Oxygen and carbon isotope compositions of middle Cretaceous vertebrates from North Africa and Brazil: Ecological and environmental significance

In order to investigate mid-Cretaceous terrestrial climates of low paleolatitudes, Moroccan, Tunisian and Brazilian vertebrate apatites have been analyzed for their oxygen and carbon isotope compositions of phosphates (δ¹⁸O_p) and carbonates (δ¹⁸O_c, δ¹³C_c). At each site, coexisting theropod dinosaurs, titanosaurid sauropods, pterosaurs, crocodilians, turtles and fish have distinct δ¹⁸O_p and δ¹³C_c values reflecting their ecologies, diets and foraging environments. Oxygen isotope compositions of surface waters (δ¹⁸O_w) estimated from turtle and crocodile δ¹⁸O_p values range from − 5.0 ± 1.0‰ to − 2.4 ± 1.0‰, which do not differ from mean annual rainwater values occurring today under inter-tropical sub-arid to arid climates. High water temperatures ranging from 21 ± 6 °C to 34 ± 2 °C deduced from fish δ¹⁸O_p values are in agreement with those published for mid-Cretaceous low latitudes. Temporary or seasonal droughts are inferred from high δ¹⁸O_p values of lungfish teeth, even though lower reptile δ¹⁸O_p values suggest the use of distinct and most likely larger or regularly renewed bodies of water. Environmental conditions of the studied low latitude regions during the Aptian-Cenomanian interval were somewhat similar to those experienced today under semi-arid to arid tropical or equatorial climates, but with higher mean surface temperatures than present-day ones.     

Oxygen isotope fractionation between crocodilian phosphate and water

Oxygen isotope compositions of phosphate (δ¹⁸O_p) were measured in tooth enamel from captive and wild individuals of 8 crocodilian species. A rough linear correlation is observed between the δ¹⁸O_p of all the studied species and the oxygen isotope composition of ambient water (δ¹⁸O_w). Differences in mean air temperature, diet and physiology could contribute significantly to the large scatter of δ¹⁸O_p values. The combination of these parameters results in a fractionation equation for which the slope (0.82) is lower than that expected (≥ 1) from predictive model equations that assume temperature and diet as fixed parameters. Taking into account large uncertainties, the observed oxygen isotope fractionation between phosphate and ambient water does not statistically differ from that formerly established for aquatic turtles. Case studies show that δ¹⁸O_p values of fossil crocodile tooth enamel can be used to discriminate between marine and freshwater living environments within a precision of about ± 2‰ only.     

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.     

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.     

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.     

Variation in the carbon and oxygen isotope composition of plant biomass and its relationship to water‐use efficiency at the leaf‐ and ecosystem‐scales in a northern Great Plains grassland

Measurements of the carbon (δ¹³C_m) and oxygen (δ¹⁸O_m) isotope composition of C₃ plant tissue provide important insights into controls on water‐use efficiency. We investigated the causes of seasonal and inter‐annual variability in water‐use efficiency in a grassland near Lethbridge, Canada using stable isotope (leaf‐scale) and eddy covariance measurements (ecosystem‐scale). The positive relationship between δ¹³C_m and δ¹⁸O_m values for samples collected during 1998–2001 indicated that variation in stomatal conductance and water stress‐induced changes in the degree of stomatal limitation of net photosynthesis were the major controls on variation in δ¹³C_m and biomass production during this time. By comparison, the lack of a significant relationship between δ¹³C_m and δ¹⁸O_m values during 2002, 2003 and 2006 demonstrated that water stress was not a significant limitation on photosynthesis and biomass production in these years. Water‐use efficiency was higher in 2000 than 1999, consistent with expectations because of greater stomatal limitation of photosynthesis and lower leaf c_i/ca during the drier conditions of 2000. Calculated values of leaf‐scale water‐use efficiency were 2–3 times higher than ecosystem‐scale water‐use efficiency, a difference that was likely due to carbon lost in root respiration and water lost during soil evaporation that was not accounted for by the stable isotope measurements.     

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.     

