Non-climatic variations in the oxygen isotopic compositions of plants

The ¹⁸O content of leaf water strongly influences the ¹⁸O contents of atmospheric CO₂ and O₂. The ¹⁸O signatures of these atmospheric gases, in turn, emerge as important indicators of large-scale gas exchange processes. Better understanding of the factors that influence the isotopic composition of leaf water is still required, however, for the quantitative utilization of these tracers. The ¹⁸O enrichment of leaf water relative to local meteoric water, is known to reflect climatic conditions. Less is known about the extent variations in the ¹⁸O content of leaf water are influenced by nonclimatic, species-specific characteristics. In a collection of 90 plant species from all continents grown under the same climatic conditions in the Jerusalem Botanical Garden we observed variations of about 9‰ in the δ¹⁸O values of stem water, δ_s, and of about 14‰ in the mid-day δ¹⁸O enrichment of bulk leaf water, δ_LW–δ_s. Differences between δ¹⁸O values predicted by a conventional evaporation model, δ_M, and δ_LW ranged between – 3.3‰ and + 11.8‰. The δ¹⁸O values of water in the chloroplasts (δ_ch) in leaves of 10 selected plants were estimated from on-line CO₂ discrimination measurements. Although much uncertainty is still involved in these estimates, the results indicated that δ_ch can significantly deviate from δ_M in species with high leaf peclet number. The δ¹⁸O values of bulk leaf water significantly correlated with δ¹⁸O values of leaf cellulose (directly) and with instantaneous water use efficiency (A/E, inversely). Differences in isotopic characteristics among conventionally defined vegetation types were not significant, except for conifers that significantly differed from shrubs in δ¹⁸O and δ¹³C values of cellulose and in their peclet numbers, and from deciduous woodland species in their δ¹⁸O and δ¹³C values of cellulose. The results indicated that predictions of the δ¹⁸O values of leaf water (δ_LW, δ_M and δ_ch) could be improved by considering plant species-specific characteristics.     

Nitrogen fertilization and δ18O of CO2 have no effect on 18O‐enrichment of leaf water and cellulose in Cleistogenes squarrosa (C4) – is VPD the sole control?

The oxygen isotope composition of cellulose (δ¹⁸O_Cel) archives hydrological and physiological information. Here, we assess previously unexplored direct and interactive effects of the δ¹⁸O of CO₂ (δ¹⁸O_CO2), nitrogen (N) fertilizer supply and vapour pressure deficit (VPD) on δ¹⁸O_Cel, ¹⁸O‐enrichment of leaf water (Δ¹⁸O_LW) and cellulose (Δ¹⁸O_Cel) relative to source water, and p_exp_x, the proportion of oxygen in cellulose that exchanged with unenriched water at the site of cellulose synthesis, in a C₄ grass (Cleistogenes squarrosa). δ¹⁸O_CO2 and N supply, and their interactions with VPD, had no effect on δ¹⁸O_Cel, Δ¹⁸O_LW, Δ¹⁸O_Cel and p_exp_x. Δ¹⁸O_Cel and Δ¹⁸O_LW increased with VPD, while p_exp_x decreased. That VPD‐effect on p_exp_x was supported by sensitivity tests to variation of Δ¹⁸O_LW and the equilibrium fractionation factor between carbonyl oxygen and water. N supply altered growth and morphological features, but not ¹⁸O relations; conversely, VPD had no effect on growth or morphology, but controlled ¹⁸O relations. The work implies that reconstructions of VPD from Δ¹⁸O_Cel would overestimate amplitudes of VPD variation, at least in this species, if the VPD‐effect on p_exp_x is ignored. Progress in understanding the relationship between Δ¹⁸O_LW and Δ¹⁸O_Cel will require separate investigations of p_ex and p_x and of their responses to environmental conditions.     

