scholarly journals Validation of a coupled <i>δ</i><sup>2</sup>H<sub><i>n</i>-alkane</sub>–<i>δ</i><sup>18</sup>O<sub>sugar</sub> paleohygrometer approach based on a climate chamber experiment

2021 ◽  
Vol 18 (19) ◽  
pp. 5363-5380
Author(s):  
Johannes Hepp ◽  
Christoph Mayr ◽  
Kazimierz Rozanski ◽  
Imke Kathrin Schäfer ◽  
Mario Tuthorn ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Vicia Faba ◽  
Isotope Composition ◽  
Leaf Water ◽  
Source Water ◽  
Climate Chamber ◽  
Chamber Experiment ◽  
Leaf Wax ◽  
Hydrogen Isotope Composition ◽  
Water Isotope

Abstract. The hydrogen isotope composition of leaf-wax-derived biomarkers, e.g., long-chain n-alkanes (δ2Hn-alkane), is widely applied in paleoclimate. However, a direct reconstruction of the isotope composition of source water based on δ2Hn-alkane alone is challenging due to the enrichment of heavy isotopes during evaporation. The coupling of δ2Hn-alkane with δ18O of hemicellulose-derived sugars (δ18Osugar) has the potential to disentangle this limitation and additionally to allow relative humidity reconstructions. Here, we present δ2Hn-alkane as well as δ18Osugar results obtained from leaves of Eucalyptus globulus, Vicia faba, and Brassica oleracea, which grew under controlled conditions. We addressed the questions of (i) whether δ2Hn-alkane and δ18Osugar values allow reconstructions of leaf water isotope composition, (ii) how accurately the reconstructed leaf water isotope composition enables relative humidity (RH) reconstruction, and (iii) whether the coupling of δ2Hn-alkane and δ18Osugar enables a robust source water calculation. For all investigated species, the n-alkane n-C29 was most abundant and therefore used for compound-specific δ2H measurements. For Vicia faba, additionally the δ2H values of n-C31 could be evaluated robustly. Regarding hemicellulose-derived monosaccharides, arabinose and xylose were most abundant, and their δ18O values were therefore used to calculate weighted mean leaf δ18Osugar values. Both δ2Hn-alkane and δ18Osugar yielded significant correlations with δ2Hleaf water and δ18Oleaf water, respectively (r2=0.45 and 0.85, respectively; p<0.001, n=24). Mean fractionation factors between biomarkers and leaf water were found to be −156 ‰ (ranging from −133 ‰ to −192 ‰) for εn-alkane/leaf water and +27.3 ‰ (ranging from +23.0 ‰ to 32.3 ‰) for εsugar/leaf water, respectively. Modeled RHair values from a Craig–Gordon model using measured Tair, δ2Hleaf water and δ18Oleaf water as input correlate highly significantly with modeled RHair values (R2=0.84, p<0.001, RMSE = 6 %). When coupling δ2Hn-alkane and δ18Osugar values, the correlation of modeled RHair values with measured RHair values is weaker but still highly significant, with R2=0.54 (p<0.001, RMSE = 10 %). Finally, the reconstructed source water isotope composition (δ2Hs and δ18Os) as calculated from our coupled approach matches the source water in the climate chamber experiment (δ2Htank water and δ18Otank water). This highlights the great potential of the coupled δ2Hn-alkane–δ18Osugar paleohygrometer approach for paleoclimate and relative humidity reconstructions.

scholarly journals Validation of a coupled δ<sup>2</sup>H<sub><i>n</i>-alkane</sub>-δ<sup>18</sup>O<sub>sugar</sub> paleohygrometer approach based on a climate chamber experiment

2019 ◽  
Author(s):  
Johannes Hepp ◽  
Bruno Glaser ◽  
Dieter Juchelka ◽  
Christoph Mayr ◽  
Kazimierz Rozanski ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Isotopic Composition ◽  
Vicia Faba ◽  
Isotope Composition ◽  
Leaf Water ◽  
Source Water ◽  
Leaf Wax ◽  
Hydrogen Isotopic Composition ◽  
Water Isotope ◽  
Isotopic Signal