Oxygen isotope analysis of human bone phosphate evidences weaning age in archaeological populations

Here we report bone phosphate oxygen (δ¹⁸O_p) values from perinates/neonates and infants (<3.5 years; n = 32); children (4–12 years; n = 12); unsexed juveniles (16–18 years; n = 2); and adult bones (n = 17) from Wharram Percy, North Yorkshire, England, in order to explore the potential of this method to investigate patterns of past breastfeeding and weaning. In prior studies, δ¹⁵N and δ¹³C analyses of bone collagen have been utilized to explore weaning age in this large and well‐studied assemblage, rendering this material highly appropriate for the testing and development of this alternative method targeting the inorganic phase of bone. Data produced reveal ¹⁸O‐enrichment in the youngest perinatal/neonatal and infant samples, and an association between age and bone δ¹⁸O_p (and previously‐published δ¹⁵N values), with high values in both these isotope systems likely due to breastfeeding. After the age of 2–3 years, δ¹⁸O_p values are lower, and all children between the ages of 4 and 12, along with the vast majority of sub‐adults and adults sampled (aged 16 to >50 years), have δ¹⁸O_p values consistent with the consumption of local modern drinking water. The implications of this study for the reconstruction of weaning practices in archaeological populations are discussed, including variations observed with bone δ¹⁵N_coll and δ¹⁸O_p co‐analysis and the influence of culturally‐modified drinking water and seasonality. The use of this method to explore human mobility and palaeoclimatic conditions are also discussed with reference to the data presented. Am J Phys Anthropol 157:226–241, 2015. © 2015 Wiley Periodicals, Inc.     

Oxygen isotope fractionations across individual leaf carbohydrates in grass and tree species

Almost no δ¹⁸O data are available for leaf carbohydrates, leaving a gap in the understanding of the δ¹⁸O relationship between leaf water and cellulose. We measured δ¹⁸O values of bulk leaf water (δ¹⁸O_LW) and individual leaf carbohydrates (e.g. fructose, glucose and sucrose) in grass and tree species and δ¹⁸O of leaf cellulose in grasses. The grasses were grown under two relative humidity (rH) conditions. Sucrose was generally ¹⁸O‐enriched compared with hexoses across all species with an apparent biosynthetic fractionation factor (ε_bio) of more than 27‰ relative to δ¹⁸O_LW, which might be explained by isotopic leaf water and sucrose synthesis gradients. δ¹⁸O_LW and δ¹⁸O values of carbohydrates and cellulose in grasses were strongly related, indicating that the leaf water signal in carbohydrates was transferred to cellulose (ε_bio = 25.1‰). Interestingly, damping factor p_exp_x, which reflects oxygen isotope exchange with less enriched water during cellulose synthesis, responded to rH conditions if modelled from δ¹⁸O_LW but not if modelled directly from δ¹⁸O of individual carbohydrates. We conclude that δ¹⁸O_LW is not always a good substitute for δ¹⁸O of synthesis water due to isotopic leaf water gradients. Thus, compound‐specific δ¹⁸O analyses of individual carbohydrates are helpful to better constrain (post‐)photosynthetic isotope fractionation processes in plants.     

The evolutionary puzzle of egg size,oxygenation and parental care in aquatic environments

Offspring fitness generally improves with increasing egg size. Yet, eggs of most aquatic organisms are small. A common but largely untested assumption is that larger embryos require more oxygen than they can acquire through diffusion via the egg surface, constraining egg size evolution. However, we found no detrimental effects of large egg size on embryo growth and survival under hypoxic conditions. We tested this in the broad-nosed pipefish, Syngnathus typhle, whose males provide extensive care (nourishment, osmoregulation and oxygenation) to their young in a brood pouch on their bodies. We took advantage of this species'' pronounced variation in egg size, correlating positively with female size, and tested the effect of hypoxia (40% dissolved oxygen) versus fully oxygenated (100%) water on embryo size and survival of large versus small eggs after 18 days of paternal brooding. Egg size did not affect embryo survival, regardless of O₂ treatment. While hypoxia affected embryo size negatively, both large and small eggs showed similar reductions in growth. Males in hypoxia ventilated more and males with large eggs swam more, but neither treatment affected their position in the water column. Overall, our results call into question the most common explanation for constrained egg size evolution in aquatic environments.     