The 18O-signal transfer from water vapour to leaf water and assimilates varies among plant species and growth forms

The ¹⁸O signature of atmospheric water vapour (δ¹⁸O_V) is known to be transferred via leaf water to assimilates. It remains, however, unclear how the ¹⁸O-signal transfer differs among plant species and growth forms. We performed a 9-hr greenhouse fog experiment (relative humidity ≥ 98%) with ¹⁸O-depleted water vapour (−106.7‰) on 140 plant species of eight different growth forms during daytime. We quantified the ¹⁸O-signal transfer by calculating the mean residence time of O in leaf water (MRT_LW) and sugars (MRT_Sugars) and related it to leaf traits and physiological drivers. MRT_LW increased with leaf succulence and thickness, varying between 1.4 and 10.8 hr. MRT_Sugars was shorter in C₃ and C₄ plants than in crassulacean acid metabolism (CAM) plants and highly variable among species and growth forms; MRT_Sugars was shortest for grasses and aquatic plants, intermediate for broadleaf trees, shrubs, and herbs, and longest for conifers, epiphytes, and succulents. Sucrose was more sensitive to δ¹⁸O_V variations than other assimilates. Our comprehensive study shows that plant species and growth forms vary strongly in their sensitivity to δ¹⁸O_V variations, which is important for the interpretation of δ¹⁸O values in plant organic material and compounds and thus for the reconstruction of climatic conditions and plant functional responses.     

The role of effective leaf mixing length in the relationship between the δ18O of stem cellulose and source water across a salinity gradient

Previous mangrove tree ring studies attempted, unsuccessfully, to relate the δ¹⁸O of trunk cellulose (δ¹⁸O_CELL) to the δ¹⁸O of source water (δ¹⁸O_SW). Here, we tested whether biochemical fractionation associated with one of the oxygen in the cellulose glucose moiety or variation in leaf water oxygen isotope fractionation (Δ_LW) can interfere with the δ¹⁸O_SW signal as it is recorded in the δ¹⁸O_CELL of mangrove (saltwater) and hammock (freshwater) plants. We selected two transects experiencing a salinity gradient, located in the Florida Keys, USA. The δ¹⁸O_CELL throughout both transects did not show the pattern expected based on that of the δ¹⁸O_SW. We found that in one of the transects, biochemical fractionation interfered with the δ¹⁸O_SW signal, while in the other transect Δ_LW differed between mangrove and hammock plants. Observed differences in Δ_LW between mangroves and hammocks were caused by a longer effective leaf mixing length (L) of the water pathway in mangrove leaves compared to those of hammock leaves. Changes in L could have caused the δ¹⁸O_CELL to record not only variations in the δ¹⁸O_SW but also in Δ_LW making it impossible to isolate the δ¹⁸O_SW signal.     

Isotopic heterogeneity of water in transpiring leaves: identification of the component that controls the δ18O of atmospheric O2 and CO2

Two direct but independent approaches were developed to identify the average δ¹⁸O value of the water fraction in the chloroplasts of transpiring leaves. In the first approach, we used the δ¹⁸O value of CO₂ in isotopic equilibrium with leaf water to reconstruct the δ¹⁸O value of water in the chloroplasts. This method was based on the idea that the enzyme carbonic anhydrase facilitates isotopic equilibrium between CO₂ and H₂O predominantly in the chloroplasts, at a rate that is several orders of magnitude faster than the non-catalysed exchange in other leaf water fractions. In the second approach, we measured the δ¹⁸O value of O₂ from photosynthetic water oxidation in the chloroplasts of intact leaves. Since O₂ is produced from chloroplast water irreversibly and without discrimination, the δ¹⁸O value of the O₂ should be identical to that of chloroplast water. In intact, transpiring leaves of sunflower (Helianthus annuus cv. giant mammoth) under the experimental conditions used, the average δ¹⁸O value of chloroplasts water was displaced by 3—10 % (depending on relative humidity and atmospheric composition) below the value predicted by the conventional Craig & Gordon model. Furthermore, this δ¹⁸O value was always lower than the δ¹⁸O value that was measured for bulk leaf water. Our results have implications for a variety of environmental studies since it is the δ¹⁸O value of water in the chloroplasts that is the relevant quantity in considering terrestrial plants influence on the δ¹⁸O values of atmospheric CO₂ and O₂, as well as in influencing the δ¹⁸O of plant organic matter.     