Abstract. The hydrogen isotopic composition of leaf wax-derived biomarkers, e.g. long chain n-alkanes (δ2Hn-alkane), is widely applied in paleoclimatology research. However, a direct reconstruction of the isotopic composition of paleoprecipitation based on δ2Hn-alkane alone can be challenging due to the overprint of the source water isotopic signal by leaf-water enrichment. The coupling of δ2Hn-alkane with δ18O of hemicellulose-derived sugars (δ18Osugar) has the potential to disentangle this effect and additionally allow relative humidity reconstructions. Here, we present δ2Hn-alkane as well as δ18Osugar results obtained from leaves of the plant species Eucalyptus globulus, Vicia faba var. minor and Brassica oleracea var. medullosa, which were grown under controlled conditions. We addressed the questions (i) do δ2Hn-alkane and δ18Osugar values allow precise reconstructions of leaf water isotope composition, (ii) how accurately does the reconstructed leaf-water-isotope composition enables relative humidity (RH) reconstruction in which the plants grew, and (iii) does the coupling of δ2Hn-alkane and δ18Osugar enable a robust source water calculation? For all investigated species, the alkane n-C29 was most abundant and therefore used for compound-specific δ2H measurements. For Vicia faba, additionally the δ2H values of n-C31 could be evaluated robustly. With regard to hemicellulose-derived monosaccharides, arabinose and xylose were most abundant and their δ18O values were therefore used to calculate weighted mean leaf δ18Osugar values. Both δ2Hn-alkane and δ18Osugar yielded significant correlations with δ2Hleaf-water and δ18Oleaf-water, respectively (r2 = 0.45 and 0.85, respectively; p 

scholarly journals Validation of a coupled δ<sup>2</sup>H<sub><i>n</i>-alkane</sub>-δ<sup>18</sup>O<sub>sugar</sub> paleohygrometer approach based on a climate chamber experiment

2020 ◽  
Author(s):  
Johannes Hepp ◽  
Christoph Mayr ◽  
Kazimierz Rozanski ◽  
Imke Kathrin Schäfer ◽  
Mario Tuthorn ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Isotopic Composition ◽  
Vicia Faba ◽  
Isotope Composition ◽  
Leaf Water ◽  
Source Water ◽  
Leaf Wax ◽  
Hydrogen Isotopic Composition ◽  
Water Isotope ◽  
Isotopic Signal

Abstract. The hydrogen isotopic composition of leaf wax-derived biomarkers, e.g. long chain n-alkanes (δ2Hn-alkane), is widely applied in paleoclimatology research. However, a direct reconstruction of the isotopic composition of source water based on δ2Hn-alkane alone can be challenging due to the alteration of the soil water isotopic signal by leaf-water heavy-isotope enrichment. The coupling of δ2Hn-alkane with δ18O of hemicellulose-derived sugars (δ18Osugar) has the potential to disentangle this effect and additionally to allow relative humidity reconstructions. Here, we present δ2Hn-alkane as well as δ18Osugar results obtained from leaves of the plant species Eucalyptus globulus, Vicia faba var. minor and Brassica oleracea var. medullosa, which grew under controlled conditions. We addressed the questions (i) do δ2Hn-alkane and δ18Osugar values allow precise reconstructions of leaf water isotope composition, (ii) how accurately does the reconstructed leaf-water-isotope composition enables relative humidity (RH) reconstruction in which the plants grew, and (iii) does the coupling of δ2Hn-alkane and δ18Osugar enable a robust source water calculation? For all investigated species, the alkane n-C29 was most abundant and therefore used for compound-specific δ2H measurements. For Vicia faba, additionally the δ2H values of n-C31 could be evaluated robustly. With regard to hemicellulose-derived monosaccharides, arabinose and xylose were most abundant and their δ18O values were therefore used to calculate weighted mean leaf δ18Osugar values. Both δ2Hn-alkane and δ18Osugar yielded significant correlations with δ2Hleaf-water and δ18Oleaf-water, respectively (r2 = 0.45 and 0.85, respectively; p 

The dominant environmental driver of leaf water stable isotope enrichment differs for H-2 compared to O-18

