What Does the Triple Isotopic Composition of Oxygen in Precipitation, Groundwater, Soil Water, Plant Water, and Phytoliths Reveal About Current and Past Hydrological Cycles? Anne Alexandre, Clement Outrequin, Christine Vallet‐Coulomb, Christophe Peugeot, Manuela Grippa, et al. Journal of Geophysical Research Biogeosciences, 2025 Quantitative data are needed to constrain the feedback loops between vegetation and hydroclimate. In this study, the amplitudes of variations in the triple oxygen isotope composition of water at the soil‐plant‐atmosphere interface are measured in savanna and dry forest contexts in West Africa (Benin and Senegal). Comparison of in situ data and model estimates reveals the following: (a) The value of 17O‐excess for reconstructing climate archives is confirmed, given its small variability in precipitation (a few per meg) compared to the very large magnitude of change in the 17O‐excess of phytoliths (hundreds of per meg) in response to RH changes. (b) At the beginning of the dry season, the 17O‐excess in soil water is lower than that of precipitation by only 30 per meg in the sandy‐loam soils and 50 per meg in the sandy soil. This shows the limited contribution of evaporated water to bulk soil water and provides clues to constrain the complex hydrological functioning of soils; (c) The regression line connecting the triple oxygen isotope composition of water in the stems and leaves of grasses and trees can be used to determine the origin of the water absorbed by the roots. Semi‐evergreen trees draw their water from the water table during the dry season, whereas grasses and semi‐evergreen trees use surface water during the wet season. These original data open up new perspectives for the use of the triple oxygen isotope composition of water and phytoliths to better understand current and past hydrological cycles.
A global compilation of diatom silica oxygen isotope records from lake sediment - trends and implications for climate reconstruction Philip Meister, Anne Alexandre, Hannah Bailey, Philip Barker, Boris K. Biskaborn, et al. Climate of the Past, 2024 Oxygen isotopes in biogenic silica (δ18OBSi) from lake sediments allow for quantitative reconstruction of past hydroclimate and proxy-model comparison in terrestrial environments. The signals of individual records have been attributed to different factors, such as air temperature (Tair), atmospheric circulation patterns, hydrological changes, and lake evaporation. While every lake has its own local set of drivers of δ18O variability, here we explore the extent to which regional or even global signals emerge from a series of paleoenvironmental records. This study provides a comprehensive compilation and combined statistical evaluation of the existing lake sediment δ18OBSi records, largely missing in other summary publications (i.e. PAGES network). For this purpose, we have identified and compiled 71 down-core records published to date and complemented these datasets with additional lake basin parameters (e.g. lake water residence time and catchment size) to best characterize the signal properties. Records feature widely different temporal coverage and resolution, ranging from decadal-scale records covering the past 150 years to records with multi-millennial-scale resolution spanning glacial–interglacial cycles. The best coverage in number of records (N = 37) and data points (N = 2112) is available for Northern Hemispheric (NH) extratropical regions throughout the Holocene (roughly corresponding to Marine Isotope Stage 1; MIS 1). To address the different variabilities and temporal offsets, records were brought to a common temporal resolution by binning and subsequently filtered for hydrologically open lakes with lake water residence times < 100 years. For mid- to high-latitude (> 45° N) lakes, we find common δ18OBSi patterns among the lake records during both the Holocene and Common Era (CE). These include maxima and minima corresponding to known climate episodes, such as the Holocene Thermal Maximum (HTM), Neoglacial Cooling, Medieval Climate Anomaly (MCA) and the Little Ice Age (LIA). These patterns are in line with long-term air temperature changes supported by previously published climate reconstructions from other archives, as well as Holocene summer insolation changes. In conclusion, oxygen isotope records from NH extratropical lake sediments feature a common climate signal at centennial (for CE) and millennial (for Holocene) timescales despite stemming from different lakes in different geographic locations and hence constitute a valuable proxy for past climate reconstructions.
The triple oxygen isotope composition of phytoliths, a new proxy of atmospheric relative humidity: Controls of soil water isotope composition, temperature, CO2 concentration and relative humidity Clément Outrequin, Anne Alexandre, Christine Vallet-Coulomb, Clément Piel, Sébastien Devidal, et al. Climate of the Past, 2021 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.