Reconstructing the δ18O of atmospheric water vapour via the CAM epiphyte Tillandsia usneoides: seasonal controls on δ18O in the field and large‐scale reconstruction of δ18Oa

Using both oxygen isotope ratios of leaf water (δ¹⁸O_L) and cellulose (δ¹⁸O_C) of Tillandsia usneoides in situ, this paper examined how short‐ and long‐term responses to environmental variation and model parameterization affected the reconstruction of the atmospheric water vapour (δ¹⁸O_a). During sample‐intensive field campaigns, predictions of δ¹⁸O_L matched observations well using a non‐steady‐state model, but the model required data‐rich parameterization. Predictions from the more easily parameterized maximum enrichment model (δ¹⁸O_L–M) matched observed δ¹⁸O_L and observed δ¹⁸O_a when leaf water turnover was less than 3.5 d. Using the δ¹⁸O_L–M model and weekly samples of δ¹⁸O_L across two growing seasons in Florida, USA, reconstructed δ¹⁸O_a was ?12.6 ± 0.3‰. This is compared with δ¹⁸O_a of ?12.4 ± 0.2‰ resolved from the growing‐season‐weighted δ¹⁸O_C. Both of these values were similar to δ¹⁸O_a in equilibrium with precipitation, ?12.9‰. δ¹⁸O_a was also reconstructed through a large‐scale transect with δ¹⁸O_L and the growing‐season‐integrated δ¹⁸O_C across the southeastern United States. There was considerable large‐scale variation, but there was regional, weather‐induced coherence in δ¹⁸O_a when using δ¹⁸O_L. The reconstruction of δ¹⁸O_a with δ¹⁸O_C generally supported the assumption of δ¹⁸O_a being in equilibrium with precipitation δ¹⁸O (δ¹⁸O_ppt), but the pool of δ¹⁸O_ppt with which δ¹⁸O_a was in equilibrium – growing season versus annual δ¹⁸O_ppt – changed with latitude.     

Reconstruction of source water using the δ18O of tree ring phenylglucosazone: A potential tool in paleoclimate studies

The oxygen isotope ratios of tree ring cellulose have a great potential as proxy for the oxygen isotope ratios of source water, which is related to climate. However, source water isotopic signatures can be masked by plant physiological and biochemical processes during cellulose synthesis. To minimize biochemical effects in the recording of source water, we modified the cellulose molecule to phenylglucosazone, which only has oxygen attached to carbon 3–6 (O_C3–6) of the cellulose glucose moieties, thus eliminating the oxygen attached to carbon 2 of the cellulose glucose moieties (O_C-2). Here we developed a method to use small amounts of inter and intra-annual tree ring cellulose for phenylglucosazone synthesis. Using this new method we tested if the oxygen isotope ratios of source water reconstructed from tree ring phenylglucosazone (δ¹⁸O_sw^PG) and the observed source water (δ¹⁸O_sw^obs) would have a better agreement than those reconstructed from the tree ring cellulose molecule. Annual tree ring samples were obtained from Pinus sylvestris (1997–2003) (Finland) and Picea abies (1971–1992) (Switzerland) and intra-annual tree ring samples were obtained from Pinus radiata (October 2004–March 2006) (New Zealand), each near a meteorological station where precipitation and relative humidity (RH) were measured periodically. The δ¹⁸O of tree ring cellulose and tree ring phenylglucosazone for each of the three species were then used to back calculate the δ¹⁸O of source water according to a previous published empirical equation. As expected, the δ¹⁸O of tree ring phenylglucosazone was superior than cellulose in the reconstruction of source water available to the plant. Deviation between δ¹⁸O_sw^PG and δ¹⁸O_sw^obs was in part correlated with variation in atmospheric relative humidity (RH) which was not observed for the cellulose molecule. We conclude that this new method can be applicable to inter and intra-annual tree ring studies and that the use of the tree ring phenylglucosazone will significantly improve the quality of paleoclimate studies.     