Records of palaeo‐seawater condition from oxygen‐isotope profiles of early Pleistocene fossil molluscs from the Seoguipo Formation (Korea)

Kim, J.K., Khim, B.‐K., Woo, K.S., & Yoon, S.H. 2009: Records of palaeo‐seawater condition from oxygen‐isotope profiles of early Pleistocene fossil molluscs from the Seoguipo Formation (Korea). Lethaia, Vol. 43, pp. 170–181. High‐resolution δ¹⁸O profiles of early Pleistocene fossil molluscs (Mizuhopecten tokyoensis hokurikuensis) from the shallow‐marine sedimentary Seoguipo Formation (Korea) were found to exhibit distinct annual cycles identified by their unique seasonality (δ¹⁸O amplitude). A direct comparison of fossil δ¹⁸O profiles with that of living shells (Amusium japonicum japonicumi) indicated that the palaeoseawater conditions differed from present‐day seawater. Specifically, the positive δ¹⁸O shift in the isotope profile of the fossil specimens relative to that of the living mollusc shell reflected that palaeotemperature was lower than that today. However, a comparison of the coldest palaeotemperatures (determined from the heaviest δ¹⁸O values of fossil shells), with the present‐day winter temperatures indicates that temperature variation alone cannot account for the entire positive δ¹⁸O offset. These findings indicate that variation in the seawater δ¹⁸O_w values plays a dominant role in the biogenic carbonate precipitation of fossils. Thus, the fossil shells obtained from stratigraphic units suggest different palaeoenvironmental conditions, including lower temperatures and ¹⁸O‐enriched glacial seawater, when compared with the present‐day conditions. The Seoguipo Formation records at least five cycles of relative sea‐level fluctuations, with changes in fossil δ¹⁸O amplitudes separated by sequence boundaries likely to reflect variations of unique palaeoseawater condition, although the oxygen‐isotope profile of fossil molluscs appears to provide a snap‐shot of the palaeoclimatic signature. □Early Pleistocene, mollusc fossils, oxygen isotope, palaeoenvironment, seawater temperature.     

Carbonate facies‐specific stable isotope data record climate,hydrology, and microbial communities in Great Salt Lake,UT

Organic and inorganic stable isotopes of lacustrine carbonate sediments are commonly used in reconstructions of ancient terrestrial ecosystems and environments. Microbial activity and local hydrological inputs can alter porewater chemistry (e.g., pH, alkalinity) and isotopic composition (e.g., δ¹⁸O_water, δ¹³C_DIC), which in turn has the potential to impact the stable isotopic compositions recorded and preserved in lithified carbonate. The fingerprint these syngenetic processes have on lacustrine carbonate facies is yet unknown, however, and thus, reconstructions based on stable isotopes may misinterpret diagenetic records as broader climate signals. Here, we characterize geochemical and stable isotopic variability of carbonate minerals, organic matter, and water within one modern lake that has known microbial influences (e.g., microbial mats and microbialite carbonate) and combine these data with the context provided by 16S rRNA amplicon sequencing community profiles. Specifically, we measure oxygen, carbon, and clumped isotopic compositions of carbonate sediments (δ¹⁸O_carb, δ¹³C_carb, ?₄₇), as well as carbon isotopic compositions of bulk organic matter (δ¹³C_org) and dissolved inorganic carbon (DIC; δ¹³C_DIC) of lake and porewater in Great Salt Lake, Utah from five sites and three seasons. We find that facies equivalent to ooid grainstones provide time‐averaged records of lake chemistry that reflect minimal alteration by microbial activity, whereas microbialite, intraclasts, and carbonate mud show greater alteration by local microbial influence and hydrology. Further, we find at least one occurrence of ?₄₇ isotopic disequilibrium likely driven by local microbial metabolism during authigenic carbonate precipitation. The remainder of the carbonate materials (primarily ooids, grain coatings, mud, and intraclasts) yield clumped isotope temperatures (T(?₄₇)), δ¹⁸O_carb, and calculated δ¹⁸O_water in isotopic equilibrium with ambient water and temperature at the time and site of carbonate precipitation. Our findings suggest that it is possible and necessary to leverage diverse carbonate facies across one sedimentary horizon to reconstruct regional hydroclimate and evaporation–precipitation balance, as well as identify microbially mediated carbonate formation.     

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.     

Responses of the carbon and oxygen isotope compositions of desert plants to spatial variation in soil salinity in Central Asia

