High-precision dual-inlet IRMS measurements of the stable isotopes of CO₂ and the N₂O/CO₂ ratio from polar ice core samples

An important constraint on mechanisms of past carbon cycle variability is provided by the stable isotopic composition of carbon in atmospheric carbon dioxide (δ¹³C-CO₂) trapped in polar ice cores, but obtaining very precise measurements has proven to be a significant analytical challenge. Here we describe a new technique to determine the δ¹³C of CO₂ at very high precision, as well as measuring the CO₂ and N₂O mixing ratios. In this method, ancient air is extracted from relatively large ice samples (~400 g) with a dry-extraction “ice grater” device. The liberated air is cryogenically purified to a CO₂ and N₂O mixture and analyzed with a microvolume-equipped dual-inlet IRMS (Thermo MAT 253). The reproducibility of the method, based on replicate analysis of ice core samples, is 0.02‰ for δ¹³C-CO₂ and 2 ppm and 4 ppb for the CO₂ and N₂O mixing ratios, respectively (1σ pooled standard deviation). Our experiments show that minimizing water vapor pressure in the extraction vessel by housing the grating apparatus in a ultralow-temperature freezer (-60°C) improves the precision and decreases the experimental blank of the method to -0.07 ± 0.04‰. We describe techniques for accurate calibration of small samples and the application of a mass-spectrometric method based on source fragmentation for reconstructing the N₂O history of the atmosphere. The oxygen isotopic composition of CO₂ is also investigated, confirming previous observations of oxygen exchange between gaseous CO₂ and solid H₂O within the ice archive. These data offer a possible constraint on oxygen isotopic fractionation during H₂O and CO₂ exchange below the H₂O bulk melting temperature

Global ocean heat content in the Last Interglacial

The Last Interglacial (129-116 ka) represents one of the warmest climate intervals of the last 800,000 years and the most recent time when sea level was meters higher than today. However, the timing and magnitude of peak warmth varies between reconstructions, and the relative importance of individual sources contributing to elevated sea level (mass gain versus seawater expansion) during the Last Interglacial remains uncertain. Here we present the first mean ocean temperature record for this interval from noble gas measurements in ice cores and constrain the thermal expansion contribution to sea level. Mean ocean temperature reaches its maximum value of 1.1±0.3°C warmer-than-modern at the end of the penultimate deglaciation at 129 ka, resulting in 0.7±0.3m of elevated sea level, relative to present. However, this maximum in ocean heat content is a transient feature; mean ocean temperature decreases in the first several thousand years of the interglacial and achieves a stable, comparable-to-modern value by ~127 ka. The synchroneity of the peak in mean ocean temperature with proxy records of abrupt transitions in oceanic and atmospheric circulation suggests that the mean ocean temperature maximum is related to the accumulation of heat in the ocean interior during the preceding period of reduced overturning circulation

Global ocean heat content in the Last Interglacial

The Last Interglacial (129–116 thousand years ago (ka)) represents one of the warmest climate intervals of the past 800,000 years and the most recent time when sea level was metres higher than today. However, the timing and magnitude of the peak warmth varies between reconstructions, and the relative importance of individual sources that contribute to the elevated sea level (mass gain versus seawater expansion) during the Last Interglacial remains uncertain. Here we present the first mean ocean temperature record for this interval from noble gas measurements in ice cores and constrain the thermal expansion contribution to sea level. Mean ocean temperature reached its maximum value of 1.1 ± 0.3 °C warmer-than-modern values at the end of the penultimate deglaciation at 129 ka, which resulted in 0.7 ± 0.3 m of thermosteric sea-level rise relative to present level. However, this maximum in ocean heat content was a transient feature; mean ocean temperature decreased in the first several thousand years of the interglacial and achieved a stable, comparable-to-modern value by ~127 ka. The synchroneity of the peak in mean ocean temperature with proxy records of abrupt transitions in the oceanic and atmospheric circulation suggests that the mean ocean temperature maximum is related to the accumulation of heat in the ocean interior during the preceding period of reduced overturning circulation

Triple oxygen and hydrogen isotopes of gypsum hydration water for quantitative paleo-humidity reconstruction

© 2017 Elsevier B.V. Atmospheric relative humidity is an important parameter affecting vegetation yet paleo-humidity proxies are scarce and difficult to calibrate. Here we use triple oxygen (δ17O and δ18O) and hydrogen (δD) isotopes of structurally-bound gypsum hydration water (GHW) extracted from lacustrine gypsum to quantify past changes in atmospheric relative humidity. An evaporation isotope-mass-balance model is used together with Monte Carlo simulations to determine the range of climatological conditions that simultaneously satisfy the stable isotope results of GHW, and with statistically robust estimates of uncertainty. We apply this method to reconstruct the isotopic composition of paleo-waters of Lake Estanya (NE Spain) and changes in normalized atmospheric relative humidity (RHn) over the last glacial termination and Holocene (from ∼15 to 0.6 cal. kyrs BP). The isotopic record indicates the driest conditions occurred during the Younger Dryas (YD; ∼12–13 cal. kyrs BP). We estimate a RHnof ∼40–45% during the YD, which is ∼30–35% lower than today. Because of the southward displacement of the Polar Front to ∼42°N, it was both windier and drier during the YD than the Bølling–Allerød period and Holocene. Mean atmospheric moisture gradually increased from the Preboreal to Early Holocene (∼11 to 8 cal. kyrs BP, 50–60%), reaching 70–75% RHnfrom ∼7.5 cal. kyrs BP until present-day. We demonstrate that combining hydrogen and triple oxygen isotopes in GHW provides a powerful tool for quantitative estimates of past changes in relative humidity