Identifying drivers of leaf water and cellulose stable isotope enrichment in <Emphasis Type="Italic">Eucalyptus</Emphasis> in northern Australia

Several previous studies have investigated the use of the stable hydrogen and oxygen isotope compositions in plant materials as indicators of palaeoclimate. However, accurate interpretation relies on a detailed understanding of both physiological and environmental drivers of the variations in isotopic enrichments that occur in leaf water and associated organic compounds. To progress this aim we measured δ¹⁸O and δ²H values in eucalypt leaf and stem water and δ¹⁸O values in leaf cellulose, along with the isotopic compositions of water vapour, across a north-eastern Australian aridity gradient. Here we compare observed leaf water enrichment, along with previously published enrichment data from a similar north Australian transect, to Craig–Gordon-modelled predictions of leaf water isotopic enrichment. Our investigation of model parameters shows that observed ¹⁸O enrichment across the aridity gradients is dominated by the relationship between atmospheric and internal leaf water vapour pressure while ²H enrichment is driven mainly by variation in the water vapour—source water isotopic disequilibrium. During exceptionally dry and hot conditions (RH < 21%, T > 37 °C) we observed strong deviations from Craig–Gordon predicted isotope enrichments caused by partial stomatal closure. The atmospheric–leaf vapour pressure relationship is also a strong predictor of the observed leaf cellulose δ¹⁸O values across one aridity gradient. Our finding supports a wider applicability of leaf cellulose δ¹⁸O composition as a climate proxy for atmospheric humidity conditions during the leaf growing season than previously documented.     

Interpreting species‐specific variation in tree‐ring oxygen isotope ratios among three temperate forest trees

Although considerable variation has been documented in tree‐ring cellulose oxygen isotope ratios (δ¹⁸O_cell) among co‐occurring species, the underlying causes are unknown. Here, we used a combination of field measurements and modelling to investigate the mechanisms behind variations in late‐wood δ¹⁸O_cell (δ¹⁸O_lc) among three co‐occurring species (chestnut oak, black oak and pitch pine) in a temperate forest. For two growing seasons, we quantified among‐species variation in δ¹⁸O_lc, as well as several variables that could potentially cause the δ¹⁸O_lc variation. Data analysis based on the δ¹⁸O_cell model rules out leaf water enrichment (Δ¹⁸O_lw) and tree‐ring formation period (Δt), but highlights source water δ¹⁸O (δ¹⁸O_sw) as an important driver for the measured difference in δ¹⁸O_lc between black and chestnut oak. However, the enriched δ¹⁸O_lc in pitch pine relative to the oaks could not be sufficiently explained by consideration of the above three variables only, but rather, we show that differences in the proportion of oxygen exchange during cellulose synthesis (p_ex) is most likely a key mechanism. Our demonstration of the relevance of some species‐specific features (or lack thereof) to δ¹⁸O_cell has important implications for isotope based ecophysiological/paleoclimate studies.     

Comparison of measured and modeled variations in piñon pine leaf water isotopic enrichment across a summer moisture gradient

Stable hydrogen and oxygen isotopic composition of bulk leaf water (δD_lw and δ¹⁸O_lw) in piñon pine (Pinus edulis and P. monophylla) and gas exchange parameters were measured under field conditions to examine the effects of seasonal moisture stress on leaf water isotopic enrichment. Study sites were located near the lower elevation limit for piñon in the southwestern USA. Leaf-level transpiration measurements were made four times daily in spring, summer and early autumn; simultaneously, leaf samples were collected for water extraction and stable isotope analysis. Diurnal variations in δD_lw and δ¹⁸O_lw values were small, especially when leaf water residence times (molar leaf water content divided by transpiration rate) were high. Stomatal conductance explained most of the variance (60%) in leaf water enrichment across the dataset. Observed leaf water enrichment was compared with predictions of steady-state and nonsteady-state models. Nonsteady-state predictions fit observations the best, although D enrichment was often lower than predicted by any model. Hydrogen isotope ratios of leaf water and cellulose nitrate were strongly correlated, demonstrating preservation of a leaf water signal in wood and leaf cellulose.     