2020 ◽  
Author(s):  
Matthias Cuntz ◽  
Lucas A Cernusak ◽  
Keyword(s):  
Stable Isotope ◽  
Relative Humidity ◽  
Air Temperature ◽  
Gordon Equation ◽  
Isotope Composition ◽  
Environmental Variable ◽  
Leaf Water ◽  
Source Water ◽  
Stable Isotope Composition ◽  
Water Stable Isotope

&lt;p&gt;Several important isotopic biomarkers derive at least part of their signal from the stable isotope composition of leaf water (e.g., leaf wax &amp;#948;&lt;sup&gt;2&lt;/sup&gt;H, cellulose &amp;#948;&lt;sup&gt;2&lt;/sup&gt;H and &amp;#948;&lt;sup&gt;18&lt;/sup&gt;O, lignin &amp;#948;&lt;sup&gt;18&lt;/sup&gt;O). In order to interpret these isotopic proxies, it is therefore helpful to know which environmental variable most strongly controls a given leaf water stable isotope signal. We collated observations of the stable isotope compositions of leaf water, xylem water, and atmospheric vapour, along with air temperature and relative humidity, to test whether the dominant driver of leaf water &lt;sup&gt;2&lt;/sup&gt;H concentration could differ from that of &lt;sup&gt;18&lt;/sup&gt;O concentration. Our dataset comprises 690 observations from 35 sites with broad geographical coverage. We limited our analysis to daytime observations, when the photosynthetic processes that incorporate the leaf water isotopic signal primarily take place. The Craig-Gordon equation was generally a good predictor for daytime bulk leaf water stable isotope composition for both &amp;#948;&lt;sup&gt;2&lt;/sup&gt;H (R&lt;sup&gt;2&lt;/sup&gt;=0.86, p&lt;0.001) and &amp;#948;&lt;sup&gt;18&lt;/sup&gt;O (R&lt;sup&gt;2&lt;/sup&gt;=0.63, p&lt;0.001). It showed about 10% admixture of source water was caused by unenriched water pools such as leaf veins or the P&amp;#233;clet effect. Solving the Craig-Gordon equation requires knowledge of relative humidity, air temperature, and the stable isotope compositions of source water and atmospheric vapour. However, it is not possible to invert the Craig-Gordon equation to solve for one of these parameters unless the others are known. Here we show that the two isotopic signals of &amp;#948;&lt;sup&gt;2&lt;/sup&gt;H and &amp;#948;&lt;sup&gt;18&lt;/sup&gt;O are predominantly driven by different environmental variables: leaf water &amp;#948;&lt;sup&gt;2&lt;/sup&gt;H correlated most strongly with the &amp;#948;&lt;sup&gt;2&lt;/sup&gt;H of source water (R&lt;sup&gt;2&lt;/sup&gt;=0.68, p&lt;0.001) and atmospheric vapour (R&lt;sup&gt;2&lt;/sup&gt;=0.63, p&lt;0.001), whereas leaf water &amp;#948;&lt;sup&gt;18&lt;/sup&gt;O correlated most strongly with air relative humidity (R&lt;sup&gt;2&lt;/sup&gt;=0.46, p&lt;0.001). We conclude that these two isotopic signals of leaf water are not simply mirror images of the same environmental information, but carry distinct signals of different climate factors, with crucial implications for the interpretation of downstream isotopic biomarkers.&lt;/p&gt;

scholarly journals Evaluation of bacterial glycerol dialkyl glycerol tetraether and <sup>2</sup>H–<sup>18</sup>O biomarker proxies along a central European topsoil transect

2020 ◽  
Vol 17 (3) ◽  
pp. 741-756 ◽  
Author(s):  
Johannes Hepp ◽  
Imke Kathrin Schäfer ◽  
Verena Lanny ◽  
Jörg Franke ◽  
Marcel Bliedtner ◽  
...  
Keyword(s):  
Isotopic Composition ◽  
Soil Ph ◽  
Isotope Composition ◽  
Leaf Water ◽  
Source Water ◽  
Central European ◽  
Ph Values ◽  
Stable Isotopic Composition ◽  
Stable Isotopic ◽  
Water Isotope