Improving memory effect correction to achieve high-precision analysis of δ17O, δ18O, δ2H, 17O-excess and d-excess in water using cavity ring-down laser spectroscopy Christine Vallet‐Coulomb, Martine Couapel, Corinne Sonzogni Rapid Communications in Mass Spectrometry, 2021 RationaleThe precision obtained in routine isotope analysis of water (δ17O, δ18O, δ2H, 17O‐excess and d‐excess values) using cavity ring‐down spectroscopy is usually below the instrument specifications provided by the manufacturer. This study aimed at reducing this discrepancy, with particular attention paid to mitigating the memory effect (ME).MethodsWe used a Picarro L2140i analyzer coupled with a high‐precision A0211 vaporizer and an A0325 autosampler. The magnitude and duration of the ME were estimated using 24 series of 50 successive injections of samples with contrasting compositions. Four memory correction methods were compared, and the instrument performance was evaluated over a 17‐month period of routine analysis, using two different run architectures.ResultsThe ME remains detectable after the 30th injection, implying that common correction procedures only based on the last preceding sample need to be revised. We developed a new ME correction based on the composition of several successive samples, and designed a run architecture to minimize the magnitude of the ME. The standard deviation obtained from routine measurement of a quality assurance water sample over a seven‐month period was 0.015‰ for δ17O, 0.023‰ for δ18O, 0.078‰ for δ2H, 0.006‰ for 17O‐excess and 0.173‰ for d‐excess. In addition, we provided the first δ17O and 17O‐excess values for the GRESP certified reference material.ConclusionsThis study demonstrates the long‐term persistence of the ME, which is often overlooked in routine analysis of natural samples. As already evidenced when measuring labelled water, it calls for consideration of the compositions of several previous samples to obtain an appropriate correction, a prerequisite to achieve high‐precision data.
Effects of leaf length and development stage on the triple oxygen isotope signature of grass leaf water and phytoliths: Insights for a proxy of continental atmospheric humidity Anne Alexandre, Elizabeth Webb, Amaelle Landais, Clément Piel, Sébastien Devidal, et al. Biogeosciences, 2019 Continental relative humidity (RH) is a key climate parameter, but there is a lack of quantitative RH proxies suitable for climate model–data comparisons. Recently, a combination of climate chamber and natural transect calibrations have laid the groundwork for examining the robustness of the triple oxygen isotope composition (δ′18O and 17O-excess) of phytoliths, that can preserve in sediments, as a new proxy for past changes in RH. However, it was recommended that besides RH, additional factors that may impact δ′18O and 17O-excess of plant water and phytoliths be examined. Here, the effects of grass leaf length, leaf development stage and day–night alternations are addressed from growth chamber experiments. The triple oxygen isotope compositions of leaf water and phytoliths of the grass species F. arundinacea are analysed. Evolution of the leaf water δ′18O and 17O-excess along the leaf length can be modelled using a string-of-lakes approach to which an unevaporated–evaporated mixing equation must be added. We show that for phytoliths to record this evolution, a kinetic fractionation between leaf water and silica, increasing from the base to the apex, must be assumed. Despite the isotope heterogeneity of leaf water along the leaf length, the bulk leaf phytolith δ′18O and 17O-excess values can be estimated from the Craig and Gordon model and a mean leaf water–phytolith fractionation exponent (λPhyto-LW) of 0.521. In addition to not being leaf length dependent, δ′18O and 17O-excess of grass phytoliths are expected to be impacted only very slightly by the stem vs. leaf biomass ratio. Our experiment additionally shows that because a lot of silica polymerises in grasses when the leaf reaches senescence (58 % of leaf phytoliths in mass), RH prevailing during the start of senescence should be considered in addition to RH prevailing during leaf growth when interpreting the 17O-excess of grass bulk phytoliths. Although under the study conditions 17O-excessPhyto do not vary significantly from constant day to day–night conditions, additional monitoring at low RH conditions should be done before drawing any generalisable conclusions. Overall, this study strengthens the reliability of the 17O-excess of phytoliths to be used as a proxy of RH. If future studies show that the mean value of 0.521 used for the grass leaf water–phytolith fractionation exponent λPhyto-LW is not climate dependent, then grassland leaf water 17O-excess obtained from grassland phytolith 17O-excess would inform on isotope signals of several soil–plant-atmosphere processes.