Contributions of evaporation, isotopic non-steady state transpiration and atmospheric mixing on the delta18O of water vapour in Pacific Northwest coniferous forests

Changes in the ²H and ¹⁸O of atmospheric water vapour provide information for integrating aspects of gas exchange within forest canopies. In this study, we show that diurnal fluctuations in the oxygen isotope ratio (δ¹⁸O) as high as 4‰ were observed for water vapour (δ¹⁸O_vp) above and within an old‐growth coniferous forest in the Pacific Northwest region of the United States. Values of δ¹⁸O_vp decreased in the morning, reached a minimum at midday, and recovered to early‐morning values in the late afternoon, creating a nearly symmetrical diurnal pattern for two consecutive summer days. A mass balance budget was derived and assessed for the ¹⁸O of canopy water vapour over a 2‐d period by considering the ¹⁸O‐isoflux of canopy transpiration, soil evaporation and the air entering the canopy column. The budget was used to address two questions: (1) do δ¹⁸O values of canopy water vapour reflect the biospheric influence, or are such signals swamped by atmospheric mixing? and (2) what mechanisms drive temporal variations of δ¹⁸O_vp? Model calculations show that the entry of air into the canopy column resulted in an isotopically depleted ¹⁸O‐isoflux in the morning of day 1, causing values of δ¹⁸O_vp to decrease. An isotopically enriched ¹⁸O‐isoflux resulting from transpiration then offset this decreased δ¹⁸O_vp later during the day. Contributions of ¹⁸O‐isoflux from soil evaporation were relatively small on day 1 but were more significant on day 2, despite the small H₂¹⁶O fluxes. From measurements of leaf water volume and sapflux, we determined the turnover time of leaf water in the needles of Douglas‐fir trees as ≈ 11 h at midday. Such an extended turnover time suggests that transpiration may not have occurred at the commonly assumed isotopic steady state. We tested a non‐steady state model for predicting δ¹⁸O of leaf water. Our model calculations show that assuming isotopic steady state increased isoflux of transpiration. The impact of this increase on the modelled δ ¹⁸O_vp was clearly detectable, suggesting the importance of considering isotopic non‐steady state of transpiration in studies of forest ¹⁸O water balance.     

Correlating δ13C and δ18O in cellulose of trees

We measured the carbon and oxygen isotopic composition of stem cellulose of Pinus sylvestris, Picea abies, Fagus sylvatica and Fraxinus excelsior. Several sites along a transect of a small valley in Switzerland were selected which differ in soil moisture conditions. At every site, six trees per species were sampled, and a sample representing a mean value for the period from 1940 to 1990 was analysed. For all species, the mean site δ¹³C and δ¹⁸O of stem cellulose are related to the soil moisture availability, whereby higher isotope ratios are found at drier sites. This result is consistent with isotope fractionation models when assuming enhanced stomatal resistance (thus higher δ¹³C of incorporated carbon) and increased oxygen isotope enrichment in the leaf water (thus higher δ¹⁸O) at the dry sites. δ¹⁸ O-δ¹³C plots reveal a linear relationship between the carbon and oxygen isotopes in cellulose. To interpret this relationship we developed an equation which combines the above-mentioned fractionation models. An important new parameter is the degree to which the leaf water enrichment is reflected in the stem cellulose. In the combined model the slope of the δ¹⁸O-δ¹³C plot is related to the sensitivity of the p_i/p_a of a plant to changing relative humidity.     