We examined the isotopic parameters in two C₃ species (Artemisia diffusa H. Krasch and Tamarix hispida Willd.) and a C₄ species [Haloxylon aphyllum (Minkw.) Iljin.] growing or planted in soils with different levels of salinity in a Central Asian desert. The oxygen isotope ratios of stem water (δ¹⁸O_stem) in T. hispida and H. aphyllum distributed in high-salinity zones were similar to the δ¹⁸O of artesian water (δ¹⁸O_artesian) and different from that in A. diffusa distributed in lower-salinity zones. This indicates that T. hispida and H. aphyllum depend on water with low salinity in the deeper soil layer, whereas A. diffusa depends on water in the shallower soil layer that would be affected by salt accumulation. The carbon isotope composition of leaf organic matter (δ¹³C_om) and oxygen isotope enrichment in leaf organic matter above stem water (Δ¹⁸O_om) were lower in A. diffusa than in the other species. The responses of δ¹³C_om and Δ¹⁸O_om to soil salinity observed for T. hispida suggest that the species decreased its transpiration rate and increased its intrinsic water-use efficiency in response to increasing soil salinity. The δ¹³C_om and Δ¹⁸O_om of H. aphyllum were higher than those of the C₃ species, and were not correlated with soil salinity, suggesting that H. aphyllum reduced its salt uptake by decreasing transpiration—even though it was able to access less saline water in the deeper soil layer. These results indicate that the water-use strategy of desert plants in high-salinity environments can be assessed based on their carbon and oxygen isotope ratios.     

Transpiration rate relates to within‐ and across‐species variations in effective path length in a leaf water model of oxygen isotope enrichment

Stable oxygen isotope ratio of leaf water (δ¹⁸O_L) yields valuable information on many aspects of plant–environment interactions. However, current understanding of the mechanistic controls on δ¹⁸O_L does not provide complete characterization of effective path length (L) of the Péclet effect, – a key component of the leaf water model. In this study, we collected diurnal and seasonal series of leaf water enrichment and estimated L in six field‐grown angiosperm and gymnosperm tree species. Our results suggest a pivotal role of leaf transpiration rate (E) in driving both within‐ and across‐species variations in L. Our observation of the common presence of an inverse scaling of L with E in the different species therefore cautions against (1) the conventional treatment of L as a species‐specific constant in leaf water or cellulose isotope (δ¹⁸O_p) modelling; and (2) the use of δ¹⁸O_p as a proxy for g_s or E under low E conditions. Further, we show that incorporation of a multi‐species L‐E scaling into the leaf water model has the potential to both improve the prediction accuracy and simplify parameterization of the model when compared with the conventional approach. This has important implications for future modelling of oxygen isotope ratios.     

The oxygen isotopic signature of soil‐ and plant‐derived sulphate is controlled by fertilizer type and water source

The oxygen isotope signature of sulphate (δ¹⁸O_sulphate) is increasingly used to study nutritional fluxes and sulphur transformation processes in a variety of natural environments. However, mechanisms controlling the δ¹⁸O_sulphate signature in soil–plant systems are largely unknown. The objective of this study was to determine key factors, which affect δ¹⁸O_sulphate values in soil and plants. The impact of an ¹⁸O‐water isotopic gradient and different types of fertilizers was investigated in a soil incubation study and a radish (Raphanus sativus L.) greenhouse growth experiment. Water provided 31–64% of oxygen atoms in soil sulphate formed via mineralization of organic residues (green and chicken manures) while 49% of oxygen atoms were derived from water during oxidation of elemental sulphur. In contrast, δ¹⁸O_sulphate values of synthetic fertilizer were not affected by soil water. Correlations between soil and plant δ¹⁸O_sulphate values were controlled by water δ¹⁸O values and fertilizer treatments. Additionally, plant δ³⁴S data showed that the sulphate isotopic composition of plants is a function of S assimilation. This study documents the potential of using compound‐specific isotope ratio analysis for investigating and tracing fertilization strategies in agricultural and environmental studies.     

Oxygen isotopic composition of sulfate in deep sea pore fluid: evidence for rapid sulfur cycling

We present new data of oxygen isotopes in marine sulfate (δ¹⁸O_SO4) in pore fluid profiles through organic‐rich deep‐sea sediments from 11 ODP sites around the world. In almost all sites studied sulfate is depleted with depth, through both organic matter oxidation and anaerobic methane oxidation. The δ¹⁸O_SO4 increases rapidly near the top of the sediments, from seawater values of 9 to maxima between 22 and 25, and remains isotopically heavy and constant at these values with depth. The δ¹⁸O_SO4 in these pore fluid profiles is decoupled from variations in sulfur isotopes measured on the same sulfate samples (δ³⁴S_SO4); the δ³⁴S_SO4 increases continuously with depth and exhibits a shallower isotopic increase. This isotopic decoupling between the δ³⁴S_SO4 and the δ¹⁸O_SO4 is hard to reconcile with the traditional understanding of bacterial sulfate reduction in sediments. Our data support the idea that sulfate or sulfite and water isotopically exchange during sulfate reduction and that some of the isotopically altered sulfur pool returns to the environment. We calculate that the rapid increase in the δ¹⁸O_SO4 in the upper part of these sediments requires rates of this oxygen isotope exchange that are several orders of magnitude higher than the rates of net sulfate reduction calculated from the sulfate concentration profiles and supported by the δ³⁴S_SO4. We suggest several mechanisms by which this may occur, including ‘net‐zero’ sulfur cycling, as well as further experiments through which we can test and resolve these processes.     