Diatom-oxygen isotope record from high-altitude Lake Petit (2200 m a.s.l.) in the Mediterranean Alps: Shedding light on a climatic pulse at 4.2 ka Rosine Cartier, Florence Sylvestre, Christine Paillès, Corinne Sonzogni, Martine Couapel, et al. Climate of the Past, 2019 In the Mediterranean area, the 4.2 ka BP event is recorded with contrasting expressions between regions. In the southern Alps, the high-altitude Lake Petit (Mercantour Massif, France; 2200 m a.s.l.) offers pollen and diatom-rich sediments covering the last 4800 years. A multi-proxy analysis recently revealed a detrital pulse around 4200 cal BP due to increasing erosion in the lake catchment. The involvement of a rapid climate change leading to increasing runoff and soil erosion was proposed. Here, in order to clarify this hypothesis, we measured the oxygen isotope composition of diatom silica frustules (δ18Odiatom) from the same sedimentary core. Diatoms were analysed by laser fluorination isotope ratio mass spectrometry after an inert gas flow dehydration. We additionally enhanced the accuracy of the age–depth model using the Bacon R package. The δ18Odiatom record allows us to identify a 500-year time lapse, from 4400 to 3900 cal BP, where δ18Odiatom reached its highest values (>31 ‰). δ18Odiatom was about 3 ‰ higher than the modern values and the shifts at 4400 and 3900 cal BP were of similar amplitude as the seasonal δ18Odiatom shifts occurring today. This period of high δ18Odiatom values can be explained by the intensification of 18O-enriched Mediterranean precipitation events feeding the lake during the ice-free season. This agrees with other records from the southern Alps suggesting runoff intensification around 4200 cal BP. Possible changes in other climatic parameters may have played a concomitant role, including a decrease in the contribution of 18O-depleted Atlantic winter precipitation to the lake water due to snow deficit. Data recording the 4.2 ka BP event in the north-western Mediterranean area are still sparse. In the Lake Petit watershed, the 4.2 ka BP event translated into a change in precipitation regime from 4400 to 3900 cal BP. This record contributes to the recent efforts to characterize and investigate the geographical extent of the 4.2 ka BP event in the Mediterranean area.
The Lake CHAd Deep DRILLing project (CHADRILL) - targeting ~ 10 million years of environmental and climate change in Africa Florence Sylvestre, Mathieu Schuster, Hendrik Vogel, Moussa Abdheramane, Daniel Ariztegui, et al. Scientific Drilling, 2018 At present, Lake Chad (∼ 13∘′ N, ∼ 14∘ E) is a shallow freshwater lake located in the Sahel/Sahara region of central northern Africa. The lake is primarily fed by the Chari–Logone river system draining a ∼ 600 000 km2 watershed in tropical Africa. Discharge is strongly controlled by the annual passage of the intertropical convergence zone (ITCZ) and monsoon circulation leading to a peak in rainfall during boreal summer. During recent decades, a large number of studies have been carried out in the Lake Chad Basin (LCB). They have mostly focused on a patchwork of exposed lake sediments and outcrops once inhabited by early hominids. A dataset generated from a 673 m long geotechnical borehole drilled in 1973, along with outcrop and seismic reflection studies, reveal several hundred metres of Miocene–Pleistocene lacustrine deposits. CHADRILL aims to recover a sedimentary core spanning the Miocene–Pleistocene sediment succession of Lake Chad through deep drilling. This record will provide significant insights into the modulation of orbitally forced changes in northern African hydroclimate under different climate boundary conditions such as high CO2 and absence of Northern Hemisphere ice sheets. These investigations will also help unravel both the age and the origin of the lake and its current desert surrounding. The LCB is very rich in early hominid fossils (Australopithecus bahrelghazali; Sahelanthropus tchadensis) of Late Miocene age. Thus, retrieving a sediment core from this basin will provide the most continuous climatic and environmental record with which to compare hominid migrations across northern Africa and has major implications for understanding human evolution. Furthermore, due to its dramatic and episodically changing water levels and associated depositional modes, Lake Chad's sediments resemble maybe an analogue for lake systems that were once present on Mars. Consequently, the study of the subsurface biosphere contained in these sediments has the potential to shed light on microbial biodiversity present in this type of depositional environment. We propose to drill a total of ∼ 1800 m of poorly to semi-consolidated lacustrine, fluvial, and eolian sediments down to bedrock at a single on-shore site close to the shoreline of present-day Lake Chad. We propose to locate our drilling operations on-shore close to the site where the geotechnical Bol borehole (13∘28′ N, 14∘44′ E) was drilled in 1973. This is for two main reasons: (1) nowhere else in the Chad Basin do we have such detailed information about the lithologies to be drilled; and (2) the Bol site is close to the depocentre of the Chad Basin and therefore likely to provide the stratigraphically most continuous sequence.
The triple oxygen isotope composition of phytoliths as a proxy of continental atmospheric humidity: Insights from climate chamber and climate transect calibrations Anne Alexandre, Amarelle Landais, Christine Vallet-Coulomb, Clément Piel, Sébastien Devidal, et al. Biogeosciences, 2018 Continental atmospheric relative humidity (RH) is a key climate parameter. Combined with atmospheric temperature, it allows us to estimate the concentration of atmospheric water vapor, which is one of the main components of the global water cycle and the most important gas contributing to the natural greenhouse effect. However, there is a lack of proxies suitable for reconstructing, in a quantitative way, past changes of continental atmospheric humidity. This reduces the possibility of making model–data comparisons necessary for the implementation of climate models. Over the past 10 years, analytical developments have enabled a few laboratories to reach sufficient precision for measuring the triple oxygen isotopes, expressed by the 17O-excess (17O-excess = ln (δ17O + 1) – 0.528 × ln (δ18O + 1)), in water, water vapor and minerals. The 17O-excess represents an alternative to deuterium-excess for investigating relative humidity conditions that prevail during water evaporation. Phytoliths are micrometric amorphous silica particles that form continuously in living plants. Phytolith morphological assemblages from soils and sediments are commonly used as past vegetation and hydrous stress indicators. In the present study, we examine whether changes in atmospheric RH imprint the 17O-excess of phytoliths in a measurable way and whether this imprint offers a potential for reconstructing past RH. For that purpose, we first monitored the 17O-excess evolution of soil water, grass leaf water and grass phytoliths in response to changes in RH (from 40 to 100 %) in a growth chamber experiment where transpiration reached a steady state. Decreasing RH from 80 to 40 % decreases the 17O-excess of phytoliths by 4.1 per meg/% as a result of kinetic fractionation of the leaf water subject to evaporation. In order to model with accuracy the triple oxygen isotope fractionation in play in plant water and in phytoliths we recommend direct and continuous measurements of the triple isotope composition of water vapor. Then, we measured the 17O-excess of 57 phytolith assemblages collected from top soils along a RH and vegetation transect in inter-tropical West and Central Africa. Although scattered, the 17O-excess of phytoliths decreases with RH by 3.4 per meg/%. The similarity of the trends observed in the growth chamber and nature supports that RH is an important control of 17O-excess of phytoliths in the natural environment. However, other parameters such as changes in the triple isotope composition of the soil water or phytolith origin in the plant may come into play. Assessment of these parameters through additional growth chambers experiments and field campaigns will bring us closer to an accurate proxy of changes in relative humidity.
A new helicosphaera-syracolithus combination coccosphere (haptophyta) from the western mediterranean sea1 Martine J. J. Couapel, Luc Beaufort, and Jeremy R. Young Journal of Phycology, 2009 A new combination coccosphere of the heterococcolithophore Helicosphaera wallichii ( Lohman 1902 ) Okada and McIntyre 1977 and holococcolithophore Syracolithus ponticuliferus ( Kamptner 1941 ) Kleijne and Jordan 1990 is documented. This combination coccosphere was observed within a rich and diverse assemblage collected during late summer at a 20 m water depth from the NW Mediterranean Sea.