Tree age,site and climate controls on tree ring cellulose δ18O: A case study on oak trees from south-western France

A main concern of dendroclimatic reconstruction is to distinguish in the tree ring proxy the influence of the climate variables of interest from other controlling factors. In order to investigate age, site and climate controls on tree ring width and cellulose δ¹⁸O, measurements have been performed in nearby groups of young (145 years old) and older (310–405 years old) oak trees in south-western France, covering the period 1860–2010.Within a given site, inter-tree deviations are small, pointing to a common climatic signal. Despite a similar inter-annual variability, the average level of cellulose δ¹⁸O in the young tree group is ∼0.8‰ higher than in the old trees. Such offsets might be caused by different soil properties and differences in the fraction of the source water used by trees from different depths. The δ¹⁸O of water in the top soil layer is directly related to the current growing season precipitation, while deeper water can have a lower and more constant δ¹⁸O. Local cave drip waters at 10 m depth indeed show a constant isotopic composition, which corresponds to pluri-annual mean precipitation.A 2‰ increasing trend is observed in cellulose δ¹⁸O of young trees in the first 30 years of growth, during a period when no trend is visible in older trees. This increase can be quantitatively explained by humidity gradients under the forest canopy, and a changing microclimate around the crown as trees grow higher.While relationships between tree ring width and climate appear complex, the isotopic composition of cellulose is strongly correlated with summer maximum temperature, relative humidity and evapotranspiration (r ≈ 0.70). Weaker correlations (r ≈ 0.40) are identified with precipitation δ¹⁸O from a 15-year long local record and from the REMOiso model output. These results imply that leaf water enrichment has a stronger control on the inter-annual variability of cellulose δ¹⁸O than the δ¹⁸O of precipitation.This study demonstrates the suitability of oak tree ring cellulose δ¹⁸O for reconstructing past summer climate variability in south-western France, provided that the sampling and pooling strategy accounts for the fact that trees from different sites and of different age can introduce non-climatic signals.     

Aerial decay influence on the stable oxygen and carbon isotope ratios in tree ring cellulose

Sub-fossil wood is often affected by the decaying process that introduces uncertainties in the measurement of oxygen and carbon stable isotope composition in cellulose. Although the cellulose stable isotopes are widely used as climatic proxies, our understanding of processes controlling their behavior is very limited. We present here a comparative study of stable oxygen and carbon isotope ratios in tree ring cellulose in decayed and non-decayed wood samples of Swiss stone pine (Pinus cembra) trees. The intra-ring stable isotope variability (around the circumference of a single ring) was between 0.1 and 0.5‰ for δ¹⁸O values and between 0.5 and 1.6‰ for δ¹³C values for both decayed and non-decayed wood. Observed intra-tree δ¹⁸O variability is less than that reported in the literature (0.5–1.5‰), however, for δ¹³C it is larger than the reported values (0.7–1.2‰). The inter-tree variability for non-decayed wood ranges between 1.1 and 2.3‰ for δ¹⁸O values, and between 2 and 4.7‰ for δ¹³C values. The inter-tree differences for δ¹⁸O values are similar to those reported in the literature (1–2‰ for oxygen and 1–3‰ for carbon) but are larger for δ¹³C values. We have found that the differences for δ¹⁸O and δ¹³C values between decayed and non-decayed wood are smaller than the variation among different trees from the same site, suggesting that the decayed wood can be used for isotopic paleoclimate research.     

Hydrogen isotope response to changing salinity and rainfall in Australian mangroves

Hydrogen isotope ratios (²H/¹H, δ²H) of leaf waxes covary with those in precipitation and are therefore a useful paleohydrologic proxy. Mangroves are an exception to this relationship because their δ²H values are also influenced by salinity. The mechanisms underlying this response were investigated by measuring leaf lipid δ²H and leaf and xylem water δ²H and δ¹⁸O values from three mangrove species over 9.5 months in a subtropical Australian estuary. Net ²H/¹H fractionation between surface water and leaf lipids decreased by 0.5–1.0‰ ppt^?1 for n‐alkanes and 0.4–0.8‰ ppt^?1 for isoprenoids. Xylem water was ²H depleted relative to surface water, reflecting ²H discrimination of 4–10‰ during water uptake at all salinities and opportunistic uptake of freshwater at high salinity. However, leaf water ²H enrichment relative to estuary water was insensitive to salinity and identical for all species. Therefore, variations in leaf and xylem water δ²H values cannot explain the salinity‐dependent ²H depletion in leaf lipids, nor the 30‰ range in leaf lipid δ²H values among species. Biochemical changes in direct response to salt stress, such as increased compatible solute production or preferential use of stored carbohydrates, and/or the timing of lipid production and subsequent turnover rates, are more likely causes.     