Abstract. Molecular fossils, like bacterial branched glycerol dialkyl glycerol tetraethers (brGDGTs), and the stable isotopic composition of biomarkers, such as δ2H of leaf wax-derived n-alkanes (δ2Hn-alkane) or δ18O of hemicellulose-derived sugars (δ18Osugar), are increasingly used for the reconstruction of past climate and environmental conditions. Plant-derived δ2Hn-alkane and δ18Osugar values record the isotopic composition of plant source water (δ2Hsource-water and δ18Osource-water), which usually reflects mean annual precipitation (δ2Hprecipiation and δ18Oprecipiation), modulated by evapotranspirative leaf water enrichment and biosynthetic fractionation (εbio). Accuracy and precision of respective proxies should be ideally evaluated at a regional scale. For this study, we analysed topsoils below coniferous and deciduous forests as well as grassland soils along a central European transect in order to investigate the variability and robustness of various proxies and to identify effects related to vegetation. Soil pH values derived from brGDGTs correlate reasonably well with measured soil pH values but are systematically overestimated (ΔpH = 0.6±0.6). The branched vs. isoprenoid tetraether index (BIT) can give some indication whether the pH reconstruction is reliable. Temperatures derived from brGDGTs overestimate mean annual air temperatures slightly (ΔTMA=0.5 ∘C ± 2.4). Apparent isotopic fractionation (εn-alkane/precipitation and εsugar∕precipitation) is lower for grassland sites than for forest sites due to signal damping; i.e. grass biomarkers do not record the full evapotranspirative leaf water enrichment. Coupling δ2Hn-alkane with δ18Osugar allows us to reconstruct the stable isotopic composition of the source water more accurately than without the coupled approach (Δδ2H = ∼-21 ‰ ± 22 ‰ and Δδ18O = ∼-2.9 ‰ ± 2.8 ‰). Similarly, relative humidity during daytime and the vegetation period (RHMDV) can be reconstructed using the coupled isotope approach (ΔRHMDV=∼-17±12). Especially for coniferous sites, reconstructed RHMDV values as well as source water isotope composition underestimate the measured values. This can likely be explained by understorey grass vegetation at the coniferous sites contributing significantly to the n-alkane pool but only marginally to the sugar pool in the topsoils. Vegetation-dependent variable signal damping and εbio (regarding 2H between n-alkanes and leaf water) along our European transect are difficult to quantify but likely contribute to the observed underestimation in the source water isotope composition and RH reconstructions. Microclimate variability could cause the rather large uncertainties. Vegetation-related effects do, by contrast, not affect the brGDGT-derived reconstructions. Overall, GDGTs and the coupled δ2Hn-alkane–δ18Osugar approach have great potential for more quantitative paleoclimate reconstructions.

scholarly journals 18O enrichment of leaf cellulose correlated with 18O enrichment of leaf sucrose but not bulk leaf water in a C3 grass across contrasts of atmospheric CO2 concentration and air humidity

2021 ◽  
Author(s):  
Juan C. Baca Cabrera ◽  
Regina T. Hirl ◽  
Rudi Schäufele ◽  
Jianjun Zhu ◽  
Haitao Liu ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Spatial Heterogeneity ◽  
Lolium Perenne ◽  
Co2 Concentration ◽  
Leaf Water ◽  
Atmospheric Co2 ◽  
Cellulose Synthesis ◽  
Source Water ◽  
Sucrose Synthesis ◽  
Air Humidity

