energies are estimated to be 211 (±31) kJ/mol for diffusion parallel [100] and 185 (±28) kJ/mol for diffusion parallel [010]. Lattice diffusion of hydrogen is decelerated by more than one order of magnitude when Cr is dissolved in enstatite. In comparison to the chemical composition, pressure seems to have only a minor influence on hydrogen diffusion. Compared to other minerals in the Earth’s upper mantle, enstatite exhibits the highest activation energy for hydrogen diffusion, suggesting faster diffusion than in other mafic minerals at mantle temperatures, but slower diffusion at crustal conditions. Thus under upper mantle conditions, physical properties that are expected to be influenced by hydrogen mobility, such as electrical conductivity, may in enstatite be more intensely affected by the presence of hydrogen than in other upper mantle minerals.