A high-temperature water vapor equilibration method to determine non-exchangeable hydrogen isotope ratios of sugar,starch and cellulose

The analysis of the non-exchangeable hydrogen isotope ratio (δ²H_ne) in carbohydrates is mostly limited to the structural component cellulose, while simple high-throughput methods for δ²H_ne values of non-structural carbohydrates (NSC) such as sugar and starch do not yet exist. Here, we tested if the hot vapor equilibration method originally developed for cellulose is applicable for NSC, verified by comparison with the traditional nitration method. We set up a detailed analytical protocol and applied the method to plant extracts of leaves from species with different photosynthetic pathways (i.e., C₃, C₄ and CAM). δ²H_ne of commercial sugars and starch from different classes and sources, ranging from ?157.8 to +6.4‰, were reproducibly analysed with precision between 0.2‰ and 7.7‰. Mean δ²H_ne values of sugar are lowest in C₃ (?92.0‰), intermediate in C₄ (?32.5‰) and highest in CAM plants (6.0‰), with NSC being ²H-depleted compared to cellulose and sugar being generally more ²H-enriched than starch. Our results suggest that our method can be used in future studies to disentangle ²H-fractionation processes, for improving mechanistic δ²H_ne models for leaf and tree-ring cellulose and for further development of δ²H_ne in plant carbohydrates as a potential proxy for climate, hydrology, plant metabolism and physiology.     

Dentine oxygen isotopes (δ18O) as a proxy for odontocete distributions and movements

Spatial variation in marine oxygen isotope ratios (δ¹⁸O) resulting from differential evaporation rates and precipitation inputs is potentially useful for characterizing marine mammal distributions and tracking movements across δ¹⁸O gradients. Dentine hydroxyapatite contains carbonate and phosphate that precipitate in oxygen isotopic equilibrium with body water, which in odontocetes closely tracks the isotopic composition of ambient water. To test whether dentine oxygen isotope composition reliably records that of ambient water and can therefore serve as a proxy for odontocete distribution and movement patterns, we measured δ¹⁸O values of dentine structural carbonate (δ¹⁸O_SC) and phosphate (δ¹⁸O_P) of seven odontocete species (n = 55 individuals) from regional marine water bodies spanning a surface water δ¹⁸O range of several per mil. Mean dentine δ¹⁸O_SC (range +21.2 to +25.5‰ VSMOW) and δ¹⁸O_P (+16.7 to +20.3‰) values were strongly correlated with marine surface water δ¹⁸O values, with lower dentine δ¹⁸O_SC and δ¹⁸O_P values in high‐latitude regions (Arctic and Eastern North Pacific) and higher values in the Gulf of California, Gulf of Mexico, and Mediterranean Sea. Correlations between dentine δ¹⁸O_SC and δ¹⁸O_P values with marine surface water δ¹⁸O values indicate that sequential δ¹⁸O measurements along dentine, which grows incrementally and archives intra‐ and interannual isotopic composition over the lifetime of the animal, would be useful for characterizing residency within and movements among water bodies with strong δ¹⁸O gradients, particularly between polar and lower latitudes, or between oceans and marginal basins.     

Effects of leaf water evaporative 2H‐enrichment and biosynthetic fractionation on leaf wax n‐alkane δ2H values in C3 and C4 grasses

Leaf wax n‐alkane δ²H values carry important information about environmental and ecophysiological processes in plants. However, the physiological and biochemical drivers that shape leaf wax n‐alkane δ²H values are not completely understood. It is particularly unclear why n‐alkanes in grasses are typically ²H‐depleted compared with plants from other taxonomic groups such as dicotyledonous plants and why C3 grasses are ²H‐depleted compared with C4 grasses. To resolve these uncertainties, we quantified the effects of leaf water evaporative ²H‐enrichment and biosynthetic hydrogen isotope fractionation on n‐alkane δ²H values for a range of C3 and C4 grasses grown in climate‐controlled chambers. We found that only a fraction of leaf water evaporative ²H‐enrichment is imprinted on the leaf wax n‐alkane δ²H values in grasses. This is interesting, as previous studies have shown in dicotyledonous plants a nearly complete transfer of this ²H‐enrichment to the n‐alkane δ²H values. We thus infer that the typically observed ²H‐depletion of n‐alkanes in grasses (as opposed to dicots) is because only a fraction of the leaf water evaporative ²H‐enrichment is imprinted on the δ²H values. Our experiments also show that differences in n‐alkane δ²H values between C3 and C4 grasses are largely the result of systematic differences in biosynthetic fractionation between these two plant groups, which was on average ?198‰ and?159‰ for C3 and C4 grasses, respectively.     

Variations in the natural abundance of oxygen-18 and deuterium in plant carbohydrates

Variations in the natural abundance of ¹⁸O and ²H in plant cellulose are influenced by the isotopic composition of the water directly involved in metabolism—the metabolic water fraction. The isotopic distinction between the metabolic source water and total tissue water must reflect the formation of isotopic gradients within the tissue that are influenced by the rate of water turnover, by properties of the water conducting system and by environmental conditions. It seems that the ¹⁸O abundance in the metabolic water is conserved in cellulose with a relatively constant isotope effect. The relationship of the ²H abundance between metabolic water and cellulose is more complex. Hydrogen incorporated into photosynthetic products during primary reduction steps is highly depleted in ²H. However, a large proportion of these hydrogens are subsequently replaced by exchange with water, leading to ²H enrichment during heterotrophic metabolism. Deciphering the oxygen isotope ratio of cellulose could help in providing insights into the carbon and oxygen fluxes exchanged between plants and the atmosphere. This is because the ¹⁸O abundance in cellulose records the ¹⁸O abundance in the metabolic water, which in turn, controls the oxygen isotopic signatures of the CO₂ and O₂ released by plants into the atmosphere. The hydrogen isotope effects associated with carbohydrate metabolism provide insights into the autotrophic state of a plant tissue. This is because the hydrogen isotope ratio of carbohydrates must reflect the net effects of the two opposing isotope effects associated with photosynthesis and heterotrophic metabolism.     

Stable and radiogenic isotope analyses on shark teeth from the Early to the Middle Permian (Sakmarian–Roadian) of the southwestern USA

δ¹⁸O_P values and ⁸⁷Sr/⁸⁶Sr ratios were determined on disarticulated xenacanthiform, hybodontid and ctenacanthid shark tooth material from several Early Permian (Sakmarian–Kungurian) continental bone beds of northern Texas and southern Oklahoma as well as from the marine Middle Permian (Roadian) of northern Arizona. The δ¹⁸O_P values derived from the teeth of bone beds are in the range of 17.6–23.5‰ VSMOW, and are mostly depleted in ¹⁸O by 0.5–5‰ relative to proposed coeval marine δ¹⁸O_P values. This indicates an adaptation to freshwater habitats on the Early Permian coastal plain by several sharks. Distinctly higher δ¹⁸O_P values from two bone beds are attributed to significant evaporative enrichment in ¹⁸O in flood plain ponds. ⁸⁷Sr/⁸⁶Sr ratios of around 0.71077 are notably more radiogenic than ⁸⁷Sr/⁸⁶Sr of contemporaneous seawater. In contrast, the isotopic composition of teeth from the marine Kaibab Formation is characterised by low δ¹⁸O_P values in the range of 13.4–15.6‰ VSMOW while ⁸⁷Sr/⁸⁶Sr ratios of around 0.70821 are closer to the Roadian seawater value. The distinctly depleted δ¹⁸O_P values cannot be readily explained by fluvially affected freshening in a nearshore marine environment, so a diagenetic alteration of the Kaibab material seems to be more likely, excluding it from further interpretation.