Abstract · The 18O composition of plant cellulose is often used to reconstruct past climate and plant function. However, uncertainty remains regarding the estimation of the leaf sucrose 18O signal and its subsequent attenuation by 18O exchange with source water during cellulose synthesis.· We grew Lolium perenne at three CO2 concentrations (200, 400 or 800 mmol mol-1) and two relative humidity (RH) levels (50% or 75%), and determined 18O enrichment of leaf sucrose (Δ18OSucrose), bulk leaf water (Δ18OLW), leaf cellulose (Δ18OCellulose) and water at the site of cellulose synthesis (Δ18OCelSynW). · Δ18OCellulose correlated with Δ18OSucrose (R2=0.87) but not with Δ18OLW (R2=0.04), due to a variable 18O discrepancy (range 2.0-9.0‰) between sucrose synthesis water (Δ18OSucSynW, estimated from Δ18OSucrose) and bulk leaf water. The discrepancy resulted mainly from an RH effect. The proportion of oxygen in cellulose that exchanged with medium water during cellulose formation (pex), was near-constant when referenced to Δ18OSucSynW (pex-SucSynW = 0.52±0.02 SE), but varied when related to bulk leaf water (pex-LW = –0.01 to 0.46). · We conclude that previously reported RH-dependent variations of pex-LW in grasses are related to a discrepancy between Δ18OSucSynW and Δ18OLW that may result from spatial heterogeneity in 18O gradients of leaf water and photosynthetic sucrose synthesis.

scholarly journals The triple oxygen isotope composition of phytoliths, a new proxy of atmospheric relative humidity: controls of soil water isotope composition, temperature, CO<sub>2</sub> concentration and relative humidity

2021 ◽  
Author(s):  
Clément Outrequin ◽  
Anne Alexandre ◽  
Christine Vallet-Coulomb ◽  
Clément Piel ◽  
Sébastien Devidal ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Oxygen Isotope ◽  
Soil Water ◽  
Isotope Composition ◽  
Co2 Concentration ◽  
Oxygen Isotope Composition ◽  
Growth Chamber ◽  
Starting Point ◽  
Atmospheric Relative Humidity ◽  
Water Isotope

Abstract. Continental atmospheric relative humidity is a major climate parameter whose variability is poorly understood by global climate models. Models’improvement relies on model-data comparisons for past periods. However, there are no truly quantitative indicators of relative humidity for the pre-instrumental period. Previous studies highlighted a quantitative relationship between the triple oxygen isotope composition of phytoliths, and particularly the 17O-excess of phytoliths, and atmospheric relative humidity. Here, as part of a series of calibrations, we examine the respective controls of soil water isotope composition, temperature, CO2 concentration and relative humidity on phytolith 17O-excess. For that purpose, the grass species Festuca arundinacea was grown in growth chambers where these parameters were varying. The setup was designed to control the evolution of the triple oxygen isotope composition of phytoliths and all the water compartments of the soil-plant-atmosphere continuum. Different analytical techniques (cavity ring-down spectroscopy and isotope ratio mass spectrometry) were used to analyse water and silica. An inter-laboratory comparison allowed to strengthen the isotope data matching. Water and phytolith isotope compositions were compared to previous datasets obtained from growth chamber and natural tropical sites. The results show that the δ'18O value of the source water governs the starting point from which the triple oxygen isotope composition of leaf water, phytolith-forming water and phytoliths evolve. However, since the 17O-excess varies little in the growth chamber and natural source waters, this has no impact on the strong relative humidity-dependency of the 17O-excess of phytoliths, demonstrated for the 40–80 % relative humidity range. This relative humidity-dependency is not impacted by changes in air temperature or CO2 concentration either. A relative humidity proxy equation is proposed. Each per meg of change in phytolith 17O-excess reflects a change in atmospheric relative humidity of ca. 0.2 %. The ±15 per meg reproducibility on the measurement of phytolith 17O-excess corresponds to a ± 3.6 % precision on the reconstructed relative humidity. The low sensitivity of phytolith 17O-excess to climate parameters other than relative humidity makes it particularly suitable for quantitative reconstructions of continental relative humidity changes in the past.

Oxygen isotope composition of phloem sap in relation to leaf water in Ricinus communis

2003 ◽  
Vol 30 (10) ◽  
pp. 1059 ◽  
Author(s):  
Lucas A. Cernusak ◽  
S. Chin Wong ◽  
Graham D. Farquhar
Keyword(s):  
Oxygen Isotope ◽  
Dry Matter ◽  
Organic Molecules ◽  
Ricinus Communis ◽  
Isotope Composition ◽  
Leaf Water ◽  
Oxygen Isotope Composition ◽  
Source Water ◽  
Phloem Sap ◽  
Site Water