Seasonal variation in δ13C and δ18O of cellulose from growth rings of Pinus radiata

Seasonal variation in δ¹³C and δ¹⁸O of cellulose (δ¹³C_c and δ¹⁸O_c) was measured within two annual rings of Pinus radiata growing at three sites in New Zealand. In general, both δ¹³C_c and δ¹⁸O_c increased to a peak over summer. The three sites differed markedly in annual water balance, and these differences were reflected in δ¹³C_c and δ¹⁸O_c. Average δ¹³C_c and δ¹⁸O_c from each site were positively related, so that the driest site had the most enriched cellulose. δ¹³C_c and δ¹⁸O_c were also related within each site, although both the slope and the closeness of fit of the relationship varied between sites. Supporting the theory, the site with the lowest average relative humidity also had the greatest change in δ¹⁸O_c‰ change in δ¹³C_c. Specific climatic events, such as drought or high rainfall, were recorded as a peak or a trough in enrichment, respectively. These results suggest that seasonal and between‐site variation in δ¹³C_c and δ¹⁸O_c are driven by the interaction between variation in climatic conditions and soil water availability, and plant response to this variation.     

Investigating the potential for Southern Hemisphere climate reconstruction using stable isotopes in Tasmanian tree rings

Few annually dated stable isotope records exist across Oceania. Stable carbon and oxygen isotope ratios have the potential to enhance climate reconstructions currently reliant on tree ring width chronologies. The purpose of this study is to explore the sources of variability in a stable oxygen isotope chronology derived from A. selaginoides from Mount Read, Tasmania. This high elevation site receives abundant rainfall throughout the year and is ∼130 km from the Global Network of Isotopes in Precipitation (GNIP) site at Cape Grim. We crossdated 10 new tree core samples against an existing ring width chronology (954–2011 CE) and analyzed the δ¹⁸O from the individual rings for the period 1960–2018. Using high resolution (0.25 degrees) climate data and ECMWF ERA5 reanalysis data, we disentangled the effects of local climate and source region on the isotopic signatures recorded in the annual rings. In addition, we used HYSPLIT backward trajectory analysis to characterize the source region of precipitation to Mount Read and whether the source region has influence over the δ¹⁸O_TR series. Median δ¹⁸O_TR (n = 10) is correlated with local temperature and vapor pressure deficit in the early growing season. In addition, spatial correlations reveal that median δ¹⁸O_TR is positively correlated with temperature and negatively correlated with precipitation in the source region. However, measurements of δ¹⁸O_TR exhibit high inter-tree variation, particularly between 1960 and 1990. Our results indicate that this δ¹⁸O_TR proxy may provide additional information about past moisture conditions during the growing season, potentially contributing to more robust reconstructions of the Southern Hemisphere climate dynamics; however, additional sampling may be necessary to resolve inter-tree variation in δ¹⁸O_TR.     

Turnover time of the non‐structural carbohydrate pool influences δ18O of leaf cellulose

Certainty regarding the degree to which organic molecules exchange oxygen with local water during plant cellulose synthesis (p_ex) is necessary for cellulose oxygen isotope (δ¹⁸O_cell)‐based applications in environmental and ecological studies. However, the currently accepted notion that p_ex is a constant of ca. 0.42 appears inconsistent with biochemical theory, which predicts that marked variation may be present in p_ex, in relation to variation in the turnover time (τ) of the carbohydrate pool available for cellulose synthesis. The above prediction was tested in the present study with the analysis of data collected from leaves of Ricinus communis grown in controlled environmental conditions that varied in light intensity and vapour pressure deficit. The results revealed the existence of considerable variation in both p_ex and τ across plants in the various growth environments. Moreover, despite uncertainties in estimates of the proportion of source water in the synthesis water (p_x) and of the biochemical fractionation factor (ε_o), our experiment yielded strong evidence that p_ex exhibits a significant, positive relationship with τ, consistent with biochemical theory. The observed variation in p_ex in association with τ has important implications for the interpretation of δ¹⁸O_cell data in environmental/ecological studies.