Low atmospheric CO2 levels during the Little Ice Age due to cooling-induced terrestrial uptake

Low atmospheric carbon dioxide (CO2) concentration during the Little Ice Age has been used to derive the global carbon cycle sensitivity to temperature. Recent evidence confirms earlier indications that the low CO2 was caused by increased terrestrial carbon storage. It remains unknown whether the terrestrial biosphere responded to temperature variations, or there was vegetation re-growth on abandoned farmland. Here we present a global numerical simulation of atmospheric carbonyl sulfide concentrations in the pre-industrial period. Carbonyl sulfide concentration is linked to changes in gross primary production and shows a positive anomaly during the Little Ice Age. We show that a decrease in gross primary production and a larger decrease in ecosystem respiration is the most likely explanation for the decrease in atmospheric CO2 and increase in atmospheric carbonyl sulfide concentrations. Therefore, temperature change, not vegetation re-growth, was the main cause of the increased terrestrial carbon storage. We address the inconsistency between ice-core CO2 records from different sites measuring CO2 and δ13CO2 in ice from Dronning Maud Land (Antarctica). Our interpretation allows us to derive the temperature sensitivity of pre-industrial CO2 fluxes for the terrestrial biosphere (γL = -10 to -90 Pg C K-1), implying a positive climate feedback and providing a benchmark to reduce model uncertainties

Southern Ocean carbon sink enhanced by sea-ice feedbacks at the Antarctic Cold Reversal

The Southern Ocean occupies some 14% of the planet’s surface and plays a fundamental role in the global carbon cycle and climate. It provides a direct connection to the deep ocean carbon reservoir through biogeochemical processes that include surface primary productivity, remineralisation at depth, and the upwelling of carbon-rich water masses. However, the role of these different processes in modulating past and future air-sea carbon flux remains poorly understood. A key period in this regard is the Antarctic Cold Reversal (ACR, 14.6-12.7 kyr BP), a period of mid- to high-latitude cooling that coincided with a sustained plateau in deglacial atmospheric rise in CO2 globally. Here we reconstruct high-latitude Southern Ocean surface productivity from marine derived aerosols captured in a highly-resolved horizontal ice core. Our multiproxy reconstruction reveals a coherent signal of enhanced productivity across the ACR. Transient climate modelling indicates this period coincided with maximum seasonal variability in sea-ice extent, implying that sea-ice biological feedbacks enhanced CO2 sequestration, creating a significant regional marine carbon sink that contributed to the sustained plateau in CO2 at the ACR. Our results highlights the role Antarctic sea ice plays in controlling global CO2, and demonstrates the need to incorporate such feedbacks in climate-carbon models

Precise interpolar phasing of abrupt climate change during the last ice age

The last glacial period exhibited abrupt Dansgaard–Oeschger climatic oscillations, evidence of which is preserved in a variety of Northern Hemisphere palaeoclimate archives¹. Ice cores show that Antarctica cooled during the warm phases of the Greenland Dansgaard–Oeschger cycle and vice versa[superscript 2,3], suggesting an interhemispheric redistribution of heat through a mechanism called the bipolar seesaw[superscript 4–6]. Variations in the Atlantic meridional overturning circulation (AMOC) strength are thought to have been important, but much uncertainty remains regarding the dynamics and trigger of these abrupt events[superscript 7–9]. Key information is contained in the relative phasing of hemispheric climate variations, yet the large, poorly constrained difference between gas age and ice age and the relatively low resolution of methane records from Antarctic ice cores have so far precluded methane-based synchronization at the required sub-centennial precision[superscript 2,3,10]. Here we use a recently drilled high-accumulation Antarctic ice core to show that, on average, abrupt Greenland warming leads the corresponding Antarctic cooling onset by 218 ± 92 years (2σ) for Dansgaard–Oeschger events, including the Bølling event; Greenland cooling leads the corresponding onset of Antarctic warming by 208 ± 96 years. Our results demonstrate a north-to-south directionality of the abrupt climatic signal, which is propagated to the Southern Hemisphere high latitudes by oceanic rather than atmospheric processes. The similar interpolar phasing of warming and cooling transitions suggests that the transfer time of the climatic signal is independent of the AMOC background state. Our findings confirm a central role for ocean circulation in the bipolar seesaw and provide clear criteria for assessing hypotheses and model simulations of Dansgaard–Oeschger dynamics

Online Differential Thermal Isotope Analysis of Hydration Water in Minerals by Cavity Ringdown Laser Spectroscopy

We have developed a new method for measuring the isotopic composition (δ18O and δD) of different types of bonded water (e.g., molecular water, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves precisely step-heating a mineral sample, allowing the separation of the different types of waters that are released at different temperatures. Simultaneously, the water vapor evolved from the mineral sample is analyzed for oxygen and hydrogen isotopes by CRDS. Isotopic values for the separate peaks are calculated by integrating the product of the water amounts and its isotopic values, after correcting for background. We provide examples of the application of the differential thermal isotope analysis (DTIA) method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous silica (opal). The isotopic compositions of the total water evolved from a set of natural gypsum samples by DTIA are compared with the results of a conventional offline water extraction method followed by CRDS analysis. The results from both methods are in excellent agreement, and precisions (1σ) for δ18O (±0.12‰) and δD (±0.8‰) of the total gypsum hydration water from the DTIA method are comparable to that obtained by the offline method. A range of analytical challenges and solutions (e.g., spectroscopic interferences produced by VOCs in natural samples, isotopic exchange with structural oxygen, etc.) are discussed. The DTIA method has wide ranging applications for addressing fundamental problems across many disciplines in earth and planetary sciences, including paleoclimatology, sedimentology, volcanology, water exchange between the solid earth and hydrosphere, and water on Mars and other planetary bodies

Online differential thermal isotope analysis of hydration water in minerals by cavity ringdown laser spectroscopy

We have developed a new method for measuring the isotopic composition (δ18O and δD) of different types of bonded water (e.g., molecular water, hydroxyl) contained in hydrated minerals by coupling a thermal gravimeter (TG) and a cavity ringdown laser spectrometer (CRDS). The method involves precisely step-heating a mineral sample, allowing the separation of the different types of waters that are released at different temperatures. Simultaneously, the water vapor evolved from the mineral sample is analyzed for oxygen and hydrogen isotopes by CRDS. Isotopic values for the separate peaks are calculated by integrating the product of the water amounts and its isotopic values, after correcting for background. We provide examples of the application of the differential thermal isotope analysis (DTIA) method to a variety of hydrous minerals and mineraloids including gypsum, clays, and amorphous silica (opal). The isotopic compositions of the total water evolved from a set of natural gypsum samples by DTIA are compared with the results of a conventional offline water extraction method followed by CRDS analysis. The results from both methods are in excellent agreement, and precisions (1σ) for δ18O (±0.12‰) and δD (±0.8‰) of the total gypsum hydration water from the DTIA method are comparable to that obtained by the offline method. A range of analytical challenges and solutions (e.g., spectroscopic interferences produced by VOCs in natural samples, isotopic exchange with structural oxygen, etc.) are discussed. The DTIA method has wide ranging applications for addressing fundamental problems across many disciplines in earth and planetary sciences, including paleoclimatology, sedimentology, volcanology, water exchange between the solid earth and hydrosphere, and water on Mars and other planetary bodies.</p

High-precision dual-inlet IRMS measurements of the stable isotopes of CO₂ and the N₂O / CO₂ ratio from polar ice core samples

An important constraint on mechanisms of past carbon cycle variability is provided by the stable isotopic composition of carbon in atmospheric carbon dioxide (δ¹³C-CO₂) trapped in polar ice cores, but obtaining very precise measurements has proven to be a significant analytical challenge. Here we describe a new technique to determine the δ¹³C of CO₂ at very high precision, as well as measuring the CO₂ and N₂O mixing ratios. In this method, ancient air is extracted from relatively large ice samples (~400 g) with a dry-extraction "ice grater" device. The liberated air is cryogenically purified to a CO₂ and N₂O mixture and analyzed with a microvolume-equipped dual-inlet IRMS (Thermo MAT 253). The reproducibility of the method, based on replicate analysis of ice core samples, is 0.02&permil; for δ¹³C-CO₂ and 2 ppm and 4 ppb for the CO₂ and N₂O mixing ratios, respectively (1σ pooled standard deviation). Our experiments show that minimizing water vapor pressure in the extraction vessel by housing the grating apparatus in a ultralow-temperature freezer (−60 °C) improves the precision and decreases the experimental blank of the method to −0.07 ± 0.04&permil;. We describe techniques for accurate calibration of small samples and the application of a mass-spectrometric method based on source fragmentation for reconstructing the N₂O history of the atmosphere. The oxygen isotopic composition of CO₂ is also investigated, confirming previous observations of oxygen exchange between gaseous CO₂ and solid H₂O within the ice archive. These data offer a possible constraint on oxygen isotopic fractionation during H₂O and CO₂ exchange below the H₂O bulk melting temperature