We measured the oxygen isotope composition of both the water and dry matter components of phloem sap exported from photosynthesising Ricinus communis L. leaves. The 18O / 16O composition of exported dry matter matched almost exactly that expected for equilibrium with average lamina leaf water (leaf water exclusive of water associated with primary veins) with an isotope effect of αo=1.027, where αo=Ro / Rw , and Ro and Rw are 18O / 16O of organic molecules and water, respectively. Average lamina leaf water was enriched by 14–22‰ compared with source water under our experimental conditions, and depleted by 4–7‰, compared with evaporative site water. This showed that it is the average lamina leaf water 18O / 16O signal that is exported from photosynthesising leaves rather than a signal more closely related to that of evaporative site water or source water. Additionally, we found that water exported in phloem sap from photosynthesising leaves was enriched compared with source water; the mean phloem water enrichment observed for leaf petioles was 4.0 ± 1.5‰ (mean ± 1 s.d., n = 27). Phloem water collected from stem bases was also enriched compared with source water. However, the enrichment was approximately 0.8 times that observed for leaf petioles, suggesting some mixing between enriched phloem water and unenriched xylem water occurred during translocation. Results validated the assumption that organic molecules exported from photosynthesising leaves are enriched by 27‰ compared with average lamina leaf water. Furthermore, results suggest that the potential influence of enriched phloem water should be considered when interpreting the 18O / 16O signatures of plant organic material and plant cellulose.

scholarly journals The triple oxygen isotope composition of phytoliths, a new proxy of atmospheric relative humidity: controls of soil water isotope composition, temperature, CO<sub>2</sub> concentration and relative humidity

2021 ◽  
Vol 17 (5) ◽  
pp. 1881-1902
Author(s):  
Clément Outrequin ◽  
Anne Alexandre ◽  
Christine Vallet-Coulomb ◽  
Clément Piel ◽  
Sébastien Devidal ◽  
...  
Keyword(s):  
Relative Humidity ◽  
Oxygen Isotope ◽  
Soil Water ◽  
Isotope Composition ◽  
Co2 Concentration ◽  
Oxygen Isotope Composition ◽  
Growth Chamber ◽  
Starting Point ◽  
Atmospheric Relative Humidity ◽  
Water Isotope

Abstract. Continental atmospheric relative humidity is a major climate parameter whose variability is poorly understood by global climate models. Models' improvement relies on model–data comparisons for past periods. However, there are no truly quantitative indicators of relative humidity for the pre-instrumental period. Previous studies highlighted a quantitative relationship between the triple oxygen isotope composition of phytoliths, particularly the 17O excess of phytoliths, and atmospheric relative humidity. Here, as part of a series of calibrations, we examine the respective controls of soil water isotope composition, temperature, CO2 concentration and relative humidity on phytolith 17O excess. For that purpose, the grass species Festuca arundinacea was grown in growth chambers where these parameters were varying. The setup was designed to control the evolution of the triple oxygen isotope composition of phytoliths and all the water compartments of the soil–plant–atmosphere continuum. Different analytical techniques (cavity ring-down spectroscopy and isotope ratio mass spectrometry) were used to analyze water and silica. An inter-laboratory comparison allowed to strengthen the isotope data matching. Water and phytolith isotope compositions were compared to previous datasets obtained from growth chamber and natural tropical sites. The results show that the δ′18O value of the source water governs the starting point from which the triple oxygen isotope composition of leaf water, phytolith-forming water and phytoliths evolves. However, since the 17O excess varies little in the growth chamber and natural source waters, this has no impact on the strong relative humidity dependency of the 17O excess of phytoliths, demonstrated for the 40 %–80% relative humidity range. This relative humidity dependency is not impacted by changes in air temperature or CO2 concentration either. A relative humidity proxy equation is proposed. Each per meg of change in phytolith 17O excess reflects a change in atmospheric relative humidity of ca. 0.2 %. The ±15 per meg reproducibility on the measurement of phytolith 17O excess corresponds to a ±3.6 % precision on the reconstructed relative humidity. The low sensitivity of phytolith 17O excess to climate parameters other than relative humidity makes it particularly suitable for quantitative reconstructions of continental relative humidity changes in the